Comparative Synthetic Strategies for the Generation of 5,10- and 5,15-Substituted Push-Pull Porphyrins

Article abstract of DOI:10.1002/ejoc.201700093

Contemporary applications in optics, medicine, solar cells, or material science are increasingly reliant on unsymmetrically substituted porphyrins. Due to their widespread applications and rise in demand we undertook a comparative analysis of synthetic strategies for meso-substituted porphyrins and present the synthesis of five different series of so-called A₂BC push-pull porphyrins. The synthetic pathways used were applied to both 5,15-substituted and 5,10-substituted porphyrins, showcasing their flexibility and adaptability for different needs. Our approach combines well-known reactions with a strategic and logical stepwise functionalization allowing researchers to change and modify the electronic properties of these systems at various points of the syntheses. This facilitates the easy optimization of the synthesis of systems of current interest, for example, porphyrins for dye-sensitized solar cells (DSSCs) or for use in nonlinear optics, as well as fast generation of compound libraries.

Full text of DOI:10.1002/ejoc.201700093

A Journal of
Accepted Article
Title: Comparative synthetic strategies for the generation of 5,10- and
5,15-substituted push-pull porphyrins
Authors: Alina Meindl, Shane Plunkett, Aoife A. Ryan, Keith J.
Flanagan, Susan Callaghan, and Mathias O. Senge
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201700093
Link to VoR: http://dx.doi.org/10.1002/ejoc.201700093
Supported by

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
Comparative synthetic strategies for the generation of 5,10- and
,15-substituted push-pull porphyrins
5
[
a]
[a]
[a]
[a]
[a]
Alina Meindl, Shane Plunkett, Aoife A. Ryan, Keith J. Flanagan, Susan Callaghan, Mathias O.
[
a]
Senge*
Abstract: Contemporary applications in optics, medicine, solar cells
or material science are increasingly reliant on unsymmetrically
substituted porphyrins. Due to their widespread applications and rise
adaptability for different needs. Our approach combines well-known
reactions with a strategic and logical stepwise functionalization
allowing researchers to change and modify the electronic properties
of these systems at various points of the syntheses. This facilitates
the easy optimization of the synthesis of systems of current interest,
e.g., porphyrins for dye-sensitized solar cells (DSSC) or for use in
nonlinear optics, as well as fast generation of compound libraries.
in demand we undertook
strategies for meso-substituted porphyrins and present the synthesis
of five different series of so-called A BC push-pull porphyrins. The
synthetic pathways used were applied to both 5,15-substituted and
,10-substituted porphyrins, showcasing their flexibility and
a comparative analysis of synthetic
2
5
Introduction
due to the pioneering work of Grätzel and coworkers on
[
8]
DSSCs. For example, Imahori and coworkers published a
series of porphyrins with either two diarylamino groups and two
carboxyphenyl groups or two diarylamino groups, one mesityl
Porphyrins are versatile organic molecules with an ever
expanding range of potential applications such as electron
transfer materials, optical limiters, as components of dye-
sensitized solar cells or photosensitizers in photodynamic
therapy, and many more. Porphyrins exhibit good chemical
stability and optical and photophysical properties suitable for
diverse industrial uses. Furthermore, their electronic
characteristics can be easily tuned and the porphyrin
[
9]
group and one carboxyphenylethynyl group where the latter
showed improved absorption properties. Push-pull porphyrins
[
1]
[10]
with triarylamine moieties have also been reported, as have
compounds with dialkylaminophenylethynyl groups which results
in broadened and red-shifted absorption maxima compared to
[
10d]
porphyrins with a meso-diarylamino moiety.
[
2]
macrocycle core modified. Many applications require mixed
meso-substituted compounds (e.g., A - or ABCD-type systems)
x
which led to an increased interest in the use of unsymmetric
porphyrins and the necessity of rational and flexible synthetic
methods thereof.
Different synthetic approaches are possible; the classic being
Donor
[
2a,3]
N
N
N
N
N
N
N
N
Zn
Donor
Donor
Zn
[
4]
mixed condensations, which can result in various isomers.
[
3a,5]
More strategic methods involve total syntheses,
organolithium reactions or transition metal-catalyzed coupling
[
2a,6]
reactions.
All of these methods enable step-wise
Acceptor
Acceptor
functionalization of the porphyrin, which allows the formation of
nearly any meso-substituted porphyrin. This is especially
relevant for studies on push-pull porphyrins which feature
prominently in current (electro)optical applications of
porphyrinoids (Figure 1).
meso-meso axis
- axis
N
N
N
Zn
N
[
7]
Pioneered by Suslick’s and Therien’s groups, push-pull
porphyrins are donor-π-acceptor systems (D–A) where electrons
are transferred from an electron-donating group through a π-
spacer to an electron-withdrawing group and have a strong
intramolecular dipole moment (Figure 1). Initially developed for
Acceptor
meso- axis
[
1d]
Figure 1. Different dipole moment orientations in push-pull porphyrins.
use in nonlinear optics (NLO), they are currently under intense
scrutiny as light-harvesting dyes in dye-sensitized solar cells due
[
8]
to their broad and strong absorption properties.
Here,
The long excited state lifetimes of porphyrins and their chemical-
and photostability have given rise to similar uses of porphyrins
as optical limiters. Again, unsymmetrically substituted porphyrins
carboxylic acid groups often feature as anchoring acceptor units
while a variety of different donor units have been explored.
Especially, meso-diarylamino porphyrins have gained attention
feature prominently, notably A
substituted porphyrins.
2
BC systems, e.g., ethynyl-aryl
NLO studies also illustrated the
[
7b,11]
impact of the orientation of the intramolecular dipole moment.
5,10-disubstituted porphyrins exhibit a unique reverse saturable
[
a]
SFI Tetrapyrrole Laboratory, School of Chemistry,
Trinity Biomedical Sciences Institute,
1
52-160 Pearse Street, Trinity College Dublin, the University of
absorption (RSA) to saturable absorption (SA) switch under
Dublin, Dublin 2, Ireland.
E-mail: sengem@tcd.ie
http://chemistry.tcd.ie/staff/people/mos/Home.html
Supporting information for this article is given via a link at the end of
the document.
[12]
nanosecond irradiation,
disubstituted systems.
a feature nonexistent in 5,15-
[
13]
These and, in particular, Grätzel’s series of 5,15-disubstituted
push-pull porphyrins (for example, 1 “YD2” and 2 “YD2-o-C8”,
[
8]
Figure 2) with very high power conversion efficiencies
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
[
21]
triggered the synthesis of considerable variations of these
porphyrins. The synthesis of 5,10-disubstituted porphyrins has
always been more onerous than the formation of 5,15-
disubstituted porphyrins. However, the use of tripyrrane
[
14]
donor-acceptor systems.
Most of the published work
concerned unsymmetrically 5,15-disubstituted porphyrins, which
have a dipole running along the meso-meso axis. The second
possible orientation of the dipole moment, along the meso-β axis
as in 4 (“ZnEP1”), was studied by Sessler’ and Kim’s group and
[
20b, 22]
precursors has simplified this synthesis remarkably.
Due to
the use of cold recrystallization it is now possible to synthesize
these important starting materials in bulk (Scheme 1), which
allows the formation of numerous different 5,10-disubstituted
porphyrins. To obtain the starting material for the future step-
wise functionalization, tripyrrane, pyrrole and the corresponding
aldehyde were condensed using TFA as catalyst. 5,10-Bis(3,5-
[
15]
gave comparable results to 3 (“YD1”, Figure 2). Due to their
difficult synthesis, the 5,10-disubstituted counterparts - with the
dipole moment along the β-β axis (Figure 1) - are only now
[
16]
emerging as candidates in DSSC studies.
di-tert-butylphenyl)porphyrin
(7a)
and
5,10-bis(2,6-
dioctyloxyphenyl)porphyrin (7b) were obtained in 6-7% yield
using a modified literature procedure.
R3
R3
t-Bu
t-Bu
[20b,23]
N
N
R2
R1
R1
R2
t-Bu
t-Bu
O
t-Bu
t-Bu
N
N
N
N
N
N
N
N
H
H (2 eq.)
HO
OH Pyrrole (10 eq.)
Zn
Zn
N
N
N
H
H
NaOH (1M, 1 mol-%)
40 oC, 16 h
H
0
2
O, HCl (cat.)
oC, dark, 1 h
H
R2
R1
R1
R2
NH
HN
5
24%
R1
6 35%
+
O
1
. TFA (cat.)
NH
N
N
H
R1
(2 eq.)
H
CH Cl , r.t., dark
2
R1
2
2
. DDQ (1 eq.)
(1 eq.)
N
HN
O
HO
O
HO
R1 = H, R2 = t-Butyl,R = C
3
H
7a R1 = 3,5-di-tert-butylphenyl 7%
7b R1 = 2,6-bis(octyloxy)phenyl 6%
13; YD2 1
6
ZnEP1
4
R1 = OC
17, R2 = H, R = C
3
8
H
6
H
13; YD2-o-C8 2
R1 = H, R2 = t-Butyl,R = t-Butyl; YD1 3
3
Scheme 1.Synthesis of tripyrrane (6) and condensation reaction to form 5,10-
disubstituted porphyrins (7a and 7b).
Figure 2: Different push-pull porphyrins.
Historically 5,10-disubstituted porphyrins have been synthesized
through mixed condensation reactions, which are tedious and
cumbersome. Other attempts such as our nucleophilic aromatic
Initial Approach Towards 5,10-D–A-systems
With the 5,10-orientation thus defined in starting porphyrins 7a
and 7b, investigations focused on the optimum sequence to
install the donor (diarylamine) and acceptor (conjugated
carboxylic acid) groups onto the preformed scaffold as well as
[
17,18]
substitution with in situ generated organolithium reagents
or
via dipyrromethane or bilane precursors have shown to yield
,10-disubstituted porphyrins, but with various limitations.
Ultimately, so-called “[3+1]” approach, involving the
condensation of tripyrrane with pyrrole and the desired aldehyde,
[
19]
5
[24]
the required metallation of the system. Initially, the sequence
a
followed was that reported in the original Grätzel porphyrin
[8c,8d]
synthesis.
The synthesis was started with 7a and details are
[
20]
provided a fast and cost-effective entry into 5,10-A
A B -type porphyrins.
2 2
2
-
and 5,10-
shown in Scheme 2. Although this tert-butyl system has been
[
18]
shown to be less effective than the octyloxy-substituted
Here we describe our efforts to investigate the synthesis of
regioisomeric push-pull porphyrins related to those currently in
use in NLO and DSSC studies. Our approach involves classical
condensation reactions followed by strategic functionalization in
a step-wise manner targeting both 5,10- and 5,15-donor-
acceptor-substituted porphyrins to allow a direct comparison of
contemporary synthetic methods.
[8c]
porphyrin,
the
known
solubility
of
(3,5-di-tert-
[25]
butylphenyl)porphyrins and their ease of characterization
made this a preferential starting point for optimization of the
various steps on the 5,10-scaffolds before moving to potentially
more active systems. The plan was to use sequential, selective,
brominations followed by Pd-catalyzed reactions to install the
desired functionality in a controlled, step-wise manner.
To employ the electron donor unit via Buchwald-Hartwig
[
26]
amination reaction, a monobrominated porphyrin was required.
Despite the fact that only 0.9 eq. of NBS was used and the
reaction was performed at 0 °C to direct monobromination, the
dibrominated species was still obtained as a minor side product.
Prior to the Sonogashira cross-coupling reaction zinc was
inserted into the porphyrin core to prevent copper insertion at
any stage to yield 9a. TIPS acetylene was installed via
Sonogashira cross-coupling reaction to avoid functional group
intolerance by the carboxylic acid moiety later on. This yielded
compound 10a in 73% yield.
Results and Discussion
Target Compounds and Starting Materials
At the onset of this study compounds such as 1–4 with
diarylamino donor units and carboxyphenyl acceptor units were
at the forefront of application studies and thus were deemed
appropriate target compounds for synthetic studies.
[
27]
As outlined before, our approach towards asymmetrical A
porphyrins incorporates condensation reactions to achieve the
-porphyrins followed by sequential introduction of various
functional groups. Previously developed syntheses were used to
2
BC-
A
2
[
20]
obtain the 5,10-disubstituted
and the 5,15-disubstituted
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
To investigate the complications observed in the Buchwald-
Hartwig amination further optimizations for this reaction were
NH
N
N
N
N
N
N
N
N
undertaken.
For
this
purpose
[5-bromo-10,20-bis(4-
N
N
(
i)
(iii)
R1
R1
R1
Zn
M
methylphenyl)-15-phenylporphyrinato]zinc(II) 14 was chosen
due to its ease of synthesis. Bis(4-tert-butylphenyl)amine 15 was
used instead of Bis(4-hexylphenyl)amine due to its commercial
availability. This group can be used for various push-pull
porphyrins and has been used previously for applications in
HN
7
a
Br
8
9
a M = 2H 72%
10a 73%
(ii)
TIPS
iv)
[
29]
a M = Zn(II) 98%
DSSCs. Since our aim was to focus on the investigation and
comparison of different synthetic approaches, this was deemed
to be a favorable alternative. In order to find the optimal
(
R1
R1
6 13
C H
[
30]
N
N
N
N
N
N
N
Buchwald-Hartwig amination
aminoporphyrins, the most common conditions were tested
through several experiments. (Table 1).
procedure for the synthesis of
(
v)
R1
R1
Zn
N
Zn
Br
N
Table 1. Optimization of Buchwald-Hartwig amination through investigation on
the impact of different catalysts, ligands, bases and solvents on the reaction.
C H
6
13
1
2a 56%
11a 95%
TIPS
TIPS
(
vi)
R1
Zn
6 13
C H
N
N
N
N
R1
N
R1 = 3,5-di-tert-butylphenyl-
6 13
C H
1
3a
O
OH
#
Catalyst
Ligand
Base
(EQ.)
Solvent
Tem
p(°C)
65
Conv
(%)
40
<10
30
[
A]
Scheme 2. Attempted synthesis of A
Buchwald-Hartwig amination and Sonogashira cross-coupling reactions. (i)
NBS, pyridine, CHCl , 0 °C, 1 h; (ii) Zn(OAc) , CHCl , MeOH, r.t., 1.5 h; (iii) 9a,
triisopropylsilylacetylene, PdCl (PPH , CuI, THF/NEt , 65 °C, 16 h; (iv) NBS,
pyridine, CHCl r.t., h; (v) Pd(OAc) bis(4-hexylphenyl)amine, NaH,
DPEPhos, THF, 65 °C, 16 h; (vi) a) TBAF, THF, r.t., 30 min; b) 4-
bromobenzoic acid, Pd (dba) , AsPh , THF/NEt , 65 °C, 16 h.
2
BC 5,10-disubstituted porphyrins using
1
2
3
4
5
Pd(OAc)
Pd
Pd(OAc)
Pd
Pd(OAc)
2
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
NaH (4)
NaH (4)
NaH (4)
NaH (4)
THF
THF
Toluene
Toluene
THF
3
2
3
2
(dba)
3
65
110
110
65
2
3
)
2
3
2
(dba)
3
66
35
3
,
1
2
,
2
t
2
KO Bu
(
4)
2
3
3
3
t
6
7
8
9
Pd
Pd(OAc)
Pd (dba)
Pd(OAc)2
Pd(OAc)
Pd (dba)
2
(dba)
3
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
BINAP
KO Bu
4)
THF
Toluene
Toluene
Toluene
THF
65
110
110
110
65
20
55
30
0
(
t
2
KO Bu
4)
(
Initial attempts using Buchwald-Hartwig amination gave
porphyrin 12a (Scheme 2) with a 56% yield. In practice this
reaction was plagued with numerous challenges, such as the
formation of debrominated starting material. The formation of
dehalogenated side products is a known problem for Buchwald-
t
2
3
KO Bu
4)
Cs CO3
(
2
(
4)
10
2
Cs
(
2
CO
4)
3
3
0
[
28]
Hartwig aminations and has been reported before.
While
11
2
3
2
2
2
2
2
2
Cs
(
2
CO
4)
Toluene
THF
110
65
0
usable quantities of 12a were nevertheless achieved, attempted
deprotection of the TIPS-acetylene and a second Sonogashira
reaction to give target acid 13a failed, resulting solely in
unidentifiable porphyrin mixtures. The issues encountered in this
synthesis ultimately led to a re-evaluation of the target route.
12
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
NaH
70
65
80
75
90
95
60
[b]
(
4)
t
13
KO Bu
THF
65
[
b]
(
4)
14
15
16
17
18
NaH
THF
65
[
b]
(
20)
t
KO Bu
THF
65
[
b]
(20)
NaH
THF
65
[
b]
2
Synthesis of 5,10-A BC D–A-systems
(20)
Cs CO
(10)
NaH
BINAP
2
3
THF
65
[
b]
Optimization and revision. Following this setback, the applied
synthetic strategy was reviewed and optimized (Scheme 3). In
lieu of using a two-step process to attach the acceptor unit an
alkynylphenyl ester was used. This enabled straightforward
purification as well as simplification of the overall synthesis. At
this stage it was also deemed beneficial to change the sequence
of the functionalization steps. Thus, the tertiary amine was
installed prior to the carboxylic ester moiety to maximize the
stability and functional group tolerance of the products.
PdCl
2
(dp
N/A
THF
65
[b]
pf)
(20)
Reaction Conditions: All reactions were performed at a 7 mM porphyrin 14
concentration with 4 eq. of amine 15, 20 mol-% catalyst and 30 mol-% ligand
under argon for 16 h.
Value is given relative to debrominated starting material.
were heated to the reaction temperature for 30 min before addition of other
reagents.
[
A]
1
Conversion is estimated based on H NMR data.
[b]
Base and amine
We
started
our
optimizations
using
bis[2-
(
diphenylphosphino)phenyl]ether (DPEPhos) as the ligand.
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
Being the most frequently reported ligand in use, we focused on
finding a suitable combination of base and precatalyst. Using
NaH as base the reaction provided higher yields in THF when
was inevitable with these reactions; however, such material
could be recycled back into the synthetic pathway affording
economic efficiency.
Pd(OAc)
solvent when using Pd
significant amount of debrominated starting material was
observed. Potassium tert-butoxide proved comparatively
efficient base, with higher yields achieved with Pd(OAc) in either
solvent (Entries 5-9). In all of these cases a significant amount of
debrominated material was present as well as target 16. By way
2 3
of contrast, Cs CO proved an entirely ineffective base, with the
sole product in all cases being debrominated starting material.
Since substantial amounts of debrominated starting material
were obtained in all trial reactions, further optimization was
necessary. By stirring the base and the amine for 30 min under
reaction conditions before the addition of other reagents, a
significant improvement was observed leading to relative
conversions of 70 and 65% when NaH and KOtBu was used
2
was employed. However, toluene was a more effective
Buchwald-Hartwig pathway. The early part of the synthesis
proceeded exactly as described previously (Scheme 3). For
example, 5,10-disubstituted porphyrin 7b was selectively
brominated to give 8b in 73% yield before quantitative metal
insertion to form 9b. Introduction of the donor group via the
optimized Buchwald-Hartwig amination conditions then
produced 17b in 68% yield. Another bromination reaction to give
2
(dba) (Entries 1-4). In all cases a
3
a
2
1
8b was followed by the introduction of the acceptor group in
one step to give 19b which was directly deprotected to the target
carboxylic acid 20b in 96% yield. A similar sequence produced
the respective 3,5-di-tert-butylphenyl derivative 20a. Attempts of
changing the order of donor and acceptor introduction led to the
formation of side products in form of amides and this was not
pursued further. The route just described provides one key
advantage over that outlined in Scheme 2, namely the
introduction of the acceptor group in one step. Analysis of the
Sonogashira cross-coupling conditions found that rather than the
troublesome two-step process employed earlier, installation of
the acceptor system through use of an alkynylphenyl ester
allowed for purification of intermediate 19a/b before deprotection
to the acid 20a/b. By removing the silyl-deprotection step and
introducing the acceptor group as the ester both the yield and
purification of this late stage compound were improved. The
one-step introduction for both the donor and acceptor groups
allows for complex groups to be synthesized separately, rather
than built on the porphyrin core – allowing for a more rational
and high-yielding synthesis of diverse electronic systems.
(
entry 12 and 13). Increasing the base to 20 eq. resulted in an
additional 10% conversion (entry 14 and 15). Changing the
ligand to 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl (BINAP)
gave 90% conversion. Applying PdCl
a reduction. A surprising outcome was observed when BINAP
and Cs CO were used together. While showing no reaction with
DPEPhos, 95% conversion (entry 17) was obtained when used
with BINAP. Although the successful use of Cs CO and BINAP
no explanation for this changed
reactivity compared to DPEPhos has been reported.
As best results were obtained when using Pd(OAc)
Cs CO in THF, these conditions were applied to further
2
(dppf) however, resulted in
2
3
2
3
[
30d,e]
is known in the literature,
2
, BINAP and
2
3
reactions.The presence of the debrominated starting material
R1
Organolithium Pathway
Buchwald-HartwigPathway
NH
N
a R1 = 3,5-di-tert-butylphenyl-
b R1 = 2,6-dioctyloxyphenyl-
R1
N
HN
R1
R1
(v)
(i)
R1
R1
Zn
7
NH
N
N
NH
N
N
N
N
N
N
N
N
N
(vi)
(iii)
R1
R1
R1
Br
R1
N
Zn
N
N
HN
HN
N
Br
21a 30-38%
1b 57%
8a 65%
8b 73%
17a
40%
2
2a 99%
2
1
7b 68%
(
ii)
(
vii)
9
9
a 99%
b 97%
(iv)
R1
R1
R1
Zn
N
N
N
N
N
N
OR3
N
N
N
N
R1
(viii)
R1
(viii)
R1
N
Zn
Br
Zn
N
N
N
O
(ix)
2
3a 85%
R2
2
3
Br
1
9a R = bis(4-t-Bu-phenyl)amino-, R = Me 75%
18a 95%
18b 95%
4a R = N,N-dimethylanilin-4-yl, R3 = Me 63-80%
2
2
2
2
3
1
9b R = bis(4-t-Bu-phenyl)amino-, R = Me N.D.
(ix)
5a R = N,N-dimethylanilin-4-yl, R3 = H 84-90%
2
2
3
2
2
0a R = bis(4-t-Bu-phenyl)amino-, R = H 95%
2
3
0b R = bis(4-t-Bu-phenyl)amino-, R = H 96%
Scheme 3. Synthesis of A
i) NBS, pyridine, CHCl , 0 °C, 1 h; (ii) Zn(OAc)
butylphenyl)amine, BINAP, dry Toluene (17a) or dry THF (17b), 65 °C, 16 h; microwave conditions: Cs
pyridine, CHCl , 0 °C or r.t., 1 h; (v) (a) 4-bromo-4-N,N-dimethylaniline, n-BuLi, dry Et O, 0 °C (21a) or -70 °C (21b), 1 h, (b) r.t., 2 h, (c) dry THF, r.t., 2-3 h, (d) sat.
NH Cl, r.t., 20 min, (e) DDQ, r.t., 1 h; (vi) NBS, pyridine, CHCl , r.t., 1 h; (vii) Zn(OAc) , CHCl , MeOH, r.t., 1.5 h; (viii) methyl-4-ethynylbenzoate, PdCl (PPh
CuI, DMF, 120 °C, 16 h; (ix) NaOH, MeOH, dry THF, 65 °C, 16 h.
2
BC 5,10-disubstituted porphyrins via organolithium reaction, Buchwald-Hartwig amination and Sonogashira cross-coupling reactions.
, CHCl , MeOH, r.t., 1.5 h; (iii) bench conditions: NaH (17a) or Cs CO (17b), Pd(OAc) , N,N-bis(4-tert-
CO , Pd(OAc) , BINAP, dry DMF, 160 °C, 6 min; (iv) NBS,
(
3
2
3
2
3
2
2
3
2
3
2
4
3
2
3
2
3 2
) ,
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
Organolithium pathway. Besides the Buchwald-Hartwig
amination, organolithium reactions were employed to vary the
donor unit. Organolithium reactions have proven to be a very
advantageous method to attach various alkyl or aryl moieties to
the porphyrin via a nucleophilic reaction without any further
modifications of the porphyrins, making this a widely used tool in
Investigating the microwave Buchwald-Hartwig reaction for 5,15-
disubstituted porphyrins, experimentation was also expanded to
the 5,10-disubstituded porphyrins. Following the procedure for
29a compound 9a (Scheme 3) was subjected to microwave
conditions yielding compound 17a in 24%. The yield was notably
lower compared to the 40% achieved under bench conditions.
[
2a,3b,17,18,20,31]
porphyrin chemistry.
In addition, this approach
2 3
Since NaH gave better yields compared to Cs CO under bench
proved to be less dependent on substituent effects than the
Buchwald-Hartwig amination, making long optimizations
redundant. Furthermore with this method it was possible to
synthesize aminated porphyrins 21a and 21b in yields
comparable to the other amination reaction (e.g., 17a and 17b)
but in much shorter time (Scheme 3). Hence, this type of
reaction provides an advantageous way of introducing a donor-
unit to the 5,10-disubstituted porphyrins compared to the
Buchwald-Hartwig amination.
conditions for this compound, this base and dry toluene were
used for a trial microwave reaction. The starting material was
consumed after 90 min but only 16% yield was achieved for
compound 17a. Following this set back compound 9b was
exposed to the original microwave conditions using Cs
2 3
CO ,
Pd(OAc) , and BINAP in dry DMF providing compound 17b in
2
only 19% yield with a considerable amount of debrominated
starting material formed as side product. Thus, it was decided
not to proceed with the microwave reaction for the 5,10-
substituted porphyrins. Sonogashira cross-coupling reaction
gave porphyrins 31a and 31b in high yield. Deprotection of 31b
yielded the final compound 32b in 96%. No further optimizations
were undertaken for the organolithium pathway since adapting
the previously used conditions gave 33a and 33b in 72 and 54%,
respectively. The following bromination and metallation of 33a
and 33b proceeded without difficulties in high yields as well as
the Sonogashira cross-coupling reaction and the subsequent
deprotection which lead to the final targets 37a and 37b in 85
and 72% (Scheme 4).
The final steps in the ‘organolithium pathway‘ then involved a
[
27]
Sonogashira
cross-coupling reaction, which is well
established especially with regard to the advantages in C-C
bond formation with porphyrin scaffolds. This high yielding
reaction was chosen to introduce the carboxylic ester group to
[
2a,32]
the porphyrins (19a/b and 24a).
final targets 20a/b and 25a.
Deprotection yielded the
2
Synthesis of 5,15-A BC D–A-systems
Buchwald-Hartwig versus organolithium pathway. The 5,15
counterparts to 20a/b were synthesized using the same method
Comparision of different synthetic pathways
(
Scheme 4). Following the Buchwald-Hartwig pathway the 5,15-
disubstituted starting materials were selectively brominated
resulting in compounds 27a and 27b. Again, precautions were
taken to minimize the formation of the dibrominated species but
this could not be avoided completely. Prior to the Buchwald-
Hartwig amination, zinc was inserted to avoid the formation of
any other metal porphyrin during the following Pd-catalyzed
reactions. This produced compounds 28a and 28b in 79% and
Both established pathways have their individual strengths. The
amination in the organolithium pathway works readily and in
good yields for both 5,10-disubstituted and 5,15-disubstituted
porphyrins. Another advantage is that bromination is used when
three of the four meso positions on the porphyrin core are
already occupied. This significantly minimizes the loss of
compound due to unwanted dibromination. Thanks to extensive
optimizations of the Buchwald-Hartwig amination step we were
able to find the most promising reaction conditions for these
kinds of porphyrins. Grätzel reported a yield of 71% and a
reaction time of 4 h for the Buchwald-Hartwig amination in the
8
7%, respectively. The previously optimized reaction conditions
for the Buchwald-Hartwig amination were employed to form
compounds 29a and 29b but the reaction was still plagued by
the formaton of the debrominated derivative.
[
8c]
Thus,
initial
attempts
included
[5-bromo-10,20-
synthesis of his dye YD2-o-C8
reaction time of 15 h for his optimized sensitizer SM371.
and a yield of 54% with a
[
8b]
diphenylporphyrinato]zinc(II) 28c (Scheme 5) which was
subjected to microwave conditions with a procedure similar to
the bench reaction. The porphyrin was heated to 160 °C for 4
Imahori reports a yield of 61% after 4 h with prior activation of
the amine with n-BuLi for the amination in the synthesis of his
[
16b]
min using Cs
5% yield. For comparison a bench reaction was set up utilizing
the same porphyrin, base, catalyst and ligand in dry THF at
6 °C for 16 h. This reaction gave the target compound in 35%
2
CO
3
, Pd(OAc)
2
and BINAP in dry DMF resulting in
ZnPBAT.
These values are comparable to the 72% yield and
4
16 h reaction time achieved with the 5,15-disubstituted porphyrin
29b and 68% yield for the 5,10-disubstituted porphyrin 17b.
Additionally, the reaction time can be significantly shortened by
applying microwave conditions. Yields of around 45% were
achieved with reaction times of 4-6 min which may provide a
synthetic benefit considering DSSC device production.
Furthermore, changing the sequence of our synthesis compared
6
yield. This clearly shows the strength of microwave reactions
reducing not just the reaction time but also increasing the
outcome of the reaction by 10%. Following this promising result
compound 28a was subjected to the same conditions giving 29a
in 35%. Bench conditions produced a favorable yield of 72% for
compound 29b and thus were chosen for this synthesis.
[
8b,8c,16b]
to Grätzel and Imahori
resulted in some practical
advantages and simplifications outlined above.
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
R1
Organolithium Pathway
Buchwald-Hartwig Pathway
NH
N
N
a R1 = 3,5-di-tert-butylphenyl-
b R1 = 2,6-dioctyloxyphenyl-
HN
R1
(i)
R1
R1
Zn
R1
(v)
R1
2
6
NH
N
N
N
N
N
N
N
N
N
NH
N
N
(
vi)
(iii)
Br
N
Zn
R1
Br
N
N
HN
N
HN
R1
3
3
4a > 99%
4b 80%
R
1
29a 36%
29b 72%
R1
2
7a 60%
27b 43%
3
3
3a 72%
3b 54%
(
vii)
(iv)
(ii)
R1
R1
Zn
R1
28a 79%
R1
Zn
2
8b 87%
N
N
N
N
N
N
OR
O
3
N
N
N
N
(
viii)
R2
(viii)
Br
N
N
Zn
Br
N
N
3
3
5a 91%
5b > 99%
R1 36a R = N,N-dimethylanilin-4-yl, R = Me 60%
2
3
R1
2
3
3
3
1a R = bis(4-t-Bu-phenyl)amino-, R = Me 69%
30a 85%
30b 96%
6b R = N,N-dimethylanilin-4-yl, R3 = Me 50%
2
3
2
3
1b R = bis(4-t-Bu-phenyl)amino-, R = Me 83%
(ix)
2
3
3
3
7a R = N,N-dimethylanilin-4-yl, R = H 85%
2
3
3
2b R = bis(4-t-Bu-phenyl)amino-, R = H 96%
2
3
7b R = N,N-dimethylanilin-4-yl, R = H 72%
Scheme 4: Synthesis of A
i) NBS, pyridine, CHCl , 0 °C, 1 h; (ii) Zn(OAc)
THF, 65 °C, 16 h; microwave conditions: Cs
dimethylaniline, n-BuLi, Et O, 0 °C, 1 h, (b) r.t., 2 h, (c) THF, r.t., 2-3 h, (d) sat. NH
Zn(OAc) , CHCl , MeOH, r.t., 1.5 h; (viii) methyl-4- ethynylbenzoate, PdCl (PPh , CuI, DMF, 120 °C, 16 h; (ix) NaOH, MeOH, THF, 65 °C, 16 h.
2
BC 5,15-disubstituted porphyrins via organolithium reaction, Buchwald-Hartwig amination and Sonogashira cross-coupling reactions.
, CHCl , MeOH, r.t., 1.5 h; (iii) bench conditions: Cs CO , Pd(OAc) , N,N-bis(4-tert-butylphenyl)amine, BINAP,
CO , Pd(OAc) , BINAP, DMF, 160 °C, 6 min; (iv) NBS, pyridine, CHCl , r.t., 1 h; (v) (a) 4-bromo-4-N,N-
Cl, r.t., 20 min, (e) DDQ, r.t., 1 h; (vi) NBS, pyridine, CHCl , r.t., 1 h; (vii)
(
3
2
3
2
3
2
2
3
2
3
2
4
3
2
3
2
3 2
)
In addition, yields of the 5,10-disubstituted and the 5,15-
disubstituted porphyrins for the various functionalization steps
to the porphyrin core was explored. Here we chose a Suzuki
[
33]
cross-coupling reaction to facilitate the synthesis of a simple
5,15-A BC-D–A system which can be generated quickly and in
(Scheme 3 and 4) are comparable. The outcome of the
2
Buchwald-Hartwig reaction using microwave conditions is
slightly lower for the 5,10-disubstituted porphyrin 17a with 25%
compared to the same reaction using 5,15-disubstituted
porphyrin 28a with 35% yield. The bench reaction for 17a gives
a slightly higher yield than the microwave reaction for 29a. When
subjected to the same conditions the 5,15-disubstituted
porphyrin 28b and the 5,10-disubstituted porphyrin 9b yielded
the desired aminoporphyrin in 72 and 68% yield. Furthermore, it
can be observed that porphyrins carrying 3,5-di-tert-butylphenyl
groups (17a and 29a) are giving lower yields for the Buchwald-
Hartwig reaction than their counterparts with 2,6-
dioctyloxyphenyl groups (17b and 29b). The Sonogashira cross-
coupling reaction provides very similar results in all cases. The
organolithium reactions gave slightly lower yields for the 5,10-
disubstituted porphyrin 21a compared to the 5,15-disubstituted
porphyrin 33a, while the yields for porphyrins 21b and 33b are
nearly identical. The condensation reaction of the 5,15-
disubstituted porphyrins facilitated much higher yields, hence
making the overall time for the synthesis of 5,15-disubstituted
porphyrins noticeably shorter. Common yields for the
condensation reaction for 5,15-disubstituted porphyrins are
around 30-50% whereas the 5,10-disubstituted porphyrins are
larger amounts and might provide a synthetic effort/cost/benefit
compromise for applications (Scheme 5). This versatile reaction
[
6a,32c,
has been effectively applied to various porphyrin systems.
34]
Metalation is not necessary prior to the reaction and thus this
method can be used to generate free base push-pull porphyrins
directly using the above mentioned organolithium reaction
[
2a,3b,17,18,20,31]
combined with a Suzuki cross-coupling reaction.
In
addition, by changing the alkynylphenyl group, which is co-
planar with the porphyrin, to a phenyl linker the electronic
conjugation of the push-pull porphyrins can be varied which
might be useful for applications. Here we decided to prepare the
zinc(II) porphyrin 39c using a step-wise strategy for comparison
with the other target compounds outlined in this contribution.
The limiting step, as observed earlier is the palladium-catalyzed
Buchwald-Hartwig reaction of bromoporphyrin and amine. Both
bench and microwave conditions were used and whilst complete
consumption of the starting material is observed, isolation of the
aminated porphyrin is quite difficult. No significant difference
was observed in yield depending on whether the reaction is
carried out on the bench or in the microwave; however, the
microwave reaction takes only six min. The next step involved
the bromination of 29c using NBS and subsequent Suzuki
coupling of the brominated product 30c with 4-
methoxycarbonylphenyl boronic acid to generate 38c in a yield
of 85% and the target compound 39c was obtained after
deprotection in 82%. The yields for the Suzuki cross-coupling
[
20b]
normally obtained in yields of 5-11%.
Suzuki approach. Besides the Sonogashira cross-coupling
reaction another option of introducing a carboxylic functionality
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
were similar to the yields obtained via Sonogashira-cross
coupling (31a and 31b, Scheme 4).
with a donor-acceptor separation of 2.70(10) Å and an angle of
155.70(50)° (O106_2-H161_2···O161_2) on one side of the
molecule and a donor-acceptor separation of 2.60(1) Å and
N
N
N
N
N
N
N
N
(i or ii)
R1
N
Zn
Br
Zn
2
8c
2
3
9c R1 = H 23-45%
0c R1 = Br 82%
(iii)
(iv)
2
R O
N
N
N
Zn
N
O
N
3
3
8c R2 = Me 85%
9c R2 = H 82%
(v)
Figure 3. Top: Molecular structure of 37a in the crystal (thermal ellipsoids
show 50% probability). Hydrogen atoms and disordered units are omitted for
clarity. Bottom: Molecular structure of 37a showing the axil ligands; 3,5-di-
tert-butylphenyl groups and hydrogen atoms have been omitted for clarity.
Scheme 5. Functionalization of 5,15-disubstituted porphyrins via Buchwald-
Hartwig amination and Suzuki cross-coupling reactions. (i) Bench conditions:
o
Cs
h; (ii) microwave conditions: Cs
iii) NBS, pyridine, CHCl , r.t., 1 h; (iv) 4-methoxycarbonylphenylboronic acid,
CO , Pd(PPh , THF/H
2
CO
3
, Pd(OAc)
2
, N,N-bis(4-tert-butylphenyl)amine, BINAP, THF, 60 C, 16
o
2
3 2
CO , Pd(OAc) , BINAP, DMF, 160 C, 6 min;
(
K
3
o
o
2
3
3
)
4
2
O, 70 C, 17 h; (v) NaOH, MeOH, THF, 70 C, 16 h.
an angle of 176.50(20)° (O106_1-H161_1···O161_1) on the
other side, forming a 1-D hydrogen bonded network. The overall
arrangement is row-by-row like, with the 3,5-di-tert-butylphenyl
groups acting as space keepers (Figure SI2).
The molecular structure of compound 26b in the crystal is shown
in Figure 4. The long alkyl arms of the 2,6-dioctyloxyphenyl
groups are oriented above and below the plane of the porphyrin
macrocycle. The alkyl chains can also be seen to be rotated
over the plane of the porphyrin reminiscent of a strap across the
plane of the porphyrin to form a steric shield. This is facilitated
by an 114.80(4)° twist angle between the phenyl rings and the
Overall the Suzuki approach is comparable to the other
pathways explored, providing an attractive alternative to the
Sonogashira cross-coupling reaction with the added option of
synthesizing free-base sensitizers which could be useful for
[
35]
applications such as photodynamic therapy.
Structural studies
Some of the compounds studied herein gave single crystals
suitable for crystallographic analysis. The crystal structure of
24-atom mean plane. The relative arrangement of the
macrocycle and the substituents is reminiscent of the chair
conformation found in cyclohexanes (see Figure SI3).
Additionally, there is a short C─H···O contact [3.41(2) Å]
between the free meso position (C5) and the oxygen of an
octyloxy group (O57). These short contacts facilitate a stepwise
packing within the unit cell with repeating units lining up in a
zigzag pattern (Figure SI4) with the alkyl chains lining up in such
a fashion as to pack the space between the macrocycles (Figure
SI5).
3
7a is an interesting example of the formation of unsymmetric
coordination dimers (Figure 3). With two molecules present in
the asymmetric unit, the Zn(II) metal center has an axial
coordination to the dimethylaniline unit of the nearest neighbor.
However, the second unit contains an axial water molecule at
the Zn(II) center and therefore does not reciprocate the
interaction. In fact, an intermolecular hydrogen bond between
the coordinated water molecule and the dimethylaniline unit is
present at a donor-acceptor distance of 2.39(3) Å. This feature is
only the major disordered part as rotation of the dimethylaniline
group results in a displacement of the water molecule (see
Figure SI1). The distance between the 24-atom mean plane
centroids is 5.30(4) Å and the two porphyrin macrocyclic planes
are tilted by 18.81(4)° against each other. The rotation of the
The structure of 40a (not shown, see SI Figure SI6) exhibits a
relatively planar scaffold on which the 3,5-di-tert-butylphenyl
groups are orientated orthogonal to the plane of the 24-atom
ring. Its structural features are similar to other A
2
B
2
porphyrins
angle (128.6(2)°) is similar
to that of previously reported (127.9 – 128.9°). Similarlary, C
(20/15)—C angles (125.1(2))° are comparable to that of the
[
36]
a m a
(with B = Br). The C —C (Br)—C
a
—
3
(
5
,5-di-tert-butylphenyl groups is orientated at 57.77(10)°
C10_1), 54.72(10)° (C20_2), 60.95(10)° (C10_2), and
8.60(10)° (C20_2) to the 24-atom mean plane. In the crystal
C
m
a
free base and zinc(II) complex (125.2 – 125.7°) with only a
noticable difference to the palladium(II) complex (123.2 –
packing, the major form present is that of a head-to-head
overlap of the porphyrins facilitated by Zn···Nax coordination.
Additionally, hydrogen bonding between two COOH groups
yields head-to-head interactions between neighboring molecules
123.3°). Compound 29c crystallized with two molecules in the
asymmetric unit. Figure 5 shows one of these molecules for the
trisubstituted complex in which the 5,15-disubstituted phenyl
residues are orientated at 60.64(5), 67.72(5)° and 73.43(6),
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
7
5.79(5)° from the 24-atom mean plane. The N-substituted aryl
molecules is characterized by an overlapping head-to-head
arrangement with the phenyl rings forming a minor groove
rings associated with the bis(4-(tert-butyl)phenyl)amine are
rotated to each other at 124.03(7)° (N51_1) and 102.50(6)°
between
stacked
porphyrins
and
the
bis(4-(tert-
(
N51_2). The C
base A B systems previously reported such as the 5-Iodo-10,20-
diphenylporphyrin and the n10-Isopropyl-5,15-diphenylporphyrin,
a
—C
m
—C
a
angles are comparable to other free
butyl)phenyl)amine forming a major groove. This offset stacking
forms a zigzag pattern in the unit cell, Figure SI7, which
compared to the almost perpendicular patterns observed in less
2
[
37]
with
1
1
C
a
—C
25.02(17) – 125.30(17)° and C
27.65° compared to 127.03(18)°.
m
(phenyl)—C
a
angles 123.76
–
124.98° versus
bulky groups such as 5-iodo-10,20-diphenylporphyrin.
a
—C (H)—C
m
a
angle of 127.49 –
[
37,38]
There are some
differences with the substituted C15 position with the C
(iodo)—C angle of 128.42° and a C —C (isopropyl)—C
angle of 123.90° versus the —C (C15)—C angle of
25.81(17)° and 126.11(17)° for compound 29c.
a
—
Conclusions
C
m
a
a
m
a
C
a
m
a
Herein we report the synthesis of different series of 5,10 and
,15-disubstituted push-pull porphyrins related to 1-3 which have
1
5
been used extensively in recent studies on DSSCs. As
promising current systems, a comparative investigation of the
synthesis of similar push-pull porphyrins with regard to synthetic
optimization and comparison of currently used methodologies,
notably comparing the synthesis of 5,15- to 5,10-disubstituted
porphyrins was undertaken.
The targets made were obtained in moderate to good yields
using selective brominations, organolithium reactions as well as
Pd-catalyzed cross-coupling reactions. This allowed us to impart
the desired functionality step-wise in a very controlled and
strategic manner, equally applicable for 5,10-disubstituted and
5,15-disubstituted porphyrins. While every approach has its
demerits and benefits, the present approach compares favorably
in terms of modality e.g., introduction of the carboxylic acid in
one step as the ester instead of a two-step synthesis via a silyl
intermediate simplified purification and the overall synthesis. In
addition, the sequence of the functionalization steps was altered.
More functional group tolerance was achieved by introducing the
tertiary amine prior to the carboxylic acid. Therefore, optimized
acceptor and donor units could be synthesized separately and
introduced step-wise to the porphyrin. This allows a fine-tuning
of the electronic properties of the porphyrin at any stage of the
synthesis. The Buchwald-Hartwig amination reaction, which
proved to be the limiting step in the synthesis, was optimized,
while microwave conditions allowed a shortening of the reaction
times to 4-6 min facilitating the preparation of materials for
Figure 4. Molecular structure of 26b (thermal displacement ellipsoids give
0% occupancy); hydrogen atoms omitted for clarity.
5
applications. Our organolithium pathway provides
straightforward, fast and easily adaptable alternative to the
Buchwald-Hartwig approach. Overall, the step-wise
a
functionalization of porphyrins is a facile synthetic route and can
be easily adapted to other porphyrin systems allowing access to
a
library of various “push-pull” porphyrins or related
porphyrinoids with unsymmetrical substituent pattern.
Experimental Section
General conditions: Details are given in the SI (1.1) or were as reported
[
39]
earlier.
(
All starting materials such as 2,5-bis(hydroxymethyl)pyrrole
[
40]
[22b]
[8c]
1),
butylbenzaldehyde
synthesized according to standard procedures.
tripyrrane (2),
2,6-dioctyloxybenzaldehyde,
3,5-di-tert-
[41]
[13b]
and 5,15-disubstituted porphyrins
were
Figure 5. Molecular structure of one of the two independent molecules of 29c
in the asymmetric unit of the crystal. Thermal ellipsoids are drawn for 50%
occupancy; hydrogen atoms and disordered units have been omitted for clarity.
General procedure A: Condensation reaction for 5,10-A
2
porphyrins:
A flask was charged with anhydrous CH Cl (1.5 L) and purged with
2
2
argon. Tripyrrane (1 eq.), Pyrrole (1 eq.), the according aldehyde (2 eq.)
and TFA (0.61 eq.) were added. The flask was shielded from light and
the reaction was stirred at r.t. for 16 h. The reaction was oxidized with
DDQ (3.8-5 eq.) followed by stirring for 30 min. The reaction was
quenched with triethylamine and the solvent was removed in vacuo. The
a m a
This shows a small flattening of the C —C (C15)—C angle
compared to other alkyl substituted porphyrins however, not to
the extent of halogen substituted porphyrins. The packing of the
2 2
reaction mixture was filtered through silica using CH Cl as eluent
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
followed by purification by column chromatography using CH
2
Cl
2
/hexane
solvents were removed in vacuo and the product was recrystallized from
(
1:2, v/v).
2 2
MeOH/ CH Cl .
General Procedure B: Monobromination of 5,10-A
neck flask was purged with argon. The porphyrin (1 eq.) was dissolved in
CHCl . The flask was shielded from light and cooled to 0 °C. NBS (0.90
eq.) and pyridine were added and the reaction was stirred TLC analyses
indicated disappearance of the starting material at which point the
reaction was quenched with acetone. The solvents were removed under
vacuum and the product was purified by column chromatography using
toluene/hexane (1:3, v/v).
2
porphyrins: A 3-
General Procedure I: Reaction with organolithium compounds: The
porphyrin (1 eq.) and 4-bromodimethylaniline (12 eq.) were heated in two
flasks for 10 minutes under vacuum and then refilled with argon. Dry
diethyl ether was added to the 4-bromodimethylaniline (12 eq.) and the
solution was cooled to 0 °C or -70 °C. n-BuLi (12 eq.) was added drop-
wise over 1 h. After the addition was completed the reaction was allowed
to stir at r.t. for 2 h. Meanwhile the porphyrin (1 eq.) was dissolved in dry
THF. The solution was added to the organolithium reagent and was
3
4
stirred at r.t. for 2 h. The reaction was hydrolyzed with sat. NH Cl solution
followed by stirring for 20 minutes. DDQ (4.50 eq.) was added and the
reaction was stirred for another hour. The solvents were removed in
vacuo. The product was purified by filtration through silica gel using
General Procedure C: Insertion of zinc(II): Bromoporphyrin (1 eq.) was
dissolved in CHCl
3
atr.t.. Zinc(II)acetate (3 eq.) was dissolved in MeOH
and added to the reaction. The reaction was stirred at r.t. and monitored
CH
CH
2
Cl
Cl
2
as eluent, followed by filtration through silica gel using hexane/
(5:1, v/v) to remove traces of starting material and a third filtration
by TLC. The products were filtered through a plug of silica using CH
as eluent and the solvent was removed.
2 2
Cl
2
2
through silica gel using CH
2 2
Cl /hexane (1:1) to obtain the pure product.
General Procedure D: Buchwald-Hartwig amination (bench
reaction): Cs CO (4 eq.) and N,N-bis(4-tert-butylphenyl)amine (4 eq.)
[
38]
5
,10-Bis(3,5-di-tert-butylphenyl)porphyrin 7a:
Porphyrin 7a was
2
3
synthesized according to general procedure A. Tripyrrane (0.92 g, 4.12
mmol), 3,5-di-tert-butylbenzaldehyde (1.80 g, 8.24 mmol), pyrrole (0.28
mL, 4.12 mmol) and TFA (0.20 mL, 0.63 eq.) were dissolved in 1.50 L dry
and dry THF were placed in an oven-dried Schlenk flask, three freeze-
thaw cycles and were reacted together for 30 min at reaction temperature.
Bromoporphyrin (1 eq.), palladium(II)acetate (10 mol-%), (S)-(−)-2,2′-
bis(diphenylphosphino)-1,1′ -binaphthalene(BINAP) (20 mol-%.) were
added and the solution was subjected to three freeze-pump-thaw cycles
before it was released to argon. The reaction mixture was heated to
CH
2 2
Cl . Recrystallization gave purple crystals (150 mg, 0.22 mmol, 5%).
[42c]
M.p.: >300 °C (lit. M.p. >300 °C). R
v/v). H NMR (400 MHz, CDCl
=
H
=
f
= 0.47 (hexane/ CH
, 25 °C): δ =10.12 (s, 1H, Hmeso), 9.74 (d, J
), 9.65 (d, J = 4.62 Hz, 1H, H ), 9.36 (d, J = 4.62 Hz, 1H,
), 9.27 (d, J = 4.62 Hz, 1H, H ), 9.00 (d, J = 4.62 Hz, 1H, H ), 8.93 (d, J
4.62 Hz, 1H, H ), 8.85-8.90 (m, 2H, H ), 8.03 (s, 4H, Ar-o-CH), 7.79 (s,
) and -2.93 ppm (s, 2H, NH).
): λmax (log ε) = 408 (6.11), 503 (4.76), 580 nm (4.35).
2 2
Cl , 1:1,
1
3
4.62 Hz, 1H, H
β
β
6
5 °C. The reaction was monitored by TLC and quenched by pouring into
water after full consumption of the starting material. The product was
extracted with CH Cl (3 × 100 mL), washed with NaHCO (3 × 100 mL)
and NaCl (3 × 100 mL) and dried over MgSO . The solvents were
removed in vacuo. The reaction mixture was filtered through a plug of
silica using CH Cl as eluent. Purification by column chromatography
using CH Cl /hexane (1:2, v/v) gave the desired product.
β
β
β
β
β
2
2
3
2
H, Ar-p-CH), 1.51 (s, 36H, t-butyl-CH
UV/Vis (CH Cl
54 4
HRMS (MALDI) m/z calcd. for C48H N (M ): 686.4348; found 686.4354.
3
4
2
2
+
2
2
2
2
5
,10-Bis(2,6-dioctyloxyphenyl)porphyrin 7b: Porphyrin 7b was
synthesized according to general procedure A. Tripyrrane (0.92 g, 4.12
mmol), 2,6-dioctoxybenzaldehyde (2.96 g, 8.24 mmol) and pyrrole (0.28
General procedure E: Buchwald-Hartwig amination (microwave
reaction): Bromoporphyrin (1 eq.), N,N-bis(4-tert-butylphenyl)amine (4
mL, 4.12 mmol) were dissolved in anhydrous CH
column chromatography (silica gel; n-hexane:CH
removal of solvents followed by recrystallization (CHCl
title compound as purple crystals (256 mg, 0.26 mmol, 6.3%). M.p 75-
2
Cl
2
(2 L). Purification by
Cl 2:1, v/v) and
/CH OH) gave the
2 3
eq.), palladium(II) acetate (0.05 eq.), (BINAP) (0.05 eq.) and Cs CO (4
2
2
,
eq.) were placed in a microwave vial, dissolved in anhydrous DMF, and
degassed with argon for 10 minutes. The vial was sealed and subjected
to microwave radiation for 6 minutes at 160 °C. Work up followed
General procedure D.
3
3
1
7
2
H
7 °C. R
5 °C): δ = 10.10 (s, 2H, Hmeso), 9.38 (s, 2H, H
), 8.92 (d, J = 4.2 Hz, 2H, H ), 8.78 (s, 2H, H
Ar-p-CH), 6.97 (d, J = 8.3 Hz, 4H, Ar-m-CH), 3.75-3.78 (m, 8H, OCH
f
= 0.31 (n-hexane:CH
2
Cl
2
, 1:1, v/v). H NMR (400 MHz, CDCl
), 9.22 (d, J = 4.2 Hz, 2H,
), 7.66 (t, J = 8.3 Hz, 2H,
),
) and -3.22 ppm (s,
, 25 °C): δ = 160.1, 130.6, 130.5,
30.4, 130.3, 130.2, 130.1, 129.9, 129.8, 120.9, 111.9, 105.3, 103.3,
8.7, 31.3, 28.6, 28.5, 28.4, 25.1, 22.2 and 13.8 ppm. UV/Vis (CH Cl ):
max (log ε) = 407 (5.60), 502 (4.24), 576 nm (3.49). HRMS (MALDI) m/z
3
,
β
β
β
β
General procedure F: Bromination of tri-substituted porphyrins: To
a solution of porphyrin (1 eq.) in CHCl , NBS (1.50 eq.) and pyridine were
3
added. The reaction was stirred at r.t., monitored by TLC and quenched
with acetone. The solvents were removed and the compound was
2 2
purified by filtration through a plug of silica using CH Cl as eluent.
2
0
2
1
6
.74-0.87 (m, 16H, CH
H, NH). C NMR (100 MHz, CDCl
2
), 0.38-0.59 (m, 44H, CH
2 3
/CH
13
3
2
2
λ
General procedure G: Sonogashira cross-coupling reaction:
Bromoporphyrin (1 eq.), methyl 4-ethynylbenzoate (5 eq.), PdCl (PPh
0.10 eq.) and CuI (0.31 eq.) were placed in an oven-dried Schlenk flask
+
calcd. for C64
86
H N
O
4 4
(M ): 974.6649; found 974.6656.
2
3 2
)
(
[
43]
1
8
0
0,15-Bis(3,5-di-tert-butylphenyl)-5-bromo-porphyrin 8a: Porphyrin
and heated under vacuum for 10 minutes. Anhydrous DMF and diethyl
amine (3:1, v/v) were added. The reaction mixture was heated to 120 °C
for 16 h until TLC analysis indicated complete consumption of the starting
material after three freeze-thaw cycles. The product was extracted with
a was synthesized according to procedure B. Porphyrin 7a (425 mg,
.69 mmol), NBS (100 mg, 0.58 mmol) and pyridine (0.15 mL) were
dissolved in CHCl
MeOH/CH Cl and gave purple crystals (386 mg, 0.50 mmol, 78%) with
analytical data identical to the literature.
hexane/CH Cl , 2:1, v/v). HRMS (MALDI) m/z calcd. for C48
64.3454; found 764.3480.
3
(150 mL). The product was recrystallized from
2
2
CH
brine (3 × 100 mL) and NaHCO
The solvents were removed and the reaction mixture was filtered through
a plug of silica using CH Cl as eluent prior to column chromatography
silica gel) using CH Cl /hexane (2:3, v/v).
2
Cl
2
(3 × 50 mL). The combined organic phases were washed with
[43]
f
M.p.: >300 °C. R = 0.56
3
(3 × 100 mL) before drying over MgSO
4
.
+
(
2
2
4
H53BrN (M ):
7
2
2
(
2
2
1
0,15-Bis(2,6-dioctyloxyphenyl)-5-bromo-porphyrin 8b: Porphyrin 8b
was synthesized according to general procedure B. Porphyrin 7b (400
mg, 0.38 mmol) was dissolved in CHCl (150 mL), purged with argon and
cooled to 0 °C. Pyridine (0.50 mL) and NBS (58 mg, 0.33 mmol) were
added and the solution stirred at 0 °C. The product was purified by
column chromatography (silica gel) using toluene/n-hexane (1:3, v/v) as
eluent. The target was obtained in the second porphyrin-containing
General Procedure H: Ester deprotection: To
a solution of the
3
porphyrin ester (1 eq.) in THF, NaOH in MeOH (2 M, 353 eq.) was added,
the solution was purged with argon and heated to 70 °C for 16 h. The
solvents were removed in vacuo. The addition of water gave a green
solution. HCl (1 M) was added drop-wise until pH 5 was reached. The
product was extracted with CH
2
Cl
2
(3 × 100 mL) and washed with brine
. The
fraction as a purple solid (292 mg, 0.28 mmol, 73%). M.p.: 72-74 °C. R
f
=
(
1 × 100 mL) and NaHCO (1 × 100 mL) before drying over MgSO
3
4
1
0
1
.44 (n-hexane:CH
0.00 (s, 1H, Hmeso), 9.68 (d, J = 4.5 Hz, 1H, H
2
Cl
2
, 1:1, v/v). H NMR (400 MHz, CDCl
3
, 25 °C): δ =
β
), 9.54 (d, J = 4.5 Hz, 1H,
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
+
H
β
), 9.30 (d, J = 4.5 Hz, 1H, H
β
), 9.14 (d, J = 4.5 Hz, 1H, H
), 7.63-7.68 (m, 2H, Ar-p-CH), 6.94-6.97 (m,
H, Ar-m-CH), 3.76-3.79 (m, 8H, OCH ), 0.85-0.93 (m, 8H, CH ), 0.71-
.77 (m, 8H, CH ), 0.37-0.57 (m, 44H, CH /CH ) and -2.86 ppm (s, 2H,
, 25 °C): δ = 160.0, 159.9, 131.3, 131.1,
31.0, 130.0, 129.9, 120.8, 120.1, 113.2, 112.4, 105.3, 105.2, 104.5,
01.1, 68.6, 31.3, 28.6, 28.5, 28.4, 25.1, 22.2 and 13.8 ppm. UV/Vis
Cl ): λmax (log ε) = 415 (5.61), 511 (4.27), 546 (3.65), 587 (3.69), 641
β
), 8.83-8.85
(4.21). HRMS (MALDI) m/z calcd. for C59
found 928.4825.
72
H N
4
SiZn (M ): 928.4818;
(
4
0
m, 2H, H
β
), 8.70 (s, 2H, H
β
2
2
2
2
3
[
(
15,20-Bis(3,5-di-tert-butylphenyl)-5-bromo-10-
triisopropylsilylethynyl)porphyrinato]zinc(II) 11a: Porphyrin 10a (200
(150 mL). Pyridine (3 mL) and
NBS (85 mg, 0.44 mmol) were added and the solution stirred at r.t until
TLC analyses indicated complete consumption of the starting material.
The solvents were removed under vacuum and the product was purified
13
NH). C NMR (100 MHz, CDCl
1
1
3
mg, 0.22 mmol) was dissolved in CHCl
3
(
CH
2
2
+
4 4
nm (3.35). HRMS (MALDI) m/z calcd. for C64H85BrN O (M ): 1052.5754;
found 1052.5739.
2 2
by column chromatography (silica gel) using CH Cl :n-hexane (1:3, v/v)
as eluent to give a purple solid (211 mg, 0.21 mmol, 95%). M.p.: 178-
1
[
10,15-Bis(3,5-di-tert-butylphenyl)-5-bromo-porphyrinato]zinc(II) 9a:
180 °C. R
25 °C): δ = 9.86 (d, J = 4.5 Hz, 1H, H
(d, J = 4.5 Hz, 1H, H ), 9.71 (d, J= 4.5 Hz, 1H, H
1H, H ), 8.97 (d, J = 4.5 Hz, 1H, H ), 8.87-8.89 (m, 2H, H
4H, Ar-o-CH), 7.81 (m, 2H, Ar-p-CH), 1.55 (s, 36H, t-butyl-CH
f
= 0.41 (n-hexane:CH
2
Cl
2
, 2:1, v/v). H NMR (600 MHz, CDCl
), 9.81 (d, J = 4.5 Hz, 1H, H ), 9.76
), 8.98 (d, J = 4.5 Hz,
), 8.02-8.03 (m,
) and 1.46-
3 3 3
1.49 ppm (m, 21H, SiCH(CH ) ). C NMR (100 MHz, CDCl , 25 °C): δ =
3
,
The title compound was synthesized according to general procedure C.
Bromoporphyrin 8a (768 mg, 1 mmol), zinc(II) acetate (652 mg, 3 mmol)
were dissolved in CHCl
gave purple crystals (839 mg, 1 mmol, >99%). M.p.: >300 °C. R
(
1
9
β
β
β
β
3
(150 mL). Recrystallization from CHCl
3
/CH
= 0.33
, 25 °C): δ = 9.75 (s,
), 9.52 (d, J = 4.62 Hz, 1H, H ),
), 9.02-9.07 (m, 5H, H ), 8.13 (s, 4H, Ar-o-
3
OH
β
β
β
f
3
1
13
hexane/CH
2
Cl
H, Hmeso), 9.71 (d, J = 4.4 Hz, 1H, H
.22 (d, J = 4.62 Hz, 1H, H
2
, 2:1, v/v). H NMR (600 MHz, CDCl
3
β
β
153.0, 152.9, 151.2, 150.5, 150.4, 149.7, 149.6, 149.2, 141.4, 133.6,
133.5, 132.7, 132.4, 132.1, 131.1, 129.6, 129.3, 124.8, 124.0, 120.9,
109.4, 105.0, 100.3, 97.8, 35.0, 31.7, 19.1 and 11.9 ppm. UV/Vis
β
β
1
3
CH), 7.84 (s, 2H, Ar-p-CH) and 1.58 ppm (s, 36H, t-butyl-CH
3
). C NMR
(
100 MHz, CDCl
3
, 25 °C): δ = 151.0, 150.9, 150.5, 150.4, 149.9, 149.7,
2 2
(CH Cl ): λmax (log ε) = 434 (5.56), 567 (4.13), 609 nm (4.06). HRMS
(MALDI) m/z calcd. for C H71BrN SiZn (M ): 1006.3923; found
59 4
1006.3917.
+
1
1
1
(
8
49.4, 149.2, 148.9, 148.8, 141.8, 141.6, 133.6, 133.3, 132.8, 132.8,
32.7, 132.5, 132.3, 131.9, 129.9, 129.9, 123.7, 122.9, 121.2, 121.1,
05.8, 103.4, 35.3 and 32.0 ppm. UV/Vis (CH
2
Cl
2
): λmax (log ε) = 417
+
5.43), 547 (3.96), 585 nm (3.16). MS (MALDI) m/z (%): 830.29 (66) [M ],
[
(
15,20-Bis(3,5-di-tert-butylphenyl)-5-(bis(4-hexylphenyl)amino)-10-
triisopropylsilylethynyl)porphyrinato]zinc(II) 12a: Porphyrin 11a (330
+
+
28.28 (100) [M ], 826.29 (66) [M ], 732.36 (24) [M-C
2 6
H Zn], 675.28 (12)
+
[
M-C10
H33]. HRMS (MALDI) m/z calcd. for C48
H51BrN
4
Zn (M ): 826.2589;
mg, 0.33 mmol) was dissolved in dry THF (30 mL) and subjected to three
freeze-pump-thaw cycles. Bis(4-hexylphenyl)amine (440 mg, 1.32 mmol),
NaH (60% dispersion, 50 mg, 1.32 mmol), Pd(OAc) (15 mg, 66 µmol)
2
found 826.2620. Anal. Calcd. for C48
found: C 69.19, H 6.25, N 6.51%.
H51BrN Zn: C 69.52, H 6.2, N 6.76%;
4
and DPEPhos (54 mg, 0.10 mmol) were added and the solution was
heated to reflux for 16 h. The solvent was removed under vacuum and
the product was purified by column chromatography (silica gel) using
[
10,15-Bis(2,6-dioctyloxyphenyl)-5-bromo-porphyrinato]zinc(II) 9b:
Porphyrin 9b was synthesized following general procedure C.
Bromoporphyrin 8b (0.25 g, 0.24 mmol) was dissolved in CHCl (70 mL)
3
CH
contained the title compound which was recrystallized from
CHCl /CH OH to give purple crystals (227 mg, 0.18 mmol, 56%). The
second porphyrin containing fraction contained debrominated starting
material (~30%). M.p.: 192-193 °C. R = 0.40 (n-hexane:CH Cl , 3:1, v/v).
, 25 °C): δ = 9.75 (d, J = 4.5 Hz, 1H, H ), 9.73
), 9.40 (d, J = 4.5 Hz, 1H, H ), 9.30 (d, J = 4.5 Hz,
), 8.98 (d, J = 4.5 Hz, 1H, H ), 8.85-8.87 (m, 2H, H ), 8.83 (d, J =
4.5 Hz, 1H, H ), 8.04 (s, 2H, Ar-o-CH), 8.01 (s, 2H, Ar-o-CH), 7.81 (s, 1H,
Ar-p-CH), 7.78 (s, 1H, Ar-p-CH), 7.25 (d, J = 8.7 Hz, 4H, N-Ar-CH), 7.01
(d, J = 8.7 Hz, 4H, N-Ar-CH), 2.51 (t, J = 7.7 Hz, 4H, hexyl-CH ), 1.56 (s,
18H, t-butyl-CH ), 1.52 (s, 18H, t-butyl-CH ), 1.44-1.48 (m, 21H,
SiCH(CH ), 1.28-1.33 (m, 16H, hexyl-CH ) and 0.87 ppm (t, J = 6.8 Hz,
6H, hexyl-CH ). C NMR (100 MHz, CDCl , 25 °C): δ = 153.0, 152.9,
2 2
Cl :n-hexane (1:4, v/v) as eluent. The first porphyrin fraction
at r.t.. Zinc(II) acetate (0.15 g, 0.72 mmol) was dissolved in methanol (5
mL) and added to the reaction. The reaction products were filtered
through a plug of silica using CH
gave a quantitative yield of purple crystals (274 mg, 0.23 mmol, 97%).
M.p.: 88-91 °C. R
3
3
2 2
Cl as eluent. The removal of solvents
f
2
2
1
1
f
= 0.39 (n-hexane:CH
2
Cl
2
, 1:1, v/v). H NMR (400 MHz,
), 9.57 (s, 1H, Hmeso), 9.23
), 9.14 (d, J = 4.6 Hz, 1H, H ), 8.98-8.99 (m, 2H, H ),
), 7.68-7.73 (m, 2H, Ar-p-CH),
), 0.89-1.05 (m, 8H,
H NMR (600 MHz, CDCl
(d, J = 4.5 Hz, 1H, H
1H, H
3
β
CDCl , 25 °C): δ = 9.68 (d, J = 4.6 Hz, 1H, H
(
3
β
β
β
d, J = 4.5 Hz, 1H, H
β
β
β
β
β
β
8
7
CH
.69 (s, 2H, H
β
), 8.68 (d, J = 4.6 Hz, 1H, H
β
β
.02-7.04 (m, 4H, Ar-m-CH), 3.85-3.88 (m, 8H, OCH
), 0.71-0.78 (m, 8H, CH ) and 0.40-0.56 ppm (m, 44H, CH
NMR (100 MHz, CDCl , 25 °C): δ = 160.0, 151.4, 151.2, 150.9, 150.8,
49.3, 148.7, 148.1, 132.3, 132.1, 131.9, 131.8, 131.7, 131.2, 129.7,
21.5, 121.4, 113.8, 112.9, 105.5, 105.4, 105.3, 105.2, 102.9, 68.7, 31.3,
1.2, 28.6, 28.5, 25.2, 25.1, 22.2 and 13.8 ppm. UV/Vis (CH Cl
2
13
2
2
2 3
/CH ).
C
2
3
3
3
1
1
3
3
)
3
2
1
3
3
3
2
2
): λmax
152.4, 151.8, 150.7, 150.4, 150.2, 149.4, 148.6, 141.3, 134.9, 133.7,
132.4, 132.1, 132.0, 131.4, 130.8, 129.3, 128.9, 124.0, 123.9, 123.2,
121.9, 120.9, 109.2, 99.9, 97.5, 35.2, 35.0, 31.8, 31.7, 31.4, 29.0, 22.6,
(
log ε) = 417 (5.58), 546 (4.14), 583 nm (2.91). HRMS (MALDI) m/z calcd.
+
4 4
for C64H85BrN O Zn (M ): 1114.4889; found 1114.4885.
1
(
1
9.1, 14.0 and 11.9 ppm. UV/Vis (CH
4.05), 625 nm (4.05). HRMS (MALDI) m/z calcd. for C83
263.7431; found 1263.7456.
2 2
Cl ): λmax (log ε) = 427 (5.37), 576
+
105 5
H N SiZn (M ):
[
(
(
(
10,15-Bis(3,5-di-tert-butylphenyl)-5-
triisopropylsilylethynyl)porphyrinato]zinc(II) 10a: Bromoporphyrin 9a
0.34 g, 0.41 mmol) was dissolved in anhydrous THF (30 mL) and NEt
5 mL) in an oven-dried Schlenk flask and subjected to three freeze-
3
[10,15-Bis(3,5-di-tert-butylphenyl)-5-N,N-bis(4-tert-
pump-thaw cycles. Triisopropylsilylacetylene (0.27 mL, 1.23 mmol),
PdCl (PPh (58 mg, 82 µmol) and CuI (26 mg, 0.14 mmol) were added
and the solution was heated to reflux for 16 h. The solvent was removed
under vacuum and the product was purified by column chromatography
butylphenyl)amino)porphyrinato]zinc(II) 17a:. Bromoporphyrin 9a
(200 mg, 0.24 mmol), N,N-bis(4-tert-butylphenyl)amine (272 mg, 0.97
mmol), palladium(II)acetate (13 mg, 0.06 mmol), BINAP (54 mg, 0.09
mmol) and NaH (23 mg, 0.97 mmol) were put into a Schlenk tube. The
compounds were heated under vacuum for 10 min. Anhydrous toluene
(24 mL) was added and the solution was subjected to three freeze-pump-
thaw cycles before it was released to argon. The reaction mixture was
heated to 110 °C. The reaction was monitored by TLC and quenched by
pouring into water after full consumption of the starting material. The
2
3 2
)
(
silica gel) using CH
from CHCl /CH OH gave purple crystals (280 mg, 0.30 mmol, 73%).
M.p.: 203-204 °C. R
MHz, CDCl , 25 °C): δ = 10.18 (s, 1H, Hmeso), 9.91 (d, J = 4.4 Hz, 1H, H
.84 (d, J = 4.4 Hz, 1H, H ), 9.42 (d, J = 4.4 Hz, 1H, H ), 9.32 (d, J = 4.4
), 9.05-9.08 (m, 2H, H ), 8.94-8.98 (m, 2H, H ), 8.05-8.06 (m,
) and 1.45-
, 25 °C): δ =
2 2
Cl :n-hexane (1:3, v/v) as eluent. Recrystallization
3
3
1
f
= 0.36 (n-hexane:CH
2
Cl
2
, 2:1, v/v). H NMR (400
),
3
β
9
β
β
Hz, 1H, H
β
β
β
product was extracted with CH
(3 × 100 mL) and NaCl (3 × 100 mL) and dried over MgSO
were removed in vacuo. The reaction mixture was filtered through a plug
of silica using CH Cl as eluent. Purification by column chromatography
using CH Cl /hexane (1:2, v/v) gave the desired porphyrin (100 mg, 0.10
2
Cl
2
(3 × 100 mL), washed with NaHCO
3
4
1
1
1
1
1
H, Ar-o-CH), 7.80 (s, 2H, Ar-p-CH), 1.53 (s, 36H, t-butyl-CH
.48 ppm (m, 21H, SiCH(CH ) ). C NMR (100 MHz, CDCl
3 3 3
3
4
. The solvents
13
52.7, 152.6, 150.3, 150.1, 150.0, 149.8, 149.6, 148.6, 148.5, 141.5,
41.4, 133.3, 133.2, 132.5, 132.4, 132.1, 131.6, 131.4, 130.8, 129.6,
29.4, 123.8, 121.0, 120.9, 109.4, 106.5, 99.5, 97.5, 35.0, 31.7, 19.2 and
2
2
2
2
mmol, 40%). Porphyrin 17a was also synthesized using general
procedure E. Bromoporphyrin 9a (50 mg, 0.06 mmol), N,N-bis(4-tert-
2 2
1.9 ppm. UV/Vis (CH Cl ): λmax (log ε) = 426 (5.78), 557 (4.29), 595 nm
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
butylphenyl)amine (67 mg, 0.24 mmol), palladium(II)acetate (0.7 mg, 3
(54 mg, 0.30 mmol) were added and the solution stirred until TLC
analysis indicated complete consumption of the starting material.
Acetone (5 mL) was added to quench the reaction. The product was
µmol), BINAP (2 mg, 3 µmol) and Cs
yielding porphyrin 17a (15 mg, 0.02 mmol, 24%). M.p.: 254-255 °C. R
2 3
CO (78 mg, 0.24 mmol) were used
f
=
1
0
1
9
4
.45 (hexane/ CH
H, Hmeso), 9.49 (d, J = 4.61 Hz, 1H, H
.33 (d, J = 4.61 Hz, 1H, H ), 9.30 (d, J = 4.61 Hz, 1H, H
.61 Hz, 1H, H ), 8.99 (d, J = 4.61 Hz, 1H, H ), 8.95 (d, J = 4.61 Hz, 1H,
), 8.93 (d, J = 4.61 Hz, 1H, H ), 8.09 (s, 2H, Ar-o-CH), 8.04 (s, 2H, Ar-
o-CH), 7.80 (s, 1H, Ar-p-CH), 7.76 (s, 1H, Ar-p-CH), 7.27 (d, J = 8.09 Hz,
2
Cl
2
2:1, v/v). H NMR (600 MHz, CDCl
), 9.40 (d, J = 4.61 Hz, 1H, H
), 9.08 (d, J =
3
): δ = 10.12 (s,
purified by column chromatography (silica gel) using n-hexane:CH
(2:1, v/v) as eluent. Recrystallization (CHCl /CH OH) gave near
quantitative yield of purple crystals (199 mg, 0.14 mmol, 95%). M.p.: 79-
2 2
Cl
β
β
),
3
3
β
β
1
β
β
82 °C. R
25 °C): δ = 9.59 (d, J = 4.5 Hz, 1H, H
(d, J = 4.4 Hz, 1H, H ), 9.19 (d, J = 4.4 Hz, 1H, H
1H, H ), 8.69-8.70 (m, 3H, H ), 7.58-7.67 (m, 2H, Ar-p-CH), 7.20 (d, J =
8.9 Hz, 4H, N-Ar-o-CH), 7.12 (d, J= 8.9 Hz, 4H, N-Ar-m-CH), 6.90-6.96
(m, 4H, Ar-m-CH), 3.75-3.80 (m, 8H, OCH ), 1.22 (s, 18H, C(CH ),
0.87-0.98 (m, 8H, CH ), 0.67-0.77 (m, 8H, CH ) and 0.43-0.55 ppm (m,
). C NMR (150 MHz, CDCl /C N, 25 °C): δ = 159.9,
f
= 0.49 (n-hexane:CH
2
Cl
2
, 2:1, v/v). H NMR (400 MHz, CDCl
), 9.56 (d, J = 4.5 Hz, 1H, H ), 9.32
), 8.82 (d, J = 4.4 Hz,
3
,
H
β
β
β
β
β
β
4
H, N-Ar-CH), 7.18 (d, J = 8.09 Hz, 4H, N-Ar-CH), 1.55 (s, 16H, t-butyl-
β
β
13
CH
3
), 1.50 (s, 20H, t-butyl-CH
, 25 °C): δ = 153.0, 152.9, 150.6, 150.5, 150.3,
49.5, 149.3, 148.8, 148.7, 143.0, 141.8, 133.6, 133.1, 132.8, 132.4,
3
) and1.24 ppm (s, 18H, t-butyl-CH
3
).
C
NMR (100 MHz, CDCl
3
2
3 3
)
1
1
1
2
2
13
32.3, 131.6, 131.4, 130.6, 129.8, 129.7, 125.9, 123.0, 122.9, 122.0,
21.7, 121.0, 121.0, 105.8, 35.2, 35.2, 34.2, 31.9, 31.9 and 31.6 ppm.
44H, CH
2
/CH
3
3
5 5
D
132.4, 132.1, 131.8, 131.5, 131.4, 130.7, 130.3, 129.4, 126.0, 125.5,
125.1, 121.3, 117.6, 117.4, 105.4, 105.3, 68.5, 68.4, 31.9, 31.5, 31.4,
31.3, 29.6, 29.4, 28.7, 28.6, 28.5, 28.3, 25.1, 24.9, 22.7, 22.3, 14.1 and
UV/Vis (CH
HRMS (MALDI) m/z calcd. for
027.5493. MS (MALDI) m/z (%): 1027.55 (100) [M ], 1012.53 (49) [M-
CH ].
2 2
Cl ): λmax (log ε) = 410 (5.49), 556 (4.24), 606 nm (4.01).
+
68 77 5
C H N Zn (M ):1027.5470; found
+
1
2 2
13.9 ppm. UV/Vis (CH Cl ): λmax (log ε) = 418 (5.30), 565 (4.12), 615 nm
+
3
108 5 4
(3.84). HRMS (MALDI) m/z calcd. for C84H N O BrZn (M ): 1393.6876;
found 1393.6910.
[
10,15-Bis(2,6-dioctyloxyphenyl)-5-(N,N-bis(4-tert-
butylphenyl)amino)porphyrinato]zinc(II) 17b: Porphyrin 17b was
synthesized following general procedure D. Bromoporphyrin 9b (210 mg,
[15,20-Bis(3,5-di-tert-butylphenyl)-10-(4-
carbomethoxyphenylethynyl)-5-(N,N-bis(4-tert-
0
.19 mmol), N,N-bis(4-tert-butylphenyl)amine (214 mg, 0.76 mmol),
palladium(II) acetate (4 mg, 19 µmol), BINAP (25 mg, 38 µmol) and
Cs CO (246 mg, 0.76 mmol) were placed in an oven-dried Schlenk flask.
Anhydrous THF (20 mL) was used to dissolve the compounds.
Recrystallization (CHCl /MeOH) gave purple crystals (170 mg, 0.13 mmol,
8%). M.p.: 85-87 °C. R
400 MHz, CDCl , 25 °C): δ = 9.99 (s, 1H, Hmeso), 9.41 (d, J = 4.5 Hz, 1H,
), 9.28 (d, J = 4.5 Hz, 1H, H ), 9.23 (d, J = 4.5 Hz, 1H, H ), 9.21 (d, J =
), 8.92 (d, J = 4.5 Hz, 1H, H ), 8.78-8.80 (m, 3H, H ), 7.60-
butylphenyl)amino)porphyrinato]zinc(II) 19a: Porphyrin 19a was
synthesized according to general procedure G. Bromoporphyrin 18a (100
mg, 0.09 mmol), methyl 4-ethynylbenzoate (79 mg, 0.48 mmol),
2
3
PdCl
and DEA (2.6 mL) were used for this reaction. The resultant porphyrin
was recrystallized from MeOH/CH Cl (57 mg, 0.05 mmol, 53%). M.p.:
>300 °C. R = 0.41 (hexane/CH Cl , 2:1, v/v). H NMR (400 MHz, CDCl
δ = 9.72-9.77 (m, 2H, H ), 9.43 (d, J = 4.85 Hz, 1H, H
Hz, 1H, H ), 9.01 (d, J = 4.85 Hz, 1H, H
2 3 2
(PPh ) (7 mg, 0.01 mmol), CuI (6 mg, 0.03 mmol), DMF (9 mL)
3
1
6
(
H
4
7
8
f
= 0.27 (n-hexane:CH
2
Cl
2
, 2:1, v/v). H NMR
2
2
1
3
f
2
2
3
):
), 9.29 (d, J = 4.85
β
β
β
β
β
.5 Hz, 1H, H
β
β
β
β
β
β
), 8.83-8.88 (m, 3H, H ), 8.16 (d,
.68 (m, 2H, Ar-p-CH), 7.24 (d, J = 8.9 Hz, 4H, N-Ar-o-CH), 7.13 (d, J =
.9 Hz, 4H, N-Ar-m-CH), 6.93-6.99 (m, 4H, Ar-m-CH), 3.76-3.80 (m, 8H,
J = 8.07 Hz, 2H, alkynyl-Ar-CH), 8.05 (s, 2H, Ar-o-CH), 8.03 (d, J = 8.07
Hz, 2H, alkynyl-Ar-CH), 7.99 (s, 2H, Ar-o-CH), 7.81 (s, 1H, Ar-p-CH),
7.78 (s, 1H, Ar-p-CH), 7.26 (d, J = 8.42 Hz, 4H, N-Ar-CH), 7.20 (d, J =
OCH
2
), 1.23 (s, 18H, C(CH
3
)
3
), 0.86-0.96 (m, 8H, CH
2
), 0.67-0.75 (m, 8H,
13
CH ) and 0.37-0.55 ppm (m, 44H, CH
2
2 3
/CH ). C NMR (100 MHz, CDCl
3
,
8.42 Hz, 4H, N-Ar-CH), 3.96 (s, 3H, OCH
1.50 (s, 18 H, t-butyl-CH ) and 1.25 ppm (s, 18H, t-butyl-CH
(100 MHz, CDCl , 25 °C): δ = 166.8, 153.4, 152.6, 152.6, 151.6, 151.1,
3
), 1.55 (s, 18H, t-butyl-CH
3
),
13
2
1
1
3
5 °C): δ = 160.0, 151.9, 151.8, 151.6, 150.9, 150.8, 150.1, 149.8, 149.4,
48.3, 142.5, 131.9, 131.7, 131.6, 131.4, 131.1, 130.3, 130.2, 129.5,
25.5, 121.6, 121.3, 121.1, 112.9, 112.8, 105.0, 68.7, 68.6, 34.0, 31.4,
1.3, 28.7, 28.6, 28.5, 28.3, 25.1, 24.9, 22.2, 22.1, 13.8 and 13.7 ppm.
3
3
). C NMR
3
150.7, 150.3, 150.2, 149.7, 148.9, 148.8, 143.2, 141.4, 141.3, 133.9,
133.6, 132.7, 132.3, 131.9, 131.8, 131.4, 130.7, 130.6, 129.9, 129.7,
129.6, 129.3, 129.2, 129.1, 126.0, 124.7, 124.5, 123.7, 121.8, 121.2,
99.0, 95.9, 95.5, 52.4, 35.2, 35.2, 34.2, 31.9, 31.9 and 31.6 ppm. UV/Vis
UV/Vis (CH
HRMS (MALDI) m/z calcd. for C84
315.7756.
2 2
Cl ): λmax (log ε) = 410 (5.08), 555 (3.98), 600 nm (3.52).
+
H
109 5 4
N O Zn (M ): 1315.7771; found
1
(CH
MALDI) m/z calcd. forC78
MS (MALDI) m/z (%): 1185.55 (100) [M ], 1170.54 (14) [M-CH
2 2
Cl ): λmax (log ε) = 438 (4.75), 579 (3.49), 631 nm (3.64). HRMS
+
(
83 5 2
H N O Zn (M ): 1185.5838; found 1185.5842.
+
3
].
[
15,20-Bis(3,5-di-tert-butylphenyl)-5-bromo-10-(N,N-bis(4-tert-
butylphenyl)amino)porphyrinato]zinc(II) 18a: Porphyrin 18a was
synthesized in accordance to general procedure F. Porphyrin 17a (120
mg, 0.12 mmol), NBS (31 mg, 0.18 mmol) and pyridine (0.3 mL) were
[15,20-Bis(3,5-di-tert-butylphenyl)-10-(4-carboxyphenylethynyl)-5-
(N,N-bis(4-tert-butylphenyl)amino)porphyrinato]zinc(II) 20a: 20a was
synthesized in accordance to general procedure H. Porphyrin 19a (64 mg,
0.0539 mmol), NaOH (760 mg, 19 mmol), THF (9.5 mL) and MeOH (9.5
dissolved in CHCl
MeOH/CH Cl yielded green crystals (100 mg, 0.09 mmol, 77%). M.p.:
300 °C. R
3
(25 mL) for this reaction. Recrystallization from
2
2
1
>
f
= 0.43 (hexane/ CH
): δ = 9.69 (d, J = 4.99 Hz, 1H, H
), 9.30 (d, J = 4.99 Hz, 1H, H
2
Cl
2
, 2:1, v/v). H NMR (600 MHz,
mL) were used. Recrystallization from MeOH/ CH
2
Cl
2
yielded a dark
= 0.21 (CH Cl
): δ = 9.76 (d, J = 4.38 Hz, 1H,
), 9.44 (d, J = 4.38 Hz, 1H, H ), 9.29 (d, J
), 9.01 (d, J = 4.38 Hz, 1H, H ), 8.82-8.88 (m, 3H, H ),
CDCl
3
β
), 9.66 (d, J = 4.99 Hz, 1H, H
β
),
green solid (60 mg, 0.05 mmol, 95%). M.p.: >300 °C. R
f
2
2
+
1
9
4
8
.40 (d, J = 4.99 Hz, 1H, H
.99 Hz, 1H, H ), 8.86-8.88 (m, 2H, H
β
β
), 8.96 (d, J =
drop of MeOH). H NMR (400 MHz, CDCl
), 9.73 (d, J = 4.38 Hz, 1H, H
= 4.38 Hz, 1H, H
3
β
β
), 8.84 (d, J = 4.99 Hz, 1H, H
β
),
H
β
β
β
.03 (s, 2H, Ar-o-CH), 7.98 (s, 2H, Ar-o-CH), 7.79 (s, 1H, Ar-p-CH), 7.75
β
β
β
(
s, 1H, Ar-p-CH), 7.23 (d, J = 8.09 Hz, 4H, N-Ar-CH), 7.17 (d, J = 8.09 Hz,
8.22 (d, J = 8.37 Hz, 2H, alkynyl-Ar-CH), 8.06 (s, 2H, Ar-o-CH), 8.05 (d, J
= 8.07 Hz, 2H, alkynyl-Ar-CH), 8.00 (s, 2H, Ar-o-CH), 7.82 (s, 1H, Ar-p-
CH), 7.76 (s, 1H, Ar-p-CH), 7.28 (d, J = 8.54 Hz, 4H, N-Ar-CH), 7.20 (d, J
4
1
1
1
1
3
H, N-Ar-CH), 1.53 (s, 20H, t-butyl-CH
3
), 1.49 (s, 16H, t-butyl-CH
3
) and
13
3
.25 ppm (s, 18H, t-butyl-CH ). C NMR (100 MHz, CDCl , 25 °C): δ =
3
53.3, 151.1, 150.9, 150.3, 150.2, 149.9, 148.9, 148.8, 148.8, 143.1,
41.5, 141.4, 134.0, 133.9, 133.7, 132.7, 132.7, 132.0, 131.0, 129.7,
29.6, 126.0, 124.0, 122.9, 121.7, 121.2, 121.1, 115.9, 104.4, 35.2, 35.2,
= 8.54 Hz, 4H, N-Ar-CH), 1.55 (s, 18H, t-butyl-CH
3
), 1.50 (s, 18 H, t-
3
). C NMR (100 MHz, CDCl ,
13
butyl-CH
3
) and 1.26 ppm (s, 18H, t-butyl-CH
3
25 °C): δ = 169.3, 153.5, 152.7, 152.6, 151.6, 151.2, 150.7, 150.4, 150.2,
149.7, 148.9, 148.8, 143.3, 141.4, 141.4, 134.0, 133.6, 132.8, 132.3,
132.0, 131.8, 131.5, 130.7, 130.6, 130.6, 130.0, 129.8, 129.6, 128.2, 126,
124.8, 124.5, 123.8, 121.8, 121.2, 98.8, 97.1, 96.5, 95.5, 35.2, 35.2, 34.3,
2 2
4.2, 31.9, 31.9, 31.7 and 31.5 ppm. UV/Vis (CH Cl ): λmax (log ε) = 418
(
4.61), 450 (3.70), 564 (3.28), 616 nm (3.15). HRMS (MALDI) m/z calcd.
+
for C68
5
H76BrN Zn (M ): 1105.4576; found 1105.4548.
3
1.9, 31.9 and 31.6 ppm. UV/Vis (CH
2 2
Cl ): λmax (log ε) = 438 (4.78), 580
+
(
3.52), 631 nm (3.68). HRMS (MALDI) m/z calcd. for C77H N O Zn (M ):
81 5 2
[
15,20-Bis(2,6-dioctyloxyphenyl)-5-bromo-10-(N,N-bis(4-tert-
+
1
1
7
171.5682; found 1171.5698. MS (MALDI) m/z (%): 1171.55 (100) [M ],
156.54 (19) [M-CH ]; IR (ATR): ν = 2954, 2189, 1603, 1508, 1262, 795,
butylphenyl)amino)porphyrinato]zinc(II) 18b: Porphyrin 18b was
prepared by bromination of porphyrin 17b using general procedure F.
3
–1
65, 750 cm
.
Aminoporphyrin 17b (200 mg, 0.15 mmol) was dissolved in CHCl
3
(50
mL), purged with argon and cooled to 0 °C. Pyridine (0.50 mL) and NBS
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
[
(
(
15,20-Bis(2,6-dioctyloxyphenyl)-10-(4-carboxyphenylethynyl)-5-
N,N-bis(4-tert-butylphenyl)amino)porphyrinato]zinc(II) 20b: 18b
150 mg, 107 µmol), methyl 4-ethynylbenzoate (87 mg, 0.54 mmol),
added and the reaction was stirred for 20 min. In the end DDQ (575 mg,
0.77 mmol) was added and the reaction was stirred for 1 h at r.t.. The
crude product was purified by a filtration through silica using CH
followed by column chromatography with first 2 L of hexane and then
hexane/ CH Cl (5:1, v/v). Recrystallization from CHCl /MeOH gave the
pure compound as purple crystals (32 mg, 0.029 mmol, 57%). M.p.: 65-
2 2
Cl
2 3 2
PdCl (PPh ) (9 mg, 11 µmol) and CuI (6 mg, 33 µmol) were placed in an
oven-dried Schlenk flask and general procedure G was used. Anhydrous
DMF (10 mL) and diethyl amine (3 mL) were added. The reaction mixture
was filtered through a plug of silica using CH
chromatography (silica gel) using n-hexane:CH
2
2
3
1
2
Cl
2
as eluent before column
Cl (3:2, v/v) as eluent
67 °C. R
25 °C): δ = 10.08 (s, 1H, Hmeso), 9.28 (d, J = 4.63 Hz, 1H, H
= 4.63 Hz, 1H, H ), 9.06 (d, J = 4.63 Hz, 1H, H ), 8.90 (m, 2H, H
(d, J = 4.63 Hz, 1H, H ), 8.75 (s, 2 H, H ), 8.11 (d, J = 8.3 Hz, 2H, N-Ar-
CH), 7.65-7.71 (m, 2H, Ar-p-CH), 7.13 (d, J = 8.3 Hz, 2H, N-Ar-CH),
6.96-7.00 (m, 4, Ar-m-CH), 3.79 (m, 8H, OCH ), 3.25 (s, 6H, N-CH ),
0.96-0.37 (m, 60H, CH (CH ) and -2.79 ppm (s, 2H, NH). C NMR (100
MHz, CDCl , 25 °C): δ = 160.3, 150.0, 135.8, 130.7, 129.9, 129.8, 121.7,
f
= 0.36 (hexane/ CH
2
Cl
2
, 1:1, v/v). H NMR (400 MHz, CDCl
), 9.21 (d, J
), 8.80
3
,
2
2
β
gave a glossy purple solid (109 mg, 66%) which was deprotected directly
using general procedure H. The product was dissolved in anhydrous THF
β
β
β
β
β
(
13 mL). NaOH in methanol (2 M, 13 mL, 26 mmol) was added and the
solution was heated to 70 °C under argon for 16 h. The solvents were
removed in vacuo and water (700 mL) was added to give a green
solution. HCl (1 M, 26 mL) was added dropwise until the pH reached 5.
2
3
13
3
2 6
)
3
The green suspension was extracted with CH
combined organic phases were washed with brine (1 × 100 mL) before
drying over MgSO . The solvents were removed and the product was
purified by column chromatography (silica gel) using CH Cl :CH OH
19:1, v/v) as eluent to give a glossy purple solid (98 mg, 67 µmol, 96%).
Analytical samples were obtained via recrystallization (CHCl /MeOH).
OH, 19:1, v/v). H NMR (400 MHz,
, 25 °C): δ = 9.66 (d, J = 4.5 Hz, 1H, H ), 9.63 (d, J = 4.4 Hz, 1H,
), 9.36 (d, J = 4.5 Hz, 1H, H ), 9.16 (d, J = 4.5 Hz, 1H, H ), 8.86 (d, J =
.4 Hz, 1H, H ), 8.68 (br s, 3H, H ), 8.07 (d, J = 7.5 Hz, 2H, alkynyl-Ar-m-
2
Cl
2
(3 × 100 mL). The
120.9, 119.7, 112.3, 111.0, 111.0, 105.7, 105.5, 103.9, 68.9, 68.8, 40.9,
31.5, 31.5, 28.8, 28.8, 28.7, 28.7, 28.6, 25.3, 22.4 and 14.0 ppm. UV/Vis
4
2 2
(CH Cl ): λmax (log ε) = 417 (5.58), 513 (4.43), 551 (4.12), 588 (3.99), 646
+
2
2
3
95 5 4
nm (3.62).HRMS (MALDI) m/z calcd. for C72H N O (M ): 1093.7384;
(
found 1093.7384.
3
1
M.p 142-145 °C. R
CDCl
H
4
f 2 2 3
= 0.19 (CH Cl :CH
1
5,20-Bis(3,5-di-tert-butylphenyl)-5-bromo-10-(N,N-
3
β
dimethylaniline)porphyrin 22a: The title compound was synthesized in
accordance with general procedure F. Porphyrin 21a (89 mg, 0.11 mmol),
β
β
β
β
β
NBS (18 mg, 0.10 mmol) were dissolved in CHCl
Recrystallization from CHCl /MeOH gave purple crystals in good yield
89 mg, 0.10 mmol, 91%). M.p.: 259-260 °C. R = 0.50 (hexane/ CH Cl
, 25 °C): δ = 9.66 (d, J = 4.86 Hz, 2H,
), 8.89-8.95 (m, 2H, H ), 8.80-8.85 (m,
), 8.07 (d, J = 8.06 Hz, 2H, N-Ar-CH), 8.03 (m, 4H, Ar-o-CH), 7.79
d, 2H, J = 8.22 Hz, Ar-p-CH), 7.12 (d, J = 8.06 Hz, 2H, N-Ar-CH), 3.25 (s,
H, N-CH ), 3.13 (s, 1H, N-CH ), 1.53 (s, 18H, t-butyl-CH ), 1.51 (s, 18H,
t-butyl-CH ), -2.64 (s, 1.6H, NH) and -2.71 ppm (s, 0.4H, NH). C NMR
100 MHz, CDCl , 25 °C): δ = 150.2, 149.0, 148.9, 141.2, 141.1, 135.9,
30.1, 129.9, 129.9, 121.8, 121.4, 121.3, 121.2, 110.9, 102.5, 44.7, 40.9,
5.2, 35.2, 31.9 and 31.8 ppm. UV/Vis (CH Cl ): λmax (log ε) = 303 (3.76),
23 (4.93), 522 (3.67), 562 (3.57), 600 (3.14), 658 nm (3.14). HRMS
(30 mL).
3
CH), 7.93 (d, J = 7.5 Hz, 2H, alkynyl-Ar-o-CH), 7.59-7.66 (m, 2H, Ar-p-
CH), 7.22 (d, J = 8.9 Hz, 4H, N-Ar-o-CH), 7.13 (d, J = 8.6 Hz, 4H, N-Ar-
3
(
1
H
3
f
2
2
,
m-CH), 6.91-6.98 (m, 4H, Ar-m-CH), 3.77-3.80 (m, 8H, OCH
2
), 1.22 (s,
), 0.71-0.74 (m, 8H, CH ) and 0.44-
5 5
). C NMR (150 MHz, CDCl /C D N, 25 °C):
1
:1, v/v). H NMR (400 MHz, CDCl
), 9.01 (d, J = 4.81 Hz, 1H, H
H, H
3
1
0
8H, C(CH
.54 ppm (m, 44H, CH
3
)
3
), 0.91-1.00 (m, 8H, CH
2
2
β
β
β
13
2
/CH
3
3
β
δ =160.0, 159.8, 152.0, 151.8, 151.3, 151.2, 150.7, 150.6, 150.4, 150.1,
(
1
1
1
9
2
49.7, 142.3, 131.9, 131.7, 131.3, 130.9, 130.8, 130.6, 130.3, 130.2,
30.0, 129.9, 129.8, 129.7, 129.4, 129.2, 126.0, 125.5, 125.4, 122.3,
21.8, 121.7, 121.3, 121.2, 117.3, 114.5, 114.2, 106.6, 105.3, 97.2, 96.9,
4.4, 68.5, 68.4, 34.0, 31.9, 31.5, 31.4, 29.7, 29.6, 29.3, 29.2, 28.7, 28.6,
8.6, 28.5, 28.3, 25.1, 24.9, 22.7, 22.3, 14.1 and 13.9 ppm. UV/Vis
5
3
3
3
13
3
(
3
1
3
4
2
2
(
(
CH
MALDI) m/z calcd. for
2 2
Cl ): λmax (log ε) = 440 (5.31), 580 (4.17), 630 nm (4.23). HRMS
+
C H N
93 113 5
6
O Zn (M ): 1459.7982; found
+
(
(
62 5
MALDI) m/z calcd. for C56H N Br (M ): 883.4189; found 883.4227. MS
MALDI) m/z (%): 885.38 (100) [M ], 870.37 (16) [M –CH
1
1
459.7936; IR (ATR): ν = 2923, 2852, 2324, 1590, 1509, 1454, 1260,
+
+
3
].
–1
095, 1001, 793, 766, 750, 714 cm
.
[
15,20-Bis(3,5-di-tert-butylphenyl)-5-bromo-10-(N,N-
1
2
0,15-Bis(3,5-di-tert-butylphenyl)-5-(N,N-dimethylaniline)porphyrin
1a: Porphyrin 21a was synthesized in accordance with general
dimethylaniline)porphyrinato]zinc(II) 23a: Porphyrin 23a was obtained
using general procedure C. Porphyrin 22a (127 mg, 0.14 mmol) and
procedure I. Porphyrin 7a (223 mg, 0.29 mmol), 4-bromo-dimethylaniline
699 mg, 3.49 mmol), n-BuLi (2.2 mL, 3.49 mmol, 1.6 in n-
hexane),diethylether (8mL) and THF (40 mL) were used.
Recrystallization from CHCl /MeOH gave purple crystals (89 mg, 0.11
mmol, 38%). M.p.: 269-270 °C. R
NMR (400 MHz, CDCl , 25 °C): δ = 10.19 (s, 1H, Hmeso), 9.34 (d, J = 4.62
Hz, 1H, H ), 9.32 (d, J = 4.62 Hz, 1H, H ), 9.13 (d, J = 4.62 Hz, 1H, H ),
), 9.01 (d, J = 4.62 Hz, 1H, H ), 8.95 (d, J =
), 8.89 (d, J = 4.62 Hz, 1H,
Zn(OAc)
Recrystallization from CHCl
mmol, 86%). M.p.: 128-129 °C. R
NMR (400 MHz, CDCl , 25 °C): δ = 9.74-9.80 (m, 2H, H
H, H ), 8.92-8.98 (m, 4H, H ), 8.06 (s, 2H, Ar-o-CH), 8.04 (s, 2H, Ar-o-
CH), 8.00 (bs, 2H, N-Ar-CH), 7.79 (d, 2H, J = 10.37 Hz, Ar-p-CH), 6.83
2
(95 mg, 0.43 mmol) were dissolved in CHCl
3
(50 mL).
(
M
3
/MeOH gave purple crystals (117 mg, 0.12
1
f
= 0.14 (hexane/ CH
2
Cl
2
, 2:1, v/v). H
3
), 9.03-9.08 (m,
3
β
1
f
2 2
= 0.30 (hexane/ CH Cl , 1:1, v/v). H
2
β
β
3
β
β
β
(
bs, 2H, N-Ar-CH), 3.13 (s, 1H, N-CH
), 2.82 (s, 5H, N-CH
), 1.53 (s, 18H,
). C NMR (100 MHz,
3
3
13
9
4
.05 (d, J = 4.62 Hz, 1H, H
β
β
t-butyl-CH
CDCl
3
) and 1.50 ppm (s, 18H, t-butyl-CH
3
.62 Hz, 1H, H
β
), 8.92 (d, J = 4.62 Hz, 1H, H
β
3
, 25 °C): δ = 151.0, 150.9, 150.9, 149.7, 148.8, 148.7, 141.9, 141.8,
41.7, 141.7, 139.6, 138.3, 135.3, 133.6, 133.0, 132.8, 132.7, 132.6,
29.8, 129.8, 121.1, 121.0, 111.0, 104.2, 44.8, 41.0, 35.2 and 31.9 ppm.
Cl ): λmax (log ε) = 425 (4.99), 556 (3.78), 598 nm (3.44).
HRMS (MALDI) m/z calcd. for C56
45.3344. MS (MALDI) m/z (%): 947.36 (100) [M ], 851.44 (12) [M –
CH Br].
H
β
), 8.14 (d, J = 8.3 Hz, 2H, N-Ar-CH), 8.11 (d, J = 2.03 Hz, 2H, Ar-o-CH),
.07 (d, J = 2.03 Hz, 2H, Ar-o-CH), 7.79-8.11 (m, 2H, Ar-p-CH), 7.15 (d, J
8.3 Hz, 2H, N-Ar-CH), 3.26 (s, 6H, NCH ), 1.55 (s, 18H, t-butyl-CH ),
.52 (s, 18H, t-butyl-CH ) and -2.88 ppm (s, 2H, NH). C NMR (100 MHz,
, 25 °C): δ =150.2, 149.1, 148.7, 142.0, 141.1, 136.1, 131.8, 130.9,
30.0, 122.0, 121.2, 121.1, 120.7, 120.6, 111.2, 104.5, 41.0, 35.3, 35.2,
2.9, 32.0 and 31.2 ppm. UV/Vis (CH Cl ): λmax (log ε) = 415 (5.09), 515
1
1
8
=
1
3
3
UV/Vis (CH
2
2
13
+
3
H
5
60BrN Zn (M ): 945.3324; found
CDCl
3
+
+
9
1
3
4
2
2
(
3.92), 556 (3.76), 590 (3.55), 646 nm (3.41). HRMS (MALDI) m/z calcd.
[
15,20-Bis(3,5-di-tert-butylphenyl)-10-(4-
+
63 5
for C56H N (M ): 805.5083; found 805.5056. MS (MALDI) m/z (%):
8
carbomethoxyphenylethynyl)-5-(N,N-
dimethylaniline)porphyrinato]zinc(II) 24a: The target compound was
obtained using general procedure G. Porphyrin 23a (94 mg, 0.10 mmol),
+
+
3
05.46 (100) [M ], 790.45 (39) [M –CH ].
1
2
0,15-Bis(2,6-dioctyloxyphenyl)-5-(N,N-dimethylaniline)porphyrin
1b: 4-Bromo-dimethylaniline (1024 mg, 5.12 mmol) was dissolved in
methyl 4-ethynylbenzoate (81 mg, 0.50 mmol), PdCl
mmol), CuI (6 mg, 0.03 mmol), DMF (9.3 mL) and DEA (2.75 mL) were
used for this reaction. Recrystallization from CHCl /MeOH gave dark
purple crystals (64 mg, 0.06 mmol, 63%). M.p.: >300 °C. R
2 3 2
(PPh ) (7 mg, 0.01
diethylether (26 mL) and cooled to -70°C and n-BuLi (2.1 mL, 5.12 mmol,
.6 M in n-hexane) was added drop-wise over 45 min. The mixture of
3
1
f
= 0.47
porphyrin 7b (50 mg, 0.05 mmol) in THF (10 mL) was cooled to –70°C
and the organolithium reagent was added drop-wise over 20 min. The
cold bath was removed and the reaction mixture was stirred for 1.5 h at
1
(
2
CH Cl
2
). H NMR (400 MHz, CDCl
3
, 25 °C): δ = 9.83 (d, J = 4.59 Hz, 1H,
H
β
), 9.80 (d, J = 4.59 Hz, 1H, H
β
β
), 9.10 (bs, 1H, H ), 9.06 (d, J = 4.61 Hz,
1
8
H, H
β
), 8.90-8.97 (m, 4H, H ), 8.15 (d, J = 8.17 Hz, 2H, alkynyl-Ar-CH),
β
4
r.t. Once all the starting material was consumed NH CL (5 mL) was
.08 (d, 2H, J = 1.86 Hz, Ar-o-CH), 8.07 (bs, 2H, N-Ar-CH), 8.04 (d, 2H, J
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
=
1.86 Hz, Ar-o-CH), 8.01 (d, J = 8.26 Hz, 2H, alkynyl-Ar-CH), 7.80 (s,
H, Ar-p-CH), 7.77 (s, 1H, Ar-p-CH), 6.85 (bs, 2H, N-Ar-CH), 3.95 (s, 3H,
MeOH (10 mL) were used to yield a purple solid (890 mg, 0.80 mmol,
1
87%). M.p.: 119 °C. R
(CH Cl ): λmax (log ε) = 417 (4.41), 546 nm (3.07). HRMS (MALDI): m/z
calcd. for C64
were as reported before.
f
2 2
= 0.75 (n-hexane : CH Cl , 2:1, v/v). UV/Vis
3
OCH ), 2.87 (s, 4H, N-CH
3
), 2.75 (s, 2H, N-CH
3
), 1.53 (s, 18H, t-butyl-
2
2
13
+
CH ) and 1.49 ppm (s, 18H, t-butyl-CH
3
3
). C NMR (100 MHz, CDCl
3
,
4 4
H83BrN O Zn (M ): 1114.4889; found 1114.4943. Other data
[8c]
2
1
1
1
5 °C): δ = 166.8, 162.5, 152.4, 152.3, 151.4, 151.0, 150.5, 150.3, 150.2,
49.6, 148.8, 148.6, 141.8, 141.7, 135.2, 133.5, 133.4, 132.6, 132.6,
32.3, 132.1, 131.4, 130.5, 130.3, 129.9, 129.7, 129.3, 129.2, 124.8,
23.5, 122.9, 121.0, 111.3, 98.5, 96.6, 95.3, 52.4, 40.9, 35.2, 35.1, 31.9
[
10,20-Bis(3,5-di-tert-butylphenyl)-5-(N,N-bis(4-(tert-
butylphenyl)amino)porphyrinato]zinc(II) 29a: [5-Bromo-10,20-bis(3,5-
di-tert-butyl)phenylporphyrinato]zinc(II) 28a (400 mg, 0.48 mmol) was
dissolved in DMF (10 mL) in a 20 mL microwave vial. Bis(4-(tert-
and 31.8 ppm. UV/Vis (CH
nm (3.80). HRMS (MALDI) m/z calcd. for C66
found 1025.4580. MS (MALDI) m/z (%): 1025.44 (100) [M ], 1010.45 (12)
2 2
Cl ): λmax (log ε) = 443 (4.88), 570 (3.56), 619
+
67 5 2
H N O Zn (M ): 1025.4586;
+
butyl)phenyl)amine (543 mg, 1.93 mmol), Pd(OAc)
BINAP (15 mg, 24 µmol) and Cs CO (629 mg, 1.93 mmol) were added
according to general procedure E. The crude residue was redissolved in
CH Cl : n-hexane, (25 mL, 1:3, v/v) and filtered through a short plug of
silica using CH Cl : hexanes, (25 mL, 1:3, v/v) as eluent. The brown/red
2
(6 mg, 24 µmol),
+
[
3
M –CH ].
2
3
[
(
15,20-Bis(3,5-di-tert-butylphenyl)-10-(4-carboxyphenylethynyl)-5-
N,N-dimethylaniline)porphyrinato]zinc(II) 25a: The title compound
2
2
2
2
was synthesized in accordance to general procedure H. Porphyrin 24a
40 mg, 0.04 mmol), NaOH (550 mg, 13.74 mmol), THF (6.9 mL) and
MeOH (6.9 mL) were used. Recrystallization yielded a dark green solid
33 mg, 0.03 mmol, 84%). M.p.: 108-110 °C. R = 0.14 (CH Cl + drop
, 25 °C): δ = 9.79-9.84 (m, 2H, H ),
), 9.06 (d, J = 4.67 Hz, 1H, H ), 8.89-8.97 (m,
), 8.23 (d, J = 8.01 Hz, 2H, alkynyl-Ar-CH), 8.11 (d, J = 8.01 Hz,
fraction was isolated (other faint fractions were discarded) and the
solvents were removed in vacuo. The residue was subjected to column
(
chromatography (CH
in color) containing the desired product. The solvents were removed in
vacuo and the purple residue was recrystallized from CH Cl /hexane to
yield a purple solid (180 mg, 0.18 mmol, 36%). M.p.: >300 °C. R = 0.32
, 50:1,
), 9.36 (d, J = 4.5
), 8.96 (d, J = 4.5 Hz, 2H, H ),
2 2
Cl : n-hexane, 1:3, v/v), with the main fraction (red
(
f
2
2
1
MeOH). H NMR (400 MHz, CDCl
3
β
2
2
9
4
2
1
2
.13 (d, J = 4.67 Hz, 1H, H
H, H
β
β
f
1
β
(CH
v/v): δ = 10.21 (s, 1H, Hmeso), 9.40 (d, J = 4.5 Hz, 2H, H
Hz, 2H, H ), 9.07 (d, J = 4.5 Hz, 2H, H
2 2 3 5
Cl :n-hexane, 1:3, v/v). H NMR (400 MHz, CDCl +pyridine-d
H, alkynyl-Ar-CH), 8.07 (d, 2H, J = 1.89 Hz, Ar-o-CH), 8.03 (d, 2H, J =
.86 Hz, Ar-o-CH), 7.80 (s, 1H, Ar-p-CH), 7.77 (s, 1H, Ar-p-CH), 7.37 (bs,
β
β
β
β
H, N-Ar-CH)
,
7.02 (bs, 2H, N-Ar-CH),3.09 (s, 6H, N-CH
3
),1.55 (s, 18H, t-
8.07-8.09 (m, 4H, Ar-o-CH), 7.78-7.80 (m, 2H, Ar-p-CH), 7.24 (d, J = 8.8
Hz, 4H, N-Ar-CH), 7.15 (d, J = 8.8 Hz, 4H, N-Ar-CH), 1.53 (s, 36H, t-
13
3
butyl-CH ) and1.51 ppm (s, 18H, t-butyl-CH
3
). C NMR (100 MHz, CDCl ,
3
13
2
1
1
9
5 °C): δ = 152.5, 152.4, 151.5, 151.1, 150.6, 150.3, 150.2, 149.8, 148.8,
48.7, 141.8, 141.6, 135.3, 133.6, 133.5, 132.7, 132.6, 132.3, 132.1,
31.5, 130.6, 130.4, 130.2, 129.8, 129.7, 124.9, 123.6, 121.1, 111.2,
3 3
butyl-CH ) and 1.21 ppm (s, 18H, t-butyl-CH ). C NMR (100 MHz,
CDCl3, 25 °C): δ = 152.6, 150.9, 150.2, 149.9, 149.9, 148.8, 142.9, 141.5,
133.5, 133.0, 131.7, 130.9, 129.9, 125.9, 122.6, 122.0, 121.6, 121.0,
8.5, 95.4, 40.9, 35.2, 35.1, 31.9 and 31.9 ppm. UV/Vis (CH
2
Cl
2
): λmax
2 2
106.6, 35.2, 34.2, 31.9 and 31.5 ppm. UV/Vis (CH Cl ): λmax (log ε) = 411
(
log ε) = 443 (3.81), 568 (2.58), 619 nm (2.73). HRMS (MALDI) m/z calcd.
(5.64), 453 (4.81), 556 (4.39), 604 nm (3.97).HRMS (MALDI): m/zcalcd.
+
+
for C65
(
2
H
65
N
5
O
2
Zn (M ): 1011.4430; found 1011.4462. MS (MALDI) m/z
77 5
for C68H N Zn (M ): 1027.5470; found 1027.5461.
+
+
3
%): 1011.43 (100) [M ], 996.41 (11) [M –CH ]; IR (ATR): ν = 2953, 2922,
–1
852, 2188, 1688, 1601, 998, 796, 767, 714 cm
.
[
10,15-Bis(2,6-dioctyloxyphenyl)-5-(N,N-bis(4-tert-
butylphenyl)amino)porphyrinato]zinc(II) 29b: Synthesized as per
general procedure D using bromoporphyrin 28b (250 mg, 0.24 mmol),
[
44]
[8c]
1
0,20-Bis(3,5-di-tert-butylphenyl)-5-bromoporphyrin
27a:
Porphyrin 27a was synthesized in accordance with general procedure B.
,15-Bis(3,5-di-tert-butylphenyl)porphyrin 26a (1.0 g, 1.46 mmol), NBS
0.23 g, 1.29 mmol) and pyridine (0.5 mL) were used. The reaction was
monitored by TLC. The product was recrystallized from CH Cl /MeOH to
yield purple crystals (680 g, 0.89 mmol, 60%). M.p.: >300 °C. R
N,N-bis(4-tert-butylphenyl)amine (268 mg, 95 mmol), palladium(II)acetate
5
(
(5 mg, 24 µmol), BINAP (30 mg, 48 µmol) and Cs
mmol). Purification by column chromatography (silica gel) using n-
hexane: CH Cl (2:1, v/v) as eluent and removal of solvents followed by
recrystallization (CHCl /CH OH) gave purple crystals (228 mg, 0.17
mmol, 72%). M.p 81-83 °C. R
NMR (400 MHz, CDCl , 25 °C): δ = 10.03 (s, 1H, Hmeso), 9.28 (d, J = 4.6
Hz, 2H, H ), 9.22 (d, J = 4.6 Hz, 2H, H ), 8.94 (d, J = 4.6 Hz, 2H, H ),
8.81 (d, J = 4.6 Hz, 2H, H ), 7.65 (t, J = 8.6 Hz, 2H, Ar-p-CH), 7.22 (d, J =
8.8 Hz, 4H, N-o-Ar-CH), 7.09 (d, J = 8.8 Hz, 4H, N-Ar-m-CH), 6.96 (d, J =
2 3
CO (155 mg, 0.48
2
2
2
2
f
= 0.76
3
3
1
1
(
n-hexane : CH
meso), 9.71 (d, J = 4.88 Hz, 2H, H
J = 4.76 Hz, 4H, H ), 8.07 (d, J = 1.76 Hz, 4H, Ar-o-CH), 7.83 (t, J = 1.80
Hz, 2H, Ar-p-CH), 1.55 (s, 36H, t-butyl-CH ) and -2.93 ppm (s, 2H, NH).
(M ):764.3454; found 764.3469.
2
Cl
2
1:5, v/v). H NMR (400 MHz, CHCl
3
): δ = 10.16 (s, 1H,
f 2 2
= 0.28 (n-hexane: CH Cl , 3:2, v/v). H
H
β
β
), 9.28 (d, J = 4.44 Hz, 2H, H ), 9.00 (t,
3
β
β
β
β
3
β
+
HRMS (ESI) m/z calcd. for C48H53BrN
4
8
2
.6 Hz, 4H, Ar-m-CH), 3.81 (t, J = 6.5 Hz, 8H, OCH ), 1.21 (s, 18H, t-
[
8c]
), 0.85-0.95 (m, 8H, CH ), 0.76-0.80 (m, 8H, CH ) and 0.42-
butyl-CH
3
2
2
1
2
0,20-Bis(2,6-dioctyloxyphenyl)-5-bromoporphyrin 27b:
7b was synthesized in accordance with general procedure B. 5,15-
(200
mL), NBS (0.38 g, 1.85 mmol), pyridine (0.5 mL) were used. The product
was obtained as a purple solid (1.8 g, 1.70 mmol, 43%). M.p.: 98 °C; R
.86 (n-hexane : toluene, 3:1, v/v). UV/Vis (CH Cl ): λmax (log ε) = 416
5.65), 512 (4.34), 548 (3.73), 588 (3.80) nm. HRMS (ESI): m/z calcd. for
Porphyrin
13
0
=
1
2
4
2 3
.60 ppm (m, 44H, CH /CH ). C NMR (100 MHz, CDCl3, 25 °C): δ
159.9, 151.9, 150.8, 149.9, 149.4, 142.4, 132.0, 131.6, 131.1, 130.3,
29.6, 125.4, 121.4, 121.1, 112.7, 105.2, 105.0, 68.6, 33.9, 31.4, 31.3,
8.5, 28.4, 25.0, 22.2, 14.1 and 13.7 ppm. UV/Vis (CH
08 (5.30), 554 (4.18), 602 nm (3.55). HRMS (MALDI) m/z calcd. for
Bis(2,6-dioctyloxyphenyl)porphyrin 26b (2.0 g, 2.05 mmol), CHCl
3
2 2
Cl ): λmax (log ε) =
f
=
0
(
2
2
+
84 109 5 4
C H N O Zn (M ): 1315.7771; found 1315.7787.
+
48 54 4
C H N (M ):1053.5832; found 1053.5841. Other data were as reported
[8c]
before.
[5-N,N-Bis(4-(tert-butyl)phenylamino)-10,20-
diphenylporphyrinato]zinc(II) 29c:
[5-Bromo-10,20-
diphenylporphyrinato]zinc(II) (200 mg, 0.331 mmol) 28c was dissolved in
DMF (2.5 mL) in a 5 mL microwave vial. Bis(4-(tert-butyl)phenyl)amine
[
2
10,20-Bis(3,5-di-tert-butylphenyl)-5-bromoporphyrinato]zinc(II)
[44,45]
8a:
Porphyrin 28a was synthesized in accordance with general
(
372 mg, 1.322 mmol), Pd(OAc)
µmol) and Cs CO (431 mg, 1.32 mmol) were added according to general
procedure E. The crude residue was redissolved in CH Cl : hexanes,
25 mL, 1:3, v/v) and filtered through a short plug of silica using CH Cl
2
(4 mg, 17 µmol), BINAP (11 mg, 17
procedure C. 5-Bromo-10,20-bis(3,5-di-tert-butylphenyl)porphyrin 27a
720 mg, 0.94 mmol), Zn(OAc) (0.52 g, 2.82 mmol), MeOH (10 mL) and
CHCl (200 mL) were used. The product was obtained as a purple solid
615 mg, 0.74 mmol, 79%). M.p.: >300 °C. R = 0.58 (n-hexane : CH Cl
Zn (M ):826.2589; found
(
2
2
3
2
2
3
(
2
2
:
(
2
8
f
2
2
,
+
hexanes, (25 mL, 1:3, v/v) as eluent. The brown/red fraction was isolated
(other faint fractions were discarded) and the solvents were removed in
:1, v/v). HRMS (ESI) m/z calcd. for C48
H51BrN
4
[44,45]
26.2624. Other data were as reported before.
vacuo. The residue was subjected to column chromatography (CH
hexanes, 1:3, v/v), with the main fraction (red in colour) containing the
desired product and the purple residue was recrystallized from CH Cl
MeOH to yield purple crystals (120 mg, 0.15 mmol, 45%). Mp >300 °C. R
2 2
Cl :
[
2
10,20-Bis(2,6-dioctyloxyphenyl)-5-bromoporphyrinato]zinc(II)
8b: The title compound was synthesized in accordance with general
[8c]
2
2
/
f
procedure C. 5-Bromo-10,20-bis(2,6-dioctyloxyphenyl)porphyrin 27b
970 mg, 0.92 mmol), CHCl (200 mL), Zn(OAc) (0.51 g, 2.77mmol) and
1
=
2 2 3
0,75 (CH Cl : hexane 1:1 v/v + 1% MeOH). H NMR (400 MHz, CDCl
(
3
2
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
+
pyridine-d
5
, 50:1, v/v): δ = 10.06 (s, 1H, Hmeso), 9.26 (d, J = 4.5 Hz, 2H,
CH), 7.08 (d, J = 7.8 Hz, 4H, N-Ar-CH), 3.96 (s, 3H, N-CH
3
) and 1.48
13
H
4
(
β
), 9.24 (d, J = 4.5 Hz, 2H, H
.5 Hz, 2H, H ), 8.13-8.15 (m, 4H, Ph-H), 7.62-7.71 (m, 6H, Ph-H), 7.12
d, J = 8.9 Hz, 4H, N-Ar-CH), 7.04 (d, J = 8.9 Hz, 4H, N-Ar-CH) and 1.18
β
), 8.91 (d, J = 4.5 Hz, 2H, H
β
), 8.76 (d, J =
ppm (s, 54H, t-butyl-CH
3
). C NMR (150 MHz, CDCl
3
+ pyridine-d , 30:1,
5
β
v/v): δ = 167.1, 152.3, 152.2, 150.2, 150.1, 150.0, 149.7, 148.4, 142.6,
141.7, 133.1, 132.9, 131.1, 130.7, 130.0, 129.8, 129.7, 129.0, 125.6,
121.4, 120.7, 98.2, 95.0, 52.2, 35.0, 34.0, 31.7 and 31.4 ppm. UV/Vis
13
3 3 5
ppm (s, 18H, t-butyl-CH ). C NMR (150 MHz, CDCl + pyridine-d , 50:1,
v/v): δ = 152.3, 150.3, 149.8, 143.2, 142.4, 134.6, 132.6, 132.1, 131.4,
30.5, 127.1, 126.3, 125.5, 121.3, 119.8, 106.1, 34.0 and 31.4 ppm.
UV/Vis (CH Cl ): λmax (log ε) = 408 (5.18), 556 (3.89), 606 nm (3.51).
HRMS (MALDI): m/zcalcd. for
03.2980.
(MeOH): λmax (log ε) = 442 (5.00), 588 (3.94), 652 nm (4.36). HRMS
+
1
83 5
(MALDI): m/z calcd. for C78H N O
2
Zn (M ):1185.5838; found 1185.5844.
2
2
+
52 45 5
C H N Zn (M ): 803.2966; found
[
10,20-Bis(2,6-dioctyloxyphenyl)-5-(N,N-bis(4-tert-
8
butylphenyl)amino)-15-(4-
carbomethoxyphenylethynyl)porphyrinato]zinc(II) 31b: Porphyrin 31b
was synthesized according to general procedure G. Bromoporphyrin 30b
(150 mg, 0.11 mmol), methyl 4-ethynylbenzoate (87 mg, 0.54 mmol),
[
10,20-Bis(3,5-di-tert-butylphenyl)-15-(N,N-bis(4-tert-
butylphenyl)amino)-5-bromo-porphyrinato]zinc(II) 30a: Porphyrin 30a
was synthesized following general procedure F. [5-N,N-Bis(4-(tert-
butylphenyl)amino)-10,20-bis(3,5-di-tert-butyl)phenylporphyrinato]zinc(II)
2
0
at r.t. and monitored by TLC. The reaction was quenched with acetone
and filtered through a plug of silica using CH Cl . The solvent was
removed and the product was obtained in 93% yield (10 mg, 0.9 µmol,
PdCl
Column chromatography (silica gel) using n-hexane: CH
eluent gave a glossy purple solid (135 mg, 91 µmol, 83%). R
f
2
(PPh
3
)
2
(9 mg, 11 µmol) and CuI (6 mg, 33 µmol) were used.
Cl (3:2, v/v) as
= 0.16 (n-
, 25 °C): δ = 9.65 (d,
), 8.87 (d, J = 4.6 Hz, 2H,
), 8.20 (d,J = 8.3 Hz, 2H, alkynyl-Ar-m-CH),
2
2
9a (10 mg. 0.01 mmol) was dissolved in CHCl
3
(10 mL). NBS (1.70 mg,
1
.01 mmol) and pyridine (0.01 mL) were added. The reaction was stirred
hexane: CH
J = 4.6 Hz, 2H, H
), 8.69 (d, J= 4.6 Hz, 2H, H
β
2
Cl
2
, 3:2, v/v). H NMR (400 MHz, CDCl
3
β
), 9.18 (d, J = 4.6 Hz, 2H, H
β
2
2
H
β
8.02 (d, J= 8.3 Hz, 2H, alkynyl-Ar-o-CH), 7.64 (t, J = 8.6 Hz, 2H, Ar-p-
CH), 7.21 (d, J = 8.8 Hz, 4H, N-Ar-o-CH), 7.12 (d, J = 8.8 Hz, 4H, N-Ar-
1
9
3%). M.p.: >300 °C. R
MHz, CDCl ): δ = 9.72 (d, J = 4.5 Hz, 2H, H
), 8.97 (d, J = 4.5 Hz, 2H, H ), 8.87 (d, J = 4.5 Hz, 2H, H
m, 4H, Ar-o-CH), 7.79 (s, 2H, Ar-p-CH), 7.23 (d, J = 8.6 Hz, 4H, N-Ar-
CH), 7.16 (d, J = 8.6 Hz, 4H, N-Ar-CH), 1.52 (s, 36H, t-butyl-CH ) and
). C NMR (100 MHz, CDCl3, 25 °C): δ =
f
= 0.39 (CH
2
Cl
2
:n-hexane, 1:3, v/v). H NMR (400
), 9.33 (d, J = 4.5 Hz, 2H,
), 8.01-8.03
3
β
m-CH), 6.95 (d, J = 8.6 Hz, 4H, Ar-m-CH), 3.98 (s, 3H, OCH
= 6.4 Hz, 8H, OCH ), 1.21 (s, 18H, t-butyl-CH ), 0.94-1.01 (m, 8H, CH
0.74-0.80 (m, 8H, CH ) and 0.45-0.63 ppm (m, 44H, CH
3
), 3.82 (t, J
),
2 3
/CH ); C NMR
H
(
β
β
β
2
3
2
13
2
3
(100 MHz, CDCl3, 25 °C): δ = 166.8, 159.8, 152.0, 151.9, 150.5, 150.3,
149.9, 142.7, 132.2, 132.0, 131.2, 130.7, 130.1, 129.8, 129.4, 129.0,
125.5, 123.1, 121.5, 120.7, 114.5, 105.1, 98.1, 96.7, 94.5, 68.6, 52.2,
13
1
1
1
.22 ppm (s, 18H, t-butyl-CH
3
53.5, 151.4, 150.2, 150.1, 149.8, 148.9, 143.1, 141.3, 133.9, 133.6,
32.8, 131.2, 129.8, 125.9, 123.1, 121.7, 121.2, 105.2, 35.2, 34.2, 31.9
33.9, 31.3, 29.7, 28.6, 28.4, 25.1, 22.2 and 13.7 ppm; UV/Vis (CH
2
Cl
2
):
and 31.5 ppm. UV/Vis (CH
nm (3.98). HRMS (MALDI): m/z calcd. for C68
2
Cl
2
): λmax (log ε) = 419 (5.38), 566 (4.05), 620
λ
max (log ε) = 440 (5.18), 576 (3.95), 637 nm (4.25). HRMS (MALDI) m/z
+
+
H
76
5
N ZnBr (M ): 1105.4576;
115 5 6
calcd. for C94H N O Zn (M ): 1473.8139; found 1473.8097.
found 1105.4561.
[
10,20-Bis(2,6-dioctyloxyphenyl)-5-(N,N-bis(4-tert-
[
10,20-Bis(2,6-dioctyloxyphenyl)-15-(bis(4-tert-butylphenyl)amino)-5-
butylphenyl)amino)-15-(4-
bromo-porphyrinato]zinc(II) 30b: Synthesized using general procedure
F with porphyrin 29b (600 mg, 0.45 mmol), pyridine (0.50 mL) and NBS
carboxyphenylethynyl)porphyrinato]zinc(II) 32b: Methyl ester 31b
(100 mg, 68 µmol) was deprotected using general procedure H. NaOH in
methanol (2 M, 12 mL, 24 mmol) was added to a solution of porphyrin in
anhydrous THF (13 mL). The solvents were removed in vacuo and water
(600 mL) added to give a green solution. HCl (1 M, 24 mL) was added
drop-wise until the pH reached 5. The green suspension was extracted
(
162 mg, 0.90 mmol) in CHCl
chromatography (silica gel) using n-hexane:CH
solvents and recrystallization (CHCl /CH OH) gave a quantitative yield of
purple crystals (604 mg, 0.43 mmol, 96%). M.p.: 139-141 °C. R
3
(300 mL). Purification by column
2
Cl (3:1, v/v), removal of
2
3
3
f
= 0.48
1
(
(
n-hexane: CH
d, J = 4.6 Hz, 2H, H
H, H ), 8.71 (d, J = 4.6 Hz, 2H, H
.20 (d, J = 8.8 Hz, 4H, N-Ar-o-CH), 7.10 (d, J = 8.8 Hz, 4H, N-Ar-m-CH),
.93 (d, J = 8.6 Hz, 4H, Ar-m-CH), 3.81 (t, J = 6.5 Hz, 8H, OCH ), 1.20 (s,
8H, t-butyl-CH ), 0.94-0.97 (m, 8H, CH ), 0.76-0.82 (m, 8H, CH ) and
.40-0.61 ppm (m, 44H, CH ). C NMR (100 MHz, CDCl3, 25 °C): δ
2
Cl
2
, 3:2, v/v). H NMR (400 MHz, CDCl
), 9.20 (d, J = 4.6 Hz, 2H, H
), 7.63 (t, J = 8.6 Hz, 2H, Ar-p-CH),
3
, 25 °C): δ = 9.58
), 8.83 (d, J= 4.6 Hz,
with CH
chromatography (silica gel) using CH
give a glossy purple solid (95 mg, 65 µmol, 96%). Analytical samples
were obtained after recrystallization (CHCl /MeOH). M.p.: 112-115 °C. R
OH, 19:1, v/v). H NMR (400 MHz, CDCl , 25 °C): δ =
9.64 (d, J = 4.6 Hz, 2H, H ), 9.18 (d, J = 4.6 Hz, 2H, H ), 8.87 (d, J = 4.6
Hz, 2H, H ), 8.68 (d, J = 4.6 Hz, 2H, H ), 8.23 (d,J = 8.2 Hz, 2H, alkynyl-
2
Cl
2
(3 × 100 mL) and the product was purified by column
β
β
2
Cl :CH OH(19:1, v/v) as eluent to
2
3
2
7
6
1
0
=
1
3
β
β
3
f
1
2
2
= 0.21 (CH Cl
2
:CH
3
3
3
2
2
β
β
13
2
/CH
3
β
β
159.8, 152.8, 151.2, 150.2, 149.9, 149.1, 145.3, 142.6, 132.5, 132.3,
32.2, 130.7, 129.8, 125.5, 121.7, 121.4, 120.7, 113.9, 105.1, 68.5, 33.9,
Ar-m-CH), 8.06 (d, J = 8.2 Hz, 2H, alkynyl-Ar-o-CH), 7.65 (t, J = 8.5 Hz,
2H, Ar-p-CH), 7.21 (d, J = 8.7 Hz, 4H, N-Ar-o-CH), 7.10 (d, J = 8.7 Hz,
4H, N-Ar-m-CH), 6.95 (d, J = 8.5 Hz, 4H, Ar-m-CH), 3.83 (t, J = 6.6 Hz,
1.4, 31.3, 28.5, 28.4, 25.1, 22.2 and 13.7 ppm. UV/Vis (CH
2 2
Cl ): λmax
(
log ε) = 417 (5.42), 568 (4.18), 616 nm (3.93). HRMS (MALDI) m/z calcd.
8H, OCH
(m, 8H, CH
CDCl /C
31.7, 131.5, 130.9, 130.4, 130.0, 129.8, 129.4, 125.2, 121.5, 121.1,
13.8, 105.2, 97.3, 97.2, 68.5, 33.9, 31.5, 31.4, 28.7, 28.6, 28.5, 25.1,
2.3 and 13.9 ppm. UV/Vis (CH Cl ): λmax (log ε) = 442 (5.28), 576 (4.09),
38 nm (4.36). HRMS (MALDI) m/z calcd. for C93
459.7982, found 1459.7926; ]; IR (ATR): ν = 2923, 2852, 2188, 1690,
2
), 1.21 (s, 18H, t-butyl-CH
) and 0.45-0.64 ppm (m, 44H, CH
5 5
D N, 25 °C): δ =159.9, 151.9, 151.5, 150.4, 150.1, 149.9, 142.1,
3
), 0.96-0.99 (m, 8H, CH
2
), 0.77-0.87
+
13
for C84
H N
108 5
4
O BrZn (M ): 1393.6876; found 1393.6908.
2
2 3
/CH ). C NMR (150 MHz,
3
1
1
2
6
1
1
[
10,20-Bis(3,5-di-tert-butylphenyl)-5-(N,N-bis(4-tert-
butyl)phenylamino)-15-
carbomethoxyphenylethynyl)porphyrinato]zinc(II) 31a: The target
porphyrin was synthesized using [5-bromo-15-N,N-Bis(4-(tert-
butyl)phenylamino)-10,20-bis(3,5-di-tert-butyl)phenylporphyrinato]zinc(II)
0a (150 mg, 0.14 mmol), methyl-4-ethynylbenzoate (108 mg, 0.68
mmol), PdCl (PPh (10 mg, 14 µmol) and copper(I)iodide (8 mg, 41
(
2
2
+
H
113 5 6
N O Zn (M ):
–1
602, 1508, 1454, 1255, 1095, 998, 793, 767, 750 cm
.
3
2
3 2
)
µmol) in dry DMF (10 mL) and diethylamine (6 mL) according to
procedure G. The crude product was filtered through a plug of silica
10,20-Bis(3,5-di-tert-butylphenyl)-5-(N,N-Dimethylaniline)porphyrin
33a: The title compound was synthesized in accordance with general
procedure I. 4-Bromo-4-N,N-dimethylalanine (699 mg, 3.49 mmol), 5,15-
Bis(3,5-di-tert-butylphenyl)porphyrin 26a (200 mg, 0.29 mmol), (8 mL), n-
using CH
CH Cl (3/2) as eluent gave a glossy purple solid (111 mg, 0.09 mmol,
9%). (Recrystallization from CH Cl /MeOH, yield 50 mg, loss due to
solubility of the product in MeOH). M.p.>300 °C. R
2 2
Cl before column chromatography (silica gel) using n-hexane:
2
2
6
2
2
BuLi (2.2 mL, 3.49 mmol), THF (40 mL), sat. aq. NH
(396 mg, 1.30 mmol) were used. The product was obtained as purple/red
crystals after recrystallization from MeOH/CHCl (170 mg, 0.21 mmol,
72%). M.p.: >300 °C. R = 0.68 (n-hexane : CH
(400 MHz, CDCl ): δ = 10.18 (s, 1H, meso-H), 9.33 (d, J = 4.6 Hz, 2H,
), 9.06 (d, J = 4.6 Hz, 2H, H ), 8.99 (d, J = 4.8 Hz, 2H, H ), 8.94 (d, J =
4.8 Hz, 2H, H ), 8.13 (d, J = 1.8 Hz, 4H, Ar-o-CH), 8.10 (d, J = 8.6 Hz, 2H,
4
Cl (2 mL) and DDQ
f
= 0.72 (CH
hexane 1:1 v/v + 1% MeOH). H NMR (400 MHz, CDCl + pyridine-d
), 9.18 (d, J = 4.6 Hz, 2H, H
), 8.72 (d, J = 4.6 Hz, 2H, H ), 8.18 (d, J = 8.2
2
Cl
2
:
,
1
3
5
3
1
3
8
0:1, v/v): δ = 9.68 (d, J = 4.6 Hz, 2H, H
.88 (d, J = 4.6 Hz, 2H, H
β
β
),
f
2 2
Cl , 1:1, v/v). H NMR
β
β
3
Hz, 2H, alkynyl-Ar-CH), 8.03 (d, J = 8.2 Hz, alkynyl-Ar-CH), 7.93-7.96 (m,
H, Ar-o-CH), 7.72-7.73 (m, 2H, Ar-p-CH), 7.11 (d, J = 7.8 Hz, 4H, N-Ar-
H
β
β
β
4
β
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
1
N-Ar-CH), 7.81 (t, J = 1.8 Hz, 2H, Ar-p-CH), 7.11 (d, J = 8.6 Hz, 4H, N-
72%). M.p.: >300 °C. R
(400 MHz, CDCl ): δ= 9.82 (d, J = 5.6Hz, 2H, H
), 9.00 (dd, J = 9.4 Hz 4H, H ), 8.44 (d, J = 1.9 Hz, 1H, N-Ar-CH), 8.11
f
= 0.42 (n-hexane : CH
2
Cl
2
, 1:1, v/v). H NMR
Ar-CH), 3.24 (s, 6H, N-CH
3
), 1.56 (s, 36H, t-butyl-CH
H, NH). C NMR (100 MHz, CDCl ): δ = 150.1, 149.0, 141.1, 135.7,
31.8, 131.7, 131.0, 130.8, 130.2, 121.6, 121.1, 120.9, 110.7, 104.2,
0.9, 35.2 and 31.9 ppm. UV/Vis (CH Cl ): λmax (log ε) = 416 (5.24), 514
3
) and -2.87 ppm (s,
3
β
), 9.10 (d, J = 4.6 Hz, 2H,
13
2
1
4
3
H
β
β
(s, 4H, Ar-o-CH), 8.07 (s, 1H, N-Ar-CH), 7.85 (s, 2H, Ar-p-CH), 7.82 (d, J
= 13.9 Hz, 1H, N-Ar-CH), 7.45 (d, J = 8.4 Hz, 1H, N-Ar-CH), 3.12 (s, 6H,
2
2
13
(
4.04), 554 (3.79), 588 (3.59), 646 nm (3.49). HRMS (MALDI): m/z calcd.
N-CH
3
) and 1.57 ppm (s, 36H, t-butyl-CH
= 151.3, 151, 150.8, 150.5, 149.7, 148.7, 148.7, 148.5, 141.4, 139.3,
38.3, 134.9, 133.6, 132.8, 132.6, 132.5, 129.9, 123.1, 121.1, 111.3,
04.1, 40.9, 35.2, 31.9 ppm. UV/Vis (CH Cl ): λmax (log ɛ) = 425 (4.79),
56 (3.52), 596 nm (3.21). HRMS (MALDI): m/z calcd. for C56 60BrN Zn
3 3
). C NMR (100 MHz, CDCl ):
+
for C56
63 5
H N (M ): 805.5083; found 805.5074.
δ
1
1
5
c
1
3
4
0,20-Bis(2,6-dioctyloxyphenyl)-5-(N,N-Dimethylaniline)porphyrin
3b: The porphyrin was prepared in accordance with general procedure I.
-Bromo-4-N,N-dimethylalanine (699 mg, 3.49 mmol), 5,15-bis(2,6-
2
2
H
5
+
(
M ): 945.3324; found 945.3356.
dioctyloxyphenyl)porphyrin 26b(284 mg, 0.29 mmol), Et
2.2 mL, 3.49 mmol) , THF (40 mL), sat. aq. NH Cl and DDQ (396 mg,
.30 mmol) were used. The product was obtained as purple/red crystals
2
O (8 mL), n-BuLi
(
1
4
[10,20-Bis(2,6-dioctyloxyphenyl)-5-bromo-15-(N,N-
dimethylaniline)porphyrinato]zinc(II) 35b: Porphyrin 35b was
synthesized in accordance with general procedure C using 5-bromo-
10,20-bis(2,6-dioctyloxyphenyl)-15-(4-N,N-dimethylanilinyl)porphyrin 34b
3
after recrystallization from MeOH/CHCl (171 mg, 0.15 mmol 54%). M.p.:
1
9
5-96 °C. R
CDCl ): δ= 10.02 (s, 1H, Hmeso), 9.20 (d, J = 4.85 Hz, 2H, H
.85 Hz, 2H, H ), 8.88 (d, J = 4.85 Hz, 2H, H ), 8.82 (d, J = 4.85 Hz, 2H,
), 8.08 (d, J = 8.6 Hz, 2H, N-Ar-CH), 7.70 (t, J = 8.4 Hz, 2H, Ar-p-CH),
f
= 0.31 (n-hexane : CH
2
Cl
2
, 1:1, v/v). H NMR (400 MHz,
3
β
), 8.92 (d, J =
(150 mg, 0.13 mmol) in CHCl
in MeOH (5 mL) was added. The crude product was filtered through silica
gel using CH Cl as eluent to yield a purple/green solid (155 mg, 0.13
mmol, 98%). M.p.: 134 °C. R
NMR (600 MHz, CDCl ): δ= 9.65 (d, J = 4.7 Hz, 2H, H
Hz, 2H, H ), 8.87 (d, J = 4.5 Hz, 2H, H ), 8.81 (d, J = 4.8 Hz, 2H, H
3 2
(50 mL) and Zn(OAc) (84 mg, 0.38 mmol)
4
H
β
β
β
2
2
1
7
.09 (d, J = 8.6 Hz, 2H, N-Ar-CH), 7.02 (d, J = 8.6 Hz, 4H, Ar-m-CH),
.83 (t, J = 6.3 Hz, 8H, OCH ), 1.00-0.93 (m, 8H, CH ), 3.23 (s, 6H, N-
), 0.44-0.92 (m, 60H, CH (CH ) and -2.82 ppm (s, 2H, NH).
NMR (100 MHz, CDCl ): δ = 159.3, 148.9, 134.7, 130.4, 128.9, 119.8,
19.1, 110.9, 109.7, 104.4, 102.2, 67.8, 39.4, 30.5, 27.8, 27.8, 24.4, 21.4
and 12.9 ppm. UV/Vis (CH Cl ): λmax (log ɛ) = 413 (5.90), 508 (4.58), 586
4.11), 644 nm (3.89). HRMS (MALDI): m/z calcd. for C56
f
= 0.42 (n-hexane : CH
2
Cl
), 8.91 (d, J = 4.7
),
2
, 1:1, v/v). H
3
CH
2
2
3
β
13
3
3
2
)
6
C
β
β
β
3
c
7.94 (d, J = 8.3 Hz, 2H, N-Ar-CH), 7.68 (t, J = 8.4 Hz, 2H, Ar-p-CH), 6.99
(d, J = 8.8 Hz, 4H, Ar-m-CH), 6.73 (d, J = 8.8 Hz, 2H, N-Ar-CH), 3.82 (t, J
1
2
2
= 6.3 Hz, 8H, CH
2
), 2.71 (s, 6H, N-CH
). C NMR (100 MHz, CDCl ): δ
132.4, 131.3, 129.8, 121.5, 114.1, 105.4, 68.8, 31.4, 28.8, 28.8, 28.7,
5.4, 22.4 and 13.9 ppm. UV/Vis (CH Cl ): λmax (log ɛ) = 426 (5.70), 555
3
) and 0.98-0.39 ppm (m, 60H,
+
13
(
C
72
H
N
95 5
O
4
(M ):
3 2
CH (CH )
6
3
c
= 160.2, 150.9, 149.2, 135.4,
1
093.7384; found 1093.7384.
2
2
2
(
(
4.50), 599 nm (4.02). HRMS (MALDI): m/z calcd. for C72
M ): 1233.5624; found 1233.4647.
5
H92BrN O
4
Zn
1
0,20-Bis(3,5-di-tert-butylphenyl)-5-bromo-15-(N,N-
+
dimethylaniline)porphyrin 34a: Porphyrin 34a was synthesized in
accordance with general procedure F. 5-(4-N,N-Dimethylanilinyl)-10,20-
bis(3,5-di-tert-butylphenyl)porphyrin 33a (250 mg, 0.31 mmol), CHCl
mL), pyridine (0.2 mL), NBS (66 mg, 0.37 mmol) and acetone (5 mL)
3
(50
[10,20-Bis(3,5-di-tert-butylphenyl)-15-(4-
carbomethoxyphenylethynyl)-5-(N,N-
were used. The product was obtained as purple crystals (200 mg, 0.23
dimethylaniline)porphyrinato]zinc(II) 36a: Porphyrin 36a was
synthesized in accordance with general procedure G. [5-Bromo-10,20-
bis(3,5-di-tert-butylphenyl)-15-(4-N,N-
1
mmol, 74%). M.p.: >300 °C. R
NMR (400 MHz, CDCl ): δ = 9.63 (d, J = 4.6 Hz, 2H, H
), 8.89 (d, J = 5.2 Hz, 2H, H ), 8.80 (d, J = 4.9 Hz, 2H, H
.04 (d, J = 2.3 Hz, 4H, Ar-o-CH), 8.03 (d, J = 4.3 Hz, 2H, N-Ar-CH),
.80-7.79 (m, 2H, Ar-p-CH), 7.08 (d, J = 8.88 Hz, 2H, N-Ar-CH), 3.21 (s,
f
= 0.60 (n-hexane : CH
2
Cl
2
, 1:1, v/v).
), 8.90 (d, J =
),
H
3
β
8
8
7
6
.81 Hz, 2H, H
β
β
β
dimethylanilinyl)porphyrinato]zinc(II) 35a(100 mg, 0.12 mmol), methyl-4-
ethylbenzonate (83 mg, 0.52 mmol), PdCl
(6 mg, 0.32 μmol), (10 mL), diethylamine (2.9 mL) and water (100 mL)
were used to yield green crystals after recrystallization from MeOH/CHCl
(60 mg, 0.06 mmol, 52%). M.p.: 182 °C. R = 0.58 (n-hexane : CH Cl , 2:1,
): δ = 9.86 (d, J = 4.5 Hz, 2H, H ). 9.09 (d,
), 9.03 (d, J = 4.8 Hz, 2H, H ), 8.94 (d, J = 4.6 Hz, 2H,
), 8.25 (d, J = 8.1 Hz, 2H, alkynyl-Ar-CH), 8.12 (d, J = 8.4 Hz, 4H,
alkynyl-Ar-CH), 8.07 (d, J = 8.1 Hz, 2H, N-Ar-CH), 7.85-7.84 (m, 2H, Ar-
p-CH), 7.10 (d, 2H, N-Ar-CH), 4.03 (s, 3H, OCH ), 3.22 (s, 6H, N-CH
). C NMR (100 MHz, CDCl ): δ
52.4, 150.9, 150.0, 148.5, 142.2, 135.5, 133.2, 132.2, 131.7, 131.2,
30.4, 130.0, 129.8, 129.0, 123.4, 120.7, 113.6, 110.9, 97.8, 97.1, 94.9,
2.4, 41.1, 35.2, 31.9 and 31.1 ppm. UV/Vis (CH Cl ):λmax (log ɛ) = 444
2 3 2
(PPh ) (7 mg, 0.12 μmol), CuI
1
3
H, N-CH
NMR (100 MHz, CDCl
3
), 1.52 (s, 36H, t-butyl-CH
): δ = 150.2, 148.9, 141.1, 135.7, 131.9, 130.2,
30.1, 122.1, 121.3, 110.9, 102.2, 40.9, 35.2 and 31.9 ppm. UV/Vis
CH Cl ); λmax (log ɛ) =423 (5.75), 524 (4.47), 565 (4.42), 603 (3.99), 659
nm (4.17). HRMS (ESI): m/z calcd. for C56
3
) and -2.66 ppm (s, 2H, NH).
C
3
3
c
f
2
2
1
1
(
v/v). H NMR (400 MHz, CDCl
J = 4.6 Hz, 2H, H
3
β
2
2
β
β
+
H62BrN
5
(M ): 884.4267; found
H
β
8
84.4265.
3
3
)
13
and 1.58 ppm (s, 36H t-butyl-CH
3
3
c
=
1
0,20-Bis(2,6-dioctyloxyphenyl)-5-bromo-15-(N,N-
1
1
5
dimethylaniline)porphyrin 34b: The porphyrin was synthesized in
accordance with general procedure F. 5-(4-N,N-Dimethylanilinyl)-10,20-
bis(2,6-dioctyloxyphenyl)porphyrin 33b (56 mg, 0.05 mmol), CHCl (20
3
2
2
(
6.31), 570 (4.98), 620 nm (5.29). HRMS (MALDI): m/z calcd. for
mL), NBS (82 mg, 0.05 mmol), pyridine (5 µL) and acetone (5 mL) were
+
66 67 5 2
C H N O Zn (M ): 1025.4586; found 1025.4613.
used to obtained the product as purple crystals (50 mg, 0.43 mmol, 84%).
1
M.p.: 52 °C. R
CDCl ): δ= 9.56 (d, J = 4.6 Hz, 2H, H
.76 (d, J = 4.7 Hz, 2H, H ), 9.56 (d, J = 4.7 Hz, 2H, N-Ar-CH), 7.72 (t, J
8.9 Hz, 2H, Ar-p-CH), 7.10 (d, J = 8.4 Hz, 2H, N-Ar-CH), 7.02 (d, J =
.6 Hz, 4H, Ar-m-CH), 3.85 (t, J = 6.4 Hz, 8H, OCH ), 1.01-0.45 (m, 60H,
) and -2.53 ppm (s, 2H, NH). C NMR (100 MHz, CDCl ): δ
f
= 0.51 (n-hexane : CH
2
Cl
2
, 1:1, v/v). H NMR (600 MHz,
3
β
), 8.85 (dd, J = 4.7, 8.5 Hz, 4H, H
β
),
[10,20-Bis(2,6-dioctyloxyphenyl)-15-(4-
carbomethoxyphenylethynyl)-5-(N,N-
dimethylaniline)porphyrinato]zinc(II) 36b: Following procedure G [5-
bromo-10,20-bis(2,6-dioctyloxyphenyl)-15-(4-N,N-
dimethylanilinyl)porphyrinato]zinc(II) 35b (140 mg, 0.12 μmol), methyl-4-
8
β
=
8
CH
2
13
3 2
(CH )
6
3
c
=
1
3
4
60.1, 149.8, 135.7, 131.2, 130.1, 120.7, 113.3, 110.8, 105.3, 68.7, 40.9,
1.5, 28.8, 28.7, 25.4, 22.4 and 13.9 ppm. UV/Vis (CH Cl ): λmax (log ɛ) =
23 (5.73), 523 (4.50), 561 (4.29), 600 (4.05), 657 nm (3.96). HRMS
ethylbenzonate (96 mg, 0.60 mmol), PdCl
CuI (7 mg, 36.50 μmol), DMF (11 mL), diethylamine (2.8 mL) gave green
crystals after recrystallization from MeOH/CHCl (80 mg, 0.06 mmol,
50%). M.p.: 87 °C. R = 0.42 (n-hexane : CH Cl , 1:2, v/v). H NMR (400
MHz, CDCl ): δ= 9.74 (d, J = 4.4 Hz, 2H, H ), 8.97 (d, J = 4.7 Hz, 2H, H ),
.91 (s, 2H, H ), 8.82 (d, J = 4.7 Hz, 2H, H ), 8.25 (d, J = 8.2 Hz, 2H,
2 3 2
(PPh ) (9 mg, 12.20 μmol),
2
2
3
+
1
(
MALDI): m/z calcd. for C72
H94BrN
5
O
4
(M ): 1171.6489; found1171.6497.
f
2
2
3
β
β
8
β
β
[
10,20-Bis(3,5-di-tert-butylphenyl)-5-bromo-15-(N,N-
alkynyl-Ar-CH), 8.04 (d, J = 8.4 Hz, 2H, alkynyl-Ar-CH), 8.06 (s, 2H, N-
Ar-CH), 7.72 (t, J = 9.4 Hz, 2H, Ar-p-CH), 7.08 (s, 2H, N-Ar-CH), 7.03 (d,
dimethylaniline)porphyrinato]zinc(II) 35a: Porphyrin 35a was
synthesized in accordance with general procedure C using 5-bromo-
3
J = 9.01 Hz, 4H, Ar-m-CH), 4.04 (s, 3H, OCH ), 3.86 (t, J = 6.6 Hz, 8H,
1
3
0,20-bis(3,5-di-tert-butylphenyl)-15-(4-N,N-dimethylanilinyl)porphyrin
4a (200 mg, 0.22 mmol) in CHCl (30 mL) and Zn(OAc) (12 mg, 0.68
13
OCH
2
), 3.20 (s, 6H, N-CH
3
), and 0.99-0.42 ppm (m, 60H, CH
3 2
(CH )
6
).
C
3
2
NMR (100 MHz, CDCl
3
): δ
c
= 160.2, 135.6, 132.0, 131.9, 131.1, 130.4,
mmol) in MeOH (10 mL) was added. The product was obtained as green
crystals after recrystallization from MeOH/CHCl (150 mg, 0.16 mmol,
1
29.9, 129.8, 129.5, 128.2, 105.4, 68.7, 52.3, 31.6, 28.9, 28.9, 25.4 and
3
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
2
2.5 ppm. UV/Vis (CH
2
Cl
2
): λmax (log ɛ) = 446 (5.69), 569 (4.42), 619 nm
8.72 (d, J = 4.3 Hz, 2H, H
2H aryl-H), 8.22 (d, J = 7.4 Hz, 2H, aryl-H), 8.10 (d, J = 6.4 Hz, 4H, Ph-H),
7.61-7.66 (m, 6H, Ph-H), 7.01-7.12 (m, 8H, aryl-H), 4.07 (s, 3H, OCH
β β
), 8.72-8.24 (m, 4H, H ), 8.36 (d, J = 7.4 Hz,
+
(
4.63). HRMS (MALDI): m/z calcd. for C82
99 5 6
H N O Zn (M ): 1313.6887;
found 1313.6887.
3
)
13
and 1.19 ppm (s, 18H, t-butyl-CH
pyridine-d , 50:1, v/v): δ = 179.6, 152.7, 150.2, 150.1, 143.1, 142.5,
34.5, 134.4, 132.8, 131.8, 131.1, 130.6, 129.0, 127.5, 127.2, 126.2,
25.5, 121.3, 120.6, 52.3, 34.0 and 31.4 ppm. UV/Vis (MeOH): λmax (log
3 3
). C NMR (100 MHz, CDCl +
[
(
10,20-Bis(3,5-di-tert-buylphenyl)-15-(4-carboxyphenylethynyl)-5-
N,N-dimethylaniline)porphyrinato]zinc(II) 37a: Porphyrin 37a was
5
1
1
synthesized using procedure H. Porphyrin 36a (150 mg, 0.15 mmol),
ε) = 416 (5.22), 568 (4.02), 618 nm (3.97). HRMS (MALDI): m/z calcd. for
C H N O Zn (M ): 937.3334; found 937.3325.
60 51 5 2
NaOH (2.06 g, 51 mmol), MeOH (25.7 mL) and THF (25.7 mL) were
+
used. Recrystallization from MeOH/ CH
2
Cl
2
yielded the desired
= 0.14
): δ = 9.76 (d, J = 4.6 Hz,
), 9.89 (d, J = 4.6 Hz, 2H, H ), 8.81 (d,
), 8.30 (d, J = 6.03 Hz, 2H, alkynyl-Ar-H), 8.09 ( d, J =
.03 Hz, 2H, alkynyl-Ar-H), 8.02-8.05 (m, 4H, Ar-o-CH), 8.02-8.05 (m, 2H,
N-Ar-CH), 7.78 (s, 2H,Ar-p-CH), 7.10 (d, J = 8.46 Hz, 2H, N-Ar-CH), 3.21
compound in 85% (128 mg, 0.13 mmol, 85%). M.p.: >300 °C. R
f
1
(
2
CH
H, H
J = 4.6 Hz, 2H, H
2
Cl
2
+ 2% MeOH). H NMR (400 MHz, CDCl
3
[15-(4-Carboxylicacid)phenyl-10,20-(diphenyl)-5-(N,N-bis(4-tert-
butyl)phenylamino)porphyrinato]zinc(II) 39c: Porphyrin 38c was
synthesized according to general procedure H. [5-N,N-Bis(4-(tert-
butyl)phenylamino)-15-(4-methoxycarbonyl)phenyl-10,20-
diphenylporphyrinato]zinc(II) 38c (170 mg, 0.14 mmol) was dissolved in
THF (15 mL) in a 100 mL RBF. NaOH (1.1 g, 0.03 mol) dissolved in
MeOH (15 mL) was added. After the workup, the residue was redissolved
β
), 8.97 (d, J = 4.6 Hz, 2H, H
β
β
β
6
(
s, 6H, N-CH
3
), 1.50 (s, 36H, t-butyl-CH
3
) and 1.26 ppm (s, 16 H, t-butyl-
13
CH
3
). C NMR (100 MHz, CDCl ): δ = 152.4, 150.9, 150.5, 150.0, 149.9,
3
c
1
1
1
49.2, 148.9, 148.7, 148.5, 142.2, 135.9, 135.7, 135.5, 135.4, 133.1,
32.2, 131.7, 131.6, 131.2, 130.3, 130.1, 124.0, 123.5, 123.2, 123.0,
20.7, 110.7, 97.4, 97.2, 95.2, 41.0, 35.2, 31.9, 29.8 and 29.5 ppm.
in CH
solvents were removed in vacuo and the residue was recrystallized from
CH Cl /MeOH:H O (3:1, v/v) to yield a green/purple solid (105 mg, 0.11
mmol, 82%). M.p.:>300 °C. R = 0.53 (CH Cl : hexane 1:1 v/v + 1%
MeOH). H NMR (400 MHz, CDCl + pyridine-d5, 30:1, v/v): δ = 9.21 (d,
J = 4.6 Hz, 2H, H ), 8.74-8.77 (m, 4H, H ), 8.70 (d, J = 4.6 Hz, 2H, H ),
2 2
Cl + 5% MeOH and filtered through a short plug of silica. The
2
2
2
UV/Vis: (THF): λmax (log ɛ) = 447 (5.14), 578 (3.71), 630 nm (4.12).
HRMS (MALDI): m/z calcd. for C65
1
CH
f
2
2
+
1
H
65
N O
5 6
Zn (M ): 1011.4430; found
3
+
+
011.4436. MS (MALDI) m/z (%): 1011.45 (100) [M ], 996.46 (9) [M –
β
β
β
–1
3
]; IR (ATR): ν = 2370, 1753, 1591, 1491, 1344, 1133, 795 cm
.
8.44 (d, J = 7.9 Hz, 2H, alkynyl-Ar-CH), 8.22 (d, J = 7.9 Hz, 2H, alkynyl-
Ar-CH), 8.09 (d, J = 6.4 Hz, 4H, Ph-H), 7.60-7.67 (m, 6H, Ph-H), 7.11 (d,
J = 7.8 Hz, 4H, N-Ar-CH), 7.03 (d, J = 7.8 Hz, 4H, N-Ar-CH) and 1.17
[
(
10,20-Bis(2,6-dioctyloxyphenyl)-15-(4-carboxyphenylethynyl)-5-
N,N-dimethylaniline)porphyrinato]zinc(II) 37b: The title compound
13
ppm (s, 18H, t-butyl-CH
3 3 5
). C NMR (150 MHz, CDCl + pyridine-d , 50:1,
v/v): δ = 152.7, 150.3, 150.2, 149.7, 143.2, 142.5, 135.7, 134.4, 132.7,
was synthesized following procedure H. Porphyrin 36b (60 mg, 0.05
1
1
31.7, 131.3, 130.6, 127.8, 127.2, 126.2, 125.5, 123.4, 122.8, 122.1,
21.3, 120.1, 34.0 and 31.4 ppm. UV/Vis (MeOH): λmax (log ε) = 416
mmol), NaOH (644 mg, 16 mmol), MeOH (8 mL) and THF (8 mL) were
used. Recrystallization from CH
28-232 °C. R = 0.36 (CH Cl
DMSO): δ = 9.56 (d, J = 4.2 Hz, 2H, H
2 2
Cl /MeOH (42 mg, 33 µmol, 72%). M.p.:
1
(4.81), 568 (3.62), 618 nm (3.55). HRMS (MALDI): m/z calcd. for
C H N O Zn (M ):923.3178; found 923.3179.
59 49 5 2
2
f
2
2
+ 2% MeOH). H NMR (400 MHz,
), 8.72 (d, J = 4.2 Hz, 2H, H ),
), 8.57 (d, J = 4.2 Hz, 2H, H ), 8.07-8.15 (m,
+
β
β
8
4
7
.66 (d, J = 4.2 Hz, 2H, H
H, alkynyl-Ar-H), 7.86 (d, J = 8.4, 2H, N-Ar-CH), 7.71 (m, 2H, Ar-p-CH),
.09 (d, J = 8.4, 4H, Ar-m-CH), 7.05 (d, J = 8.5 Hz, 2H, N-Ar-CH), 3.85
β
β
Crystal structure determinations Crystals were grown by dissolving the
compounds in CH Cl and layering with MeOH using strategies described
before. Diffraction data for all compounds were collected on a Bruker
APEX 2 DUO CCD diffractometer by using graphite-monochromated Mo-
2
2
[46]
(
m, 8H, OCH
2
), 3.13 (s, 6H, N-CH
3
)
and 0.92-0.39ppm (m, 60H,
1
3
CH
3 2
(CH )
6
). C NMR (100 MHz, CDCl
3
): δ = 159.2, 151.2, 150.3, 149.3,
c
1
1
2
49.2, 149.1, 148.8, 135.9, 135.7, 135.4, 134.9, 130.9, 129.8, 123.6,
23.3, 123.1, 120.4, 114.2, 110.3, 105.2, 67.7, 30.9, 28.2, 28.1, 28.1,
K
α
(λ = 0.71073 Å) radiation and Incoatec IμS Cu-K
α
(λ = 1.54178 Å)
radiation. Crystals were mounted on MiTeGen MicroMount and
a
4.8, 21.7 and 13.7 ppm. UV/Vis: (THF): λmax (log ɛ) = 449 (5.27), 577
collected at 100(2) K by using an Oxford Cryosystems Cobra low-
temperature device. Data was collected by using omega and phi scans
and were corrected for Lorentz and polarization effects by using the
+
(
3.86), 630 nm (4.21). HRMS (MALDI): m/z calcd. for C81
H
97
N
5 6
O
Zn (M ):
1
1
299.6730; found 1299.6735; IR (ATR): ν = 2922, 2851, 2184, 1684,
–1
[47]
602, 1454, 1092, 994, 770, 713 cm
.
APEX software suite. The structures were solved with Direct Methods
2
2
[48,
and refined against │F │ with the program OLEX by using all data.
49]
Non-hydrogen atoms were refined with anisotopically thermal
[
10,20-(Diphenyl)-15-(4-methoxycarbonyl)phenyl-5-(N,N-bis(4-tert-
butyl)phenylamino)porphyrinato]zinc(II) 38c: Using procedure
porphyrin 30c was synthesized. [5-N,N-Bis(4-(tert-butyl)phenylamino)-
0,20-diphenylporphyrinato]zinc(II) 29c (185 mg, 0.30 mmol) was
dissolved in CHCl (170 mL). N-bromosuccinimide (57 mg, 0.32 mmol)
parameters. Hydrogen atoms were generally placed into geometrically
calculated positions and refined using a riding model. The N-H hydrogen
atoms were located using different maps and refined using the standard
riding model. Details of data refinement can be found in Table SI(1). All
F
1
3
[50]
images were rendered using XP in SHELXTL.
and pyridine (0.1 mL) were added. The solvent was removed in vacuo
and the purple residue was used in the next step without further
purification (yield 218 mg, 0.25 mmol, 82%). The [5-bromo-15-N,N-bis(4-
Crystal Data for 26b: C64
a = 18.0890(7) Å, b = 18.1733(7) Å, c = 8.5224(3) Å, β = 92.298(2) , V =
2799.37(18) Å , T = 100(2) K, Z = 2, Z' = 0.5, μ(CuK
reflections measured, 5088 unique (Rint = 0.0769) which were used in all
86 4 4 r 1
H N O , M = 975.36, monoclinic, P2 /c (No. 14),
°
(
tert-butyl)phenylamino)-10,20-diphenylporphyrinato]zinc(II) 30c (170 mg,
.19 mmol) was dissolved in THF (8 mL) in a 100 mL Schlenk tube.
CO (2M in H O, 3 mL) was added and the solution was degassed via
three freeze-pump-thaw cycles. Pd(PPh (44 mg, 0.04 mmol) and 4-
3
0
K

) = 0.551, 26038
2
3
2
3
)
4
calculations. The final wR
2 1
was 0.1184 (all data) and R was 0.0434 (I >
methoxycarbonylphenylboronic acid (173 mg, 0.96 mmol) were added
and the reaction flask was heated to 66 °C and left to stir at this
temperature for 17 h. The reaction mixture was cooled to r.t. before
2(I)).
Crystal Data for 29c: C52
45 5 r 1
H N Zn, M = 805.30, monoclinic, P2 /n (No.
pouring onto H
the organic extracts were washed with sat. NaHCO
100 mL). The organic extracts were dried over Na
solvents were removed in vacuo. The residue was redissolved in CH
hexanes (1:1, v/v) and filtered through a short plug of silica using
CH Cl : hexanes (1:1, v/v) as eluent. The main purple colored fraction
was isolated and the solvents were removed in vacuo. The purple/red
residue was recrystallized from CH Cl /n-hexane to yield a pink/purple
solid (153 mg, 0.16 mmol, 85% (based on conversion of bromoporphyrin).
2
O (20 mL). The product was extracted using CH
(100 mL) and brine
SO , filtered and the
Cl
2
Cl
2
and
°
1
4), a = 25.200(2) Å, b = 10.9531(9) Å, c = 33.549(3) Å, β = 110.775(2) ,
3
3
V = 8657.9(13) Å , T = 100(2) K, Z = 8, Z' = 2, μ(MoK
reflections measured, 17128 unique (Rint = 0.0495) which were used in all
calculations. The final wR was 0.0817 (all data) and R was 0.0368 (I >
(I)). The tert-butyl group at C108_1 was modelled over two positions
a
) = 0.608, 124148
(
2
4
2
2
:
2
1
2
2
2
using restraints (SADI, DFIX) and constraints (EADP) in a 67–33%
occupancy. Excess solvent water was squeezed from the void as no
probable solution was obtained.
2
2
1
M.p.:>300 °C. R
400 MHz, CDCl
f
= 0.53 (CH
+ pyridine-d
2
Cl
2
: hexane 1:1 v/v + 1% MeOH). H NMR
),
Crystal Data for 37a: C130
a = 16.3625(10) Å, b = 20.2579(13) Å, c = 20.6165(13) Å, α =
132 10 5 2 r
H N O Zn , M
= 2045.19, triclinic, P 1ꢀ (No. 2),
(
3
5
, 50:1, v/v): δ = 9.22 (d, J = 4.3 Hz, 2H, H
β
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
°
°
°
3
1
15.108(2) , β = 108.506(2) , γ = 96.614(2) , V = 5614.1(6) Å , T = 100(2)
[6]
a) A. G. Hyslop, M. A. Kellett, P. M. Iovine, M. J. Therien, J. Am. Chem.
Soc. 1998, 120, 12676-12677; b) M. O. Senge, Acc. Chem. Res. 2005,
38, 733-743; c) N. N. Sergeeva, M. O. Senge, A. A. Ryan, in Handbook
of Porphyrin Science, K. M. Kadish, K. M. Smith, R. Guilard, eds.,
World Scientific, Singapore, 2010, Vol. 3, pp. 325-366.
K, Z = 2, Z' = 1, μ(MoK
unique (Rint = 0.0526) which were used in all calculations. The final wR
was 0.1651 (all data) and R was 0.0627 (I > 2(I)). The tert-butyl groups
a
) = 0.486, 90721 reflections measured, 22176
2
1
at C107_1, C111_1, C211_1, C107_2, C111_2 and C211_2 were all
modelled over two positions using restraints (ISOR, SADI) and
constraints (EADP) in a 55 – 45, 73 – 27, 54 – 46, 70 – 30, 61 – 39 and
[7]
[8]
a) K. S. Suslick, C. T. Chen, G. R. Meredith, L. T. Cheng, J. Am. Chem.
Soc. 1992, 114, 6928-6930; b) S. M. LeCours, H.-W. Guan, S. G.
DiMagno, C. H. Wang, M. J. Therien, J. Am. Chem. Soc. 1996, 118,
1497-1503.
5
5 – 45% occupancy, respectively. This indicates a large degree of
rotation possible with the tert-butyl groups. Similarly, the β carbon atoms
C2_1, C3_1 and C2_2, C3_2 were modelled over two positions to allow
for the removal of a short intramolecular contact of the disordered
dimethylaniline moiety in a 73 – 27% and a 74 – 26% occupancy. The
disordered dimethylaniline moiety was modelled over two positions with
using restraints (SADI) and constraints (EADP) with associated Zn(II)
coordinated and free water molecules in a 72 – 28% occupancy. Finally,
the para-carboxylic acid phenyl moiety at C10A was modelled over two
positions using restraints (ISOR) and constraints (EADP) in a 56 – 44%
occupancy.
a) M. Grätzel, J. Photochem. Photobiol. C:Photochem. Rev. 2003, 4,
145-153; b) S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B. F.
Curchod, N. Ashari-Astani, I. Tavernelli, U. Rothlisberger, M. K.
Nazeeruddin, M. Grätzel, Nat. Chem. 2014, 6, 242-247; c) A. Yella, H.-
W. Lee, H. N. Tsao, C. Yi, A. K. Chandiran, M. K. Nazeeruddin, E. W.-
G. Diau, C.-Y. Yeh, S. M. Zakeeruddin, M. Grätzel, Science 2011, 334,
629-634; d) T. Bessho, S. M. Zakeeruddin, C.-Y. Yeh, E. W.-G. Diau, M.
Grätzel, Angew. Chem., Int. Ed. 2010, 49, 6646-6649.
[9]
a) H. Imahori, Y. Matsubara, H. Iijima, T. Umeyama, Y. Matano, S. Ito,
M. Niemi, N. V. Tkachenko, H. Lemmetyinen, J. Phys. Chem. C 2010,
1
14, 10656-10665; b) K. Kurotobi, Y. Toude, K. Kawamoto, Y. Fujimori,
Crystal Data for 40a: C48
2 4 r
H52Br N , M = 844.75, monoclinic, C2/c (No. 15),
°
S. Ito, P. Chabera, V. Sundström, H. Imahori, Chem. Eur. J. 2013, 19,
a = 27.8531(16) Å, b = 17.5495(10) Å, c = 8.5438(5) Å, β = 101.219(1) ,
3
17075-17081.
V = 4096.5(4) Å , T = 100(2)K, Z = 4, Z' = 0.5, μ(MoK
reflections measured, 4715 unique (Rint = 0.0294) which were used in all
calculations. The final wR was 0.0938 (all data) and R was 0.0360 (I >
(I)). The tert-butyl group at C207 was modelled over two positions using
constraints (EADP) in a 52 – 78% occupancy.
a
) = 2.018, 34175
[
10] a) M. J. Lee, K. D. Seo, H. M. Song, M. S. Kang, Y. K. Eom, H. S. Kang,
H. K. Kim, Tetrahedron Lett. 2011, 52, 3879-3882; b) R. B. Ambre, G.-F.
Chang, C.-H. Hung, Chem. Commun. 2014, 50, 725-727; c) R. B.
Ambre, G.-F. Chang, M. R. Zanwar, C.-F. Yao, E. W.-G. Diau, C.-H.
Hung, Chem. Asian J. 2013, 8, 2144-2153; d) C.-F. Lo, S.-J. Hsu, C.-L.
Wang, Y.-H. Cheng, H.-P. Lu, E. W.-G. Diau, C.-Y. Lin, J. Phys. Chem.
C 2010, 114, 12018-12023. e) J. Lu, X. Xu, K. Cao, J. Cui, Y. Zhang, Y.
Shen, X. Shi, L. Liao, Y. Cheng, M. Wang, J. Mater. Chem. A, 2013,1,
2
1
2
CCDC-1518090 (for 40a), -1518091 (for 26b), -1518092 (for 29c) and -
518093 (for 37a) contains the supplementary crystallographic data for
this paper. These data sets can be obtained free of charge from The
Cambridge Crystallographic Data Center via
http://www.ccdc.cam.ac.uk/data_request/cif.
1
10008-10015.
[
[
[
11] T.-G. Zhang, Y. Zhao, I. Asselberghs, A. Persoons, K. Clays, M. J.
Therien, J. Am. Chem. Soc. 2005, 127, 9710-9720.
12] E. G. A. Notaras, M. Fazekas, J. J. Doyle, W. J. Blau, M. O. Senge,
Chem. Commun. 2007, 2166-2168.
Supporting Information (See footnote on the first page of this article):
Experimental details, optimization studies and spectroscopic data of all
compounds.
13] a) M. Zawadzka, J. Wang, W. J. Blau, M. O. Senge, Chem. Phys. Lett.
2009, 477, 330-335; b) M. O. Senge, M. Fazekas, M. Pintea, M.
Zawadzka, W. J. Blau, Eur. J. Org. Chem. 2011, 5797-5816; c) M.
Zawadzka, J. Wang, W. J. Blau, M. O. Senge, Photochem. Photobiol.
Sci. 2013, 12, 996-1007.
Acknowledgements
[
14] T. Higashino, H. Imahori, Dalton Trans. 2015, 44, 448-463.
15] a) M. Ishida, S. W. Park, D. Hwang, Y. B. Koo, J. L. Sessler, D. Y. Kim,
D. Kim, J. Phys. Chem. C 2011, 115, 19343-19354; b) M. Ishida, D.
Hwang, Y. B. Koo, J. Sung, D. Y. Kim, J. L. Sessler, D. Kim, Chem.
Commun. 2013, 49, 9164-9166.
[
This work was supported by grants from Science Foundation
Ireland (14/TIDA/2362 and IvP 13/IA/1894).
Keywords:Porphyrins •DSSC •Push-pull systems •Methods
[16] a) T. Higashino, K. Kawamoto, K. Sugiura, Y. Fujimori, Y. Tsuji, K.
Kurotobi, S. Ito, H. Imahori, ACS Appl. Mater. Interfaces 2016, 8,
development •Optical materials
1
5379-15390; b) K. Kurotobi, Y. Toude, K. Kawamoto, Y. Fujimori, S.
Ito, P. Chabera, V. Sundström, H. Imahori, Chem. Eur. J. 2013, 19,
7075-17081. c) T. Higashino, Y. Fujimori, K. Sugiura, Y. Tsuji, S. Ito,
[
1]
a) K. M. Kadish, K. M. Smith, R. Guilard, eds., The Porphyrin Handbook.
Volumes 1-10, Academic Press:ꢀ San Diego, 2000; b) M. R.
Wasielewski, J. Org. Chem. 2006, 71, 5051-5066; c) M. Calvete, G. Y.
Yang, M. Hanack, Synth. Met. 2004, 141, 231-243; d) M. O. Senge, M.
Fazekas, E. G. A. Notaras, W. J. Blau, M. Zawadzka, O. B. Locos, E. M.
NiꢀMhuircheartaigh, Adv. Mater. 2007, 19, 2737-2774; e) A. A. Ryan, M.
O. Senge, Photochem. Photobiol. Sci. 2015, 14, 638-660; f) E. S.
Nyman, P. H. Hynninen, J. Photochem. Photobiol. B:Biol. 2004, 73, 1-
1
H. Imahori, J. Porphyrins Phthalocyanines 2014, 18, 1-10.
[
17] a) W. W. Kalisch, M. O. Senge, Angew. Chem. Int. Ed. 1998, 37, 1107-
1109; b) M. O. Senge, W. W. Kalisch, I. Bischoff, Chem. Eur. J. 2000, 6,
2721-2738; c) X. Feng, I. Bischoff, M. O. Senge, J. Org. Chem. 2001,
66, 8693-8700.
[18] M. O. Senge, C. Ryppa, M. Fazekas, M. Zawadzka, K. Dahms, Chem.
Eur. J. 2011, 17, 13562-13573.
28.
[
19] a) R. P. Briňas and C. Brückner, Tetrahedron 2002, 58, 4375-4381; b)
D. K. Dogutan, S. H. H. Zaidi, P. Thamyongkit, J. S. Lindsey, J. Org.
Chem. 2007, 72, 7701-7714.
[
[
2]
3]
a) M. O. Senge, Chem. Commun. 2011, 47, 1943-1960; b) M. O. Senge
et al. Chem. Commun. 2015, 51, 17031-17063; c) M. O. Senge, in The
Porphyrin Handbook, K. M. Kadish, K. M. Smith, R. Guilard, eds.,
Academic Press, San Diego, 2000, Vol. 1, pp. 239-347.
[
20] a) S. Hatscher, M. O. Senge, Tetrahedron Lett. 2003, 44, 157-160; b) C.
Ryppa, M. O. Senge, S. S. Hatscher, E. Kleinpeter, P. Wacker, U.
Schilde, A. Wiehe, Chem. Eur. J. 2005, 11, 3427-3442.
a) J. S. Lindsey, Acc. Chem. Res. 2010, 43, 300-311; b) M. O. Senge,
Y. M. Shaker, M. Pintea, C. Ryppa, S. S. Hatscher, A. Ryan, Y.
Sergeeva, Eur. J. Org. Chem. 2010, 237-258.
[
21] J. S. Manka, D. S. Lawrence, Tetrahedron Lett. 1989, 30, 6989-6992.
22] a) S. Taniguchi, H. Hasegawa, S. Yanagiya, Y. Tabeta, Y. Nakano, M.
Takahashi, Tetrahedron 2001, 57, 2103-2108; b) S. Taniguchi, H.
Hasegawa, M. Nishimura, M. Takahashi, Synlett 1999, 73-74.
23] Y. Nakamura, I. W. Hwang, N. Aratani, T. K. Ahn, D. M. Ko, A. Takagi,
T. Kawai, T. Matsumoto, D. Kim and A. Osuka, J. Am. Chem. Soc.
[
[
4]
5]
J. S. Lindsey, in The Porphyrin Handbook, K. M. Kadish, K. M. Smith, R.
Guilard, eds., Academic Press, San Diego, 2000, Vol. 1, pp. 45-118.
a) D. M. Wallace, S. H. Leung, M. O. Senge, K. M. Smith, J. Org. Chem.
[
[
1993, 58, 7245-7257; b) C. H. Lee, F. R. Li, K. Iwamoto, J. Dadok, A. A.
Bothnerby, J. S. Lindsey, Tetrahedron 1995, 51, 11645-11672.
2005, 127, 236-246.
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
[
24] Typically, zinc(II) is chosen as central metal due to its utility in DSSC
and positive effect on the NLO properties. See: K. McEwan, K. Lewis,
G. Y. Yang, L. L. Chng, Y. W. Lee, W. P. Lau, K. S. Lai, Adv. Funct.
Mater. 2003, 13, 863-867. Additionally, it has a practical benefit in
preventing metal insertion during Pd-catalyzed reactions.
Blaikie, M. O. Senge, Eur. J. Org. Chem. 2011, 2011, 5817-5844; c) M.
O. Senge, J. Richter, J. Porphyrins Phthalocyanines 2004, 8, 934-953.
[33] a) N. Miyaura, T. Yanagi, A. Suzuki, Synth. Commun.1981, 11, 513-
519; b) A. Suzuki, J. Organomet. Chem. 1999, 576, 147-168
[34] a) K. S. Chan, X. Zhou, B.-S. Luo, T. C. W. Mak, J. Chem. Soc., Chem.
Commun. 1994, 271-272; b) B. Vaz, R. Alvarez, M. Nieto, A. I. Paniello,
A. R. de Lera, Tetrahedron Lett. 2001, 42, 7409-7412; c) B. Shi, R. W.
Boyle, J. Chem. Soc., Perkin Trans. 1 2002, 1397-1400; d) S. Horn, B.
Cundell, M. O. Senge, Tetrahedron Lett. 2009, 50, 2562-2565.
[35] L. Rogers, N. N. Sergeeva, E. Paszko, G. M. F. Vaz, M. O. Senge,
PLoS One. 2015; 10(5): e0125372.
[25] A. Nakano, H. Shimidzu, A. Osuka, Tetrahedron Lett. 1998, 39, 9489-
9492.
[
26] M. S. Driver, J. F. Hartwig, J. Am. Chem. Soc. 1996, 118, 7217-7218;
b) J. F. Hartwig, S. Richards, D. Barañano, F. Paul, J. Am. Chem. Soc.
1
996, 118, 3626-3633.
27] K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett. 1975, 16,
467-4470.
[
[
4
[36] M. O. Senge, M. Zawadzka, Acta Cryst. 2014, C70, 1143-1146.
[37] F. Atefi, O. B. Locos, M. O. Senge, D. P. Arnold, J. Porphyrins
Phthalocyanines 2006, 10, 176-185.
28] a) C. Fischer, B. König, Beilstein J. Org. Chem. 2011, 7, 59-74; b) J.-N.
Heo, Y. S. Song, B. T. Kim, Tetrahedron Lett. 2005, 46, 4621-4625; c)
K. Foo, T. Newhouse, I. Mori, H. Takayama, P. S. Baran, Angew. Chem.
Int. Ed. 2011, 50, 2716-2719.
[38] M.O. Senge, X. Feng, J. Chem. Soc., Perkin Trans. 1 2000, 3615-3621.
[39] A. Ryan, A. Gehrold, R. Persutti, M. Pintea, M. Fazekas, O. B. Locos, F.
Blaikie, M. O. Senge, Eur. J. Org. Chem. 2011, 29, 5817-5844.
[40] A. R. Katritzky, K. W. Law, Magn. Reson. Chem. 1988, 26, 129-133.
[41] M. S. Newman, L. F. Lee, J. Org. Chem. 1972, 37, 4468-4469.
[42] a) K.-i. Sugiura, Y. Fujimoto, Y. Sakata, Chem. Commun. 2000, 1105-
1106; b) B. Bašić, J. C. McMurtrie, D. P. Arnold, J. Porphyrins
Phthalocyanines 2010, 14, 481-493; c) T. A. Pham, F. Song, M. N.
Alberti, M.-T. Nguyen, N. Trapp, C. Thilgen, F. Diederich, M. Stohr,
Chem. Commun. 2015, 51, 14473-14476.
[
29] a) N. Robertson, Angew. Chem., Int. Ed. 2006, 45, 2338-2345; b) L.-L.
Li, E. W.-G. Diau, Chem.Soc. Rev. 2013, 42, 291-304; c) B. E. Hardin,
H. J. Snaith, M. D. McGehee, Nature Photon. 2012, 6, 162-169; d) S.
Kim, L. K. Lee, S. O. Kang, J. H. Yum, S. Fantacci, F. De Angelis, D. Di
Censo, M. K. Nazeeruddin, M. Grätzel, J. Am. Chem. Soc. 2006, 128,
16701-16707.
[
30] a) T. Bessho, S. M. Zakeeruddin, C.-Y. Yeh, E. W.-G. Diau, M. Grätzel,
Angew. Chem., Int. Ed. 2010, 49, 6646-6649; b) A.Yella, H.-W.Lee, H.
N Tsao, C. Yi, A. K.Chandiran, M. K. Nazeeruddin, E. W.-G.Diau, C.-
Y.Yeh, S. M. Zakeeruddin, M. Grätzel, Science 2011, 334, 629-634; c)
S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B. F. E. Curchod, N.
Ashari-Astani, I. Tavernelli, U. Rothlisberger, M. K. Nazeeruddin, M.
Grätzel, Nat. Chem. 2014, 6, 242-247; d) M. Ishida, D. Hwang, Y. B.
Koo, J. Sung, D. Y. Kim, J. L. Sessler, D. Kim, D. Chem. Commun.
[43] B. Bašić, J. C. McMurtrie, D. P. Arnold, Eur. J. Org. Chem. 2010, 4381-
4392.
[44] Y. Liu, H. Lin, J. T. Dy, K. Tamaki, J. Nakazaki, D. Nakayama, S.
Uchida, T. Kubo, H. Segawa, Chem. Commun. 2011, 47, 4010-4012.
[45] R. Shediac, M. H. B. Gray, H. T. Uyeda, R. C. Johnson, J. T. Hupp, P. J.
Angiolillo, M. J. Therien, J. Am. Chem. Soc. 2000, 122, 7017-7033.
[46] a) H. Hope, Prog. Inorg. Chem. 1994, 41, 1-19; b) M. O. Senge, Z.
Naturforsch. 2000, 55b, 336-344.
2
013, 49, 9164-9166; e) M. Ishida, S. W. Park, D. Hwang, Y. B. Koo, J.
L. Sessler, D. Y. Kim, D. J. Kim, J. Phys. Chem. C 2011, 115, 19343-
9354.
1
[47] Bruker. (2014). SAINT, APEX2 and SADABS. Bruker AXS Inc.,
Madison, Wisconsin, USA
[
31] a) X. D. Feng, M. O. Senge, Tetrahedron 2000, 56, 587-590; b) X. D.
Feng, M. O. Senge, J. Chem. Soc., Perkin Trans. 1 2001, 1030-1038;
c) M. O. Senge, I. Bischoff, Eur. J. Org. Chem. 2001, 1735-1751.
[48] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H.
Puschmann, J. Appl. Cryst. 2009, 42, 339-341.
[32] a) V. Lin, S. DiMagno, M. Therien, Science 1994, 264, 1105-1111; b) A.
Ryan, A. Gehrold, R. Perusitti, M. Pintea, M. Fazekas, O. B. Locos, F.
[49] G. M. Sheldrick, Acta Cryst. 2015, A71, 3-8.
[50] G. M. Sheldrick, Acta Cryst. 2008, A64, 112-122
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201700093
FULL PAPER
FULL PAPER
5,10- and 5,15-substituted push-pull
porphyrins
Alina Meindl, Shane Plunkett, Aoife A.
Ryan, Keith J. Flanagan, Susan
*
Callaghan, Mathias O. Senge
Page No. – Page No.
Comparative synthetic strategies for
the generation of 5,10- and 5,15-
substituted push-pull porphyrins
Due to the rise in demand for A
2
BC push-pull porphyrins for applications, such as in dye-
sensitized solar cells (DSSC), we undertook a comparative analysis of synthetic strategies for
both 5,10-substituted and 5,15-substituted porphyrins. This approach combines well-known
reactions with a strategic and logical stepwise functionalization, allowing researchers to
change and modify the electronic properties of these systems of interest at various points of
the syntheses.
This article is protected by copyright. All rights reserved.