Synthesis of porphyrin-bis(polyazamacrocycle) triads via Suzuki coupling reaction

Article abstract of DOI:10.1142/S1088424614500084

Suzuki-Miyaura cross-coupling reaction has been used for the synthesis of tricyclic architectures based on trans-A₂B₂-porphyrins and bisaminal-protected polyazamacrocycles which are linked directly or by a p-phenylene spacer. This mo

Full text of DOI:10.1142/S1088424614500084

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2014; 18: 35–48
DOI: 10.1142/S1088424614500084
Published at http://www.worldscinet.com/jpp/
Synthesis of porphyrin-bis(polyazamacrocycle) triads
via Suzuki coupling reaction
Julien Michalaka, Kiril P. Birina,b, Sankar Muniappana, Elena Ranyuka,
YuliaYu. Enakievaa,b, Yulia G. Gorbunova*b◊, Christine Sterna◊,
Alla Bessmertnykh-Lemeunea and Roger Guilard*a◊
a Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB, UMR 6302),
9 Avenue Alain Savary — BP 47870, 21078 Dijon Cedex, France
b Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninsky pr. 31, GSP-1, 119071 Moscow, Russia
Dedicated to Professor Aslan Tsivadze on the occasion of his 70th birthday
Received 7 January 2014
Accepted 25 January 2014
ABSTRACT: Suzuki–Miyaura cross-coupling reaction has been used for the synthesis of tricyclic
architectures based on trans-A2B2-porphyrins and bisaminal-protected polyazamacrocycles which are
linked directly or by a p-phenylene spacer. This modular approach allowed the synthesis of ligands
with various substituted porphyrin macrocycles and bisaminal-protected tetraazamacrocycles possessing
different cavity sizes. These molecules can be assembled into dimers using a DABCO linker. Deprotection
of these compounds afforded porphyrin-bis(polyazamacrocycle) triads.
KEYWORDS:A2B2-porphyrins, polyazamacrocycles, Suzuki–Miyaura coupling reaction, multi-dentate
ligands.
macrocycles and expected synergetic effects explain
INTRODUCTION
why the design of such sophisticated molecules
Over the last decades, there has been an increasing
is a promising field of research. The most simple
demand for porphyrins bearing additional donor
methodology to prepare these bicyclic ligands relies on
groups at the periphery of the tetrapyrrolic macrocycle.
a covalent bonding of two pre-formed cyclic chelators.
The presence of bimetallic sites in a number of
According to this synthetic approach, a long-chain linear
metalloenzymes has stimulated the synthesis of numerous
spacer is often a key moiety to perform the successful
biomimetic models starting from these substituted
coupling of the two precursors. In this context and
porphyrin derivatives. In this regard, compounds made
due to our continuous interest to porphyrinic multi-
of porphyrinic and polyazamacrocyclic moieties have
decker sandwich complexes, we have prepared ligands
attracted a considerable interest for applications in
containing porphyrin and polyazamacrocyclic fragments
molecular recognition, as well as for the development
linked by a short and rigid spacer. The Suzuki–Miyaura
of contrast agents for medical imaging and fluorescent
cross-coupling reaction [6–8] was a priori an appropriate
markers in molecular biology [1–5]. The outstanding
synthetic tool to obtain these compounds because this
coordination and physicochemical properties of both
coupling reaction was widely used for the preparation
of many porphyrin derivatives [9–14]. Moreover, it
has been shown that this reaction proceeds smoothly
◊SPP full member in good standing
for poly(halo)porphyrins and/or poly(dialkoxyboryl)-
porphyrins affording sophisticated molecular systems
*Correspondence to: Roger Guilard, email: roger.guilard@u-
bourgogne.fr, tel: +33 (0)380-396-111, fax: +33 (0)380-396-117
Copyright © 2014 World Scientific Publishing Company

36
J. MICHALAK ET AL.
and arrays [15–18]. However, it is known that the product
yield is strongly dependent on the nature of the coupling
partners and the experimental conditions because
numerous side reactions such as dehydrohalogenation
[19] and deborylation [20] compete with the coupling
reaction. Indeed, the choice of a practical experimental
protocol is quite challenging. According to literature
data, the starting porphyrin can be either an arylboronic
coupling partner or a halo-substituted reagent [5, 10,
21–24]. Moreover, the porphyrin used can be in the
form of a free-base or a metal complex [25]. Finally,
different catalysts and solvents have been used and have
shown their efficiency but a systematic analysis of their
influence on the product yield is still not available and
experimental conditions should be optimized according
to the substrate nature.
Herein, we report that the Suzuki–Miyaura cross-
coupling reaction can be successfully used for the
preparation of a tricyclic architecture based on trans-
A2B2-porphyrins and bisaminal-protected polyazamacro-
cycles linked directly or by a p-phenylene spacer (Chart
1). According to this approach, fine tuning of structural
parameters of sophisticated target ligands is possible
through structural modification of the pre-formed
macrocyclic components and spacers. This modular
approach was successful for the preparation of ligands
with various substituted porphyrin macrocycles and
tetraazamacrocycles characterized by different cavity sizes
andspacersofdifferentlengths. Moreover, thedeprotection
procedure leading to porphyrin-benzannulated polyaza-
macrocycle systems is discussed. These molecular
systems should offer an efficient entry in the design of
supramolecular architectures formed by coordination-
driven assembly of porphyrinic or polyazamacrocyclic
fragments [26]. Finally, our preliminary results describing
the assembly of these molecules in porphyrinic dimers
using DABCO molecule as a linker provide the first
example of such architectures.
RESULTS AND DISCUSSION
Transition metal-catalyzed reactions have been used
to develop a new powerful synthetic strategy for the post-
modification of porphyrinic macrocycles [24]. However,
these reactions are much more difficult to perform for
saturated polyazamacrocycles which are known to
be very strong chelators of transition metals [27–31].
Retrosynthetic analysis for the preparation of target
porphyrin-benzannulated polyazamacrocycle systems
points out bromo-substituted polyaza derivatives 1, 2
and porphyrins 3, 4 as starting compounds (Scheme 1).
Indeed, bromoporphyrins are readily available and are
usual intermediate derivatives in porphyrin synthesis.
Aminal derivatives of polyazamacrocycles 1 and 2 are
available according to literature procedures and these
compounds can be deprotected under acid conditions
giving the target polyazamacrocycles [32, 33]. These
compounds should be more reactive in the presence
of palladium catalysts, as compared to the parent
polyazamacrocycles. Moreover palladium complexes
of these ligands are also described in the literature [34],
indicating that the choice of experimental conditions for
coupling reactions is challenging.
The bromo-functionalized polyazamacrocycles were
prepared starting from the corresponding linear tetra-
aminesaccordingtoScheme2.Theliteratureexperimental
procedure dealing with the synthesis of bis(aminal)-
protected tetraazamacrocycles based on unsubstituted
1,2-bis(bromomethyl)benzene [35] was optimized and
the target products 1 and 2 were obtained in one step
in 37% and 53% yields, respectively. This difference in
Ph
R
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
M
M
R
Ph
R = H, Mes ; M = 2H, Zn
N
N
N
N
N
N
N
;
;
N
N
N
N
=
N
HN
NH
NH
NH
NH
HN
HN
NH
Chart 1. Schematic representation of target porphyrin-bis(polyazamacrocycle) triads
Copyright © 2014 World Scientific Publishing Company
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SYNTHESIS OF PORPHYRIN-BIS(POLYAZAMACROCYCLE) TRIADS VIA SUZUKI COUPLING REACTION
37
N
N
N
N
N
N
N
N
Br
Br
1
R
M
R
Ph
N
N
N
N
N
N
N
N
Br
Br
M
Br
Br
Ph
3H2, M = H ; 3Zn, M = Zn
R = H
4H2, M = H ; 4Zn, M = Zn
R = Mes 5H2, M = H ; 5Zn, M = Zn
Pd
Pd
R
M
R
Ph
M
N
N
N
N
N
N
O
O
O
O
O
O
B
B
B
B
O
O
N
N
Ph
6H2, M = H ; 6Zn, M = Zn
R = H
7H2, M = H ; 7Zn, M = Zn
R = Mes 8H2, M = H ; 8Zn, M = Zn
Scheme 1. The building blocks for the synthesis of porphyrin-polyazamacrocycle ligands
Br
Br
O
H
N
H
N
NH
2 H2N
N
N
N
N
n
O
Br Br
K2CO3
NH
HN
n
N
N
n
1, n = 0
2, n = 1
Scheme 2. Synthesis of bromides 1 and 2
product yields shows the major influence of the linear
polyamine structure on the course of the protection
and cyclization reactions and reflects the key role of
steric factors for the studied reactions. 1H and 13C NMR
spectra of 1 and 2 reveal two partially overlapped sets of
signals indicating the presence of two diastereoisomers
expected for these compounds taking into account a
syn arrangement of the two methyl substituents in the
bis(aminal)-protected tetraazamacrocycle bearing a non-
substituted phenyl ring [35].
be more efficient for porphyrin derivatives because
Pd-catalyzed transformations of polyazamacrocycles
is challenging taking into account the coordinating
properties of substrates. Thus, pinacolboran-substituted
free base porphyrins 6H2–8H2 and the corresponding
zinc complexes 6Zn–8Zn were prepared according to
optimized literature procedures [10, 15, 17, 18, 22, 36].
Some comments on the synthesis of dialkoxyboryl-
porphyrins which are useful intermediates in porphyrin
chemistry deserve attention.
A priori the synthesis of boronic acid esters should
be carried out to obtain the electrophilic moiety needed
for the coupling reactions. This reaction appears to
Meso-(dibromoporphyrinato)zinc 3Zn reacts smoo-
thly with pinacolborane in the presence of PdCl2(PPh3)2
and NEt3 in dichloroethane giving the target product
Copyright © 2014 World Scientific Publishing Company
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38
J. MICHALAK ET AL.
6Zn in 85% yield. Surprisingly, demetalation of this
compound in acid conditions (TFA, HCl) was not
observed and the free base porphyrin boronic acid
ester 6H2 was obtained only through borylation of
the free base porphyrin 3H2 in lower yield (23%)
because the dehalogenation of 3H2 was observed as a
side process under these reaction conditions. Meso-
(4-bromophenyl)porphyrin 5Zn does not react with
pinacolborane under these conditions and PdCl2(dppf)
which bears a chelating ligand is also inefficient for this
reaction. Using bis(pinacolato)diboron, PdCl2(dppf) and
potassium acetate in toluene led to the desired product
8Zn in moderate yield (38%). A more polar solvent
DMSO ensured a smooth coupling reaction, affording
the desired derivative in 71% yield. However, further
experiments have demonstrated that the product yield
is extremely dependent on the reagent quality and
numerous attempts to reproduce our preliminary results
were unsuccessful. These experimental difficulties point
out that it is more convenient to prepare porphyrins 7H2
and 8H2 by reacting boryl-substituted aldehyde and
dipyrromethane according to the Lindsey method [18].
The reactions of some of these precursors were then
studied. A priori, the porphyrins 7H2 and 8H2 and their
complexes 7Zn and 8Zn bearing boronic substituent
on phenyl ring, should react with aryl halides under
experimental conditions suitable to preserve the phenyl-
boronic esters. Indeed, 8H2 smoothly reacted with bromo-
benzene in THF in the presence of a Pd(OAc)2/PPh3
catalyst and 0.5 M aqueous sodium carbonate solution,
affording the double cross-coupling derivative 5,15-
bis(biphenyl)porphyrin (9H2) in 71% yield. However,
when halide 1 was reacted under the same conditions, a
complex mixture of products was obtained according to
MALDI-TOF and 1H NMR analysis (Scheme 3, Table 1,
entry 1).
derivatives, but was described for the Suzuki–Miyaura
cross-coupling reaction of electron-rich aromatic
substrates [37]. To obtain the desirable product in higher
yield, we have explored different reaction conditions,
changing the nature of the base, solvent and catalyst
(Table 1). Firstly, the reaction was carried out in the
absence of water (Table 1, entries 2–4). Only the use of
strong bases such as Cs2CO3 induced the coupling reaction
in THF or toluene. However, under these conditions,
the reaction was still non-selective giving a mixture of
the target product 10H2, as well as biphenyl and phenyl
derivatives 11H2 and 12H2 (Scheme 3). The presence of
the latter compound demonstrated that a deborylation
reaction is observed under these conditions. An electron-
donor ligand such as P(o-Tol)3 and Buchwald’s biphenyl
phosphines which were found to be efficient for coupling
of aromatic substrates [38], were also inefficient in the
presence of Cs2CO3, KF or K3PO4 (Table 1, entries 5–9).
When dppf was taken as a ligand in a two fold excess
with respect to palladium acetate, the selectivity was
significantly improved, but the reaction was too slow
(Table 1, entry 10). Somewhat surprisingly, better results
were obtained when Pd(OAc)2 and dppf were taken in
equal amount (20 mol%), even if the formation of the
bicyclic compound 11H2 was again observed as a side-
reaction under these conditions (Table 1, entry 11). 10H2
and 11H2 were isolated by column chromatography on
silica and additionally purified by a preparative exclusion
chromatography.
Thestructuralmodificationofthepolyazamacrocyclic
fragment does not change the reactivity of the bromide
precursor and when compound 2 was reacted under
these conditions, the product 14H2 was obtained in 24%
yield. Moreover, porphyrins functionalized by different
electron-withdrawing substituents at the periphery
of the macrocycle can be used as metal complex.
Indeed, the product yield does not change when Zn(II)-
porphyrinato boronic ester 7Zn was coupled with
bromide 1 and the target compound 15Zn was isolated
in 26% yield using two consecutive chromatographic
purifications.
Among the target product 10H2, two by-products 9H2
and 11H2 were formed in equal quantities. These products
resulted from the ligand inter-exchange reaction observed
through intermediate (PPh3)2Pd(aryl)2 complex. This
side reaction was never reported before for porphyrin
R
R
R
N
N
N
N
N
N
N
N
N
N
N
N
O
O
O
O
1 or 2, Pd(OAc)2, ligand
M
Y
B
X
X
+
B
M
M
X
base, toluene
R
R
R
M = Zn, R = H, 7Zn
M = 2H, R = Mes, 8H2
M = 2H, R = Mes, X = Ph, 9H2
M = 2H, R = Mes, X = A, 10H2
M = 2H, R = Mes, X = H, 13H2
M = 2H, R = Mes, X = B, 14H2
M = Zn, R = H, X = A, 15Zn
M = 2H, R = Mes, X = A, Y = Ph, 11H2
M = 2H, R = Mes, X = A, Y = H, 12H2
M = Zn, R = H, X = A, Y = Ph, 16Zn
N
N
N
N
N
N
N
N
A =
B =
Scheme 3. Synthesis of p-phenylene-linked polyazamacrocycle-porphyrin triads
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 38–48

SYNTHESIS OF PORPHYRIN-BIS(POLYAZAMACROCYCLE) TRIADS VIA SUZUKI COUPLING REACTION
Table 1. Optimization of experimental conditions for cross-coupling reaction of 8H2 with bromide 1a
39
Entry
Ligand
Base
Solvent
Ratio of products, %b
9H2
10H2
11H2
12H2g
13H2g
1
2
3
4
5
PPh3
Na2CO3c
Na2CO3
Cs2CO3
Cs2CO3
Cs2CO3
THF/H2O (4:1)
THF
20
0
40
0
20
0
0
0
0
0
PPh3
PPh3
Toluene
THF
0
60
50
10
40
40
0
0
0
PPh3
0
10
40
0
P(o-Tol)3
THF
0
50
P(tBu)2
6
Cs2CO3
Cs2CO3
KF
THF
THF
THF
0
0
0
20
15
0
0
0
0
80
60
0
0
0
0
(Me)2N
7
P(tBu)2
8d
9e
10
K3PO4
THF
0
0
0
15
20
75
0
0
0
0
0
0
0
0
dppf
dppff
Cs2CO3
Cs2CO3
Toluene
Toluene
11
25
a General reaction conditions: 0.05 mmol 8H2, 3 eq. of bromide 1, 20 mol% of Pd(OAc)2, 40 mol% of the ligand in 3 mL of solvent
was refluxed until complete conversion of the starting material. b Determined by MALDI-TOF MS analysis. c 25 equiv. of Na2CO3
(0.17 M) in THF/H2O (5:1 v/v). d Conversion was less than 80% after 24 h, bicyclic compound formed in the coupling reaction was
a major product. e Conversion was about 50% after 24 h, bicyclic compound formed in the coupling reaction was the major product.
f 20 mol% of dppf was used. g 12H2 and 13H2 were only observed by MALDI-TOF MS in optimization experiments.
Ph
M
Ph
M
Ph
M
N
N
N
N
N
N
N
N
N
N
N
N
O
O
O
O
1 or 2, Pd(OAc)2, ligand
B
B
X
Y
X
X
+
base, toluene
Ph
Ph
Ph
M = H2, 6H2
M = Zn, 6Zn
M = 2H, X = A, 17H2
M = Zn, X = A, 17Zn
M = Zn, X = B, 20Zn
M = Zn, X = A, Y = Ph, 18Zn
M = 2H, X = A, Y = H, 19H2
M = Zn, X = A, Y = H, 19Zn
N
N
N
N
N
N
N
A =
B =
N
Scheme 4. Synthesis of directly linked porphyrin-bis(polyazamacrocycle) triads
Next, the coupling reaction was used for the synthesis
of bis(polyazamacrocycle)-porphyrin triads without a
p-phenylene linker (Scheme 4).
Taking into account the steric hindrance of the
starting compounds, catalyst loading was increased up
to 50 mol% in the preliminary experiments. Firstly, the
coupling reaction of 6Zn with bromide 1 was carried
out with different ratios of THF/H2O mixtures using
Na2CO3 as a base. The reaction afforded a mixture of
three products, 17Zn–19Zn, in equal amounts due to the
reductive deborylation and the ligand exchange reactions
proceeding in parallel with the coupling (Table 2,
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 39–48

40
J. MICHALAK ET AL.
Table 2. Optimization of experimental conditions for cross-coupling of 6H2 and 6Zn with bromide 1
Entry
Ligand (mol%)
Pd(OAc)2 (mol%)
Base (eq, C)
Solvent
Ratio of products, %b
17Mc,e
18Mc,f
19Mc,f
1
2
3d
4
5
6
7
8
9
Ph3P (100)
Ph3P (100)
Ph3P (100)
Ph3P (100)
Ph3P (100)
Ph3P (100)
Ph3P (100)
Ph3P (20)
dppf (10)
50
50
50
50
50
50
50
10
10
Na2CO3 (25, 0.17 M)
Na2CO3 (25, 0.17 M)
Na2CO3 (25, 0.17 M)
Ba(OH)2 (48)
THF/H2O (5:1)
THF/H2O (20:1)
THF/H2O (20:1)
THF/H2O (20:1)
THF
33
33
33
33
—
3
33
33
33
30
33
50
40
—
—
66 (23)
66
Ba(OH)2 (10)
33
33
—
40
—
—
Cs2CO3 (10)
THF
50
Cs2CO3 (10, 0.17 M)
Cs2CO3 (10)
THF/H2O (20:1)
THF
20
100
100 (78)
Cs2CO3 (4)
Toluene
a General reaction conditions: 0.04–0.05 mmol 6Zn, 3 eq. of bromide 1 in 6 mL of solvent under reflux until complete conversion of
the starting material. b Determined by MALDI-TOF MS analysis. Isolated yields are given in parentheses. c M = Zn for all entries,
except for entry 3 where M = H2. d 6H2 was used as a starting porphyrin. e 17H2 was not fully characterized. f 18Zn, 19H2 and 19Zn
were only observed by MALDI-TOF MS in optimization experiments.
entries 1, 2). When free base 6H2 was reacted with
bromide 1 under these conditions, 17H2 was obtained as
a major product according to MALDI-TOF analysis but
was isolated only in 23% yield (Table 2, entry 3).
account that bromides 1 and 2 were obtained as mixtures
of two diastereomers possessing a syn-orientation of the
methyl substituents, one should expect the formation of
stereoisomer mixtures in the cross-coupling reaction of
these compounds with porphyrin 8H2 characterized by
two sets of signals corresponding to two diastereomers.
As a result, the protons of all methylene groups being
diastereotopic in each isomer appear as complex
multiplets. The chemical shifts of the four benzylic
protons are significantly different from one another and
their splitting pattern is more simple as compared to
other aliphatic protons. Thus, each of them appears as a
doublet giving a system of signals which are typical of the
studied derivatives. Additional evidence of the structural
assignment was obtained after deprotection of these
macrocycles (discussed below), affording an expected
simplification of the spectra as shown for compound 10H2
in Fig. 1.
The synthesized tricyclic ligands were further
subjected to acidic cleavage of aminal protective groups
(Scheme 5). The deprotection was found to be inefficient
with TFA in solutions of CH2Cl2. Under these conditions,
only demetalation of the zinc porphyrins 15Zn, 17Zn and
20Zn was observed according to MALDI-TOF analysis.
The treatment of compounds 10H2 and 11H2 with 10%
HCl aqueous solution in ethanol at room temperature
induces the bisaminal cleavage (Scheme 5). The bicyclic
and tricyclic polyazamacrocyclic-porphyrin ligands
21H2 and 22H2 were obtained in 83% and 89% yields,
respectively.
Optimization of the reaction was carried out using
the more available zinc porphyrinate 6Zn as a starting
compound. The change of the base to Ba(OH)2 afforded
a better yield of the desired derivative 17Zn, but still
did not improve the selectivity of the reaction (Table 2,
entry 4). In the absence of water (Table 2, entries 5, 6),
the deborylation reaction was suppressed when Cs2CO3
was used as a base (Table 2, entry 6), but the yield of
the target product was low due to the ligand exchange
reaction leading to 19Zn. When aqueous Cs2CO3 was
employed, the tricycle 17Zn was obtained only as a
minor product (Table 2, entry 7). Surprisingly, when
the catalyst loading was decreased up to 10 mol%, only
the coupling product was observed (Table 2, entries 8,
9). Both PPh3 and dppf were efficient ligands when the
reaction was carried out in THF or toluene, respectively.
However, the product purification was more simple in the
case of dppf. The reaction of 6Zn with bromide 2 also
proceeds smoothly at the conditions of entry 9, affording
the target compound 20Zn in 93% yield.
The newly synthesized porphyrin-bis(polyazamacro-
cycle) compounds 10H2, 14H2, 15Zn, 17Zn and 20Zn
were characterized using conventional methods. It has to
be noted, that all these compounds are strong bases. The
presence of trace acid or water in the deuterated solvents
leads to signal broadening in NMR spectra and induces
some difficulties for the characterization. For this reason,
all solvents used in this study were filtered through a short
pad of K2CO3. As shown in Fig. 1 for compound 10H2, 1H
NMR spectra of these compounds were rather complicated
indicating the presence of stereoisomers. Taking into
Surprisingly, the deprotection of polyazamacrocycle
directly attached to the porphyrin macrocycle is more
difficult and requires a 20% HCl aqueous solution.
When zinc-porphyrinate 17Zn was deprotected under
these conditions, only the free base porphyrin 23H2
Copyright © 2014 World Scientific Publishing Company
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SYNTHESIS OF PORPHYRIN-BIS(POLYAZAMACROCYCLE) TRIADS VIA SUZUKI COUPLING REACTION
41
Fig. 1. 1H NMR spectra of 10H2 and 22H2
Mes
Mes
NH
N
NH
N
N
N
10% HCl
Y
X
A'
A
EtOH
HN
HN
Mes
Mes
HN
NH
NH
X = A, 10H2
X = Ph, 11H2
X = A', Y = Ph, 21H2
X, Y = A', 22H2
A' =
NH
Ph
Ph
N
N
HN
N
N
N
20% HCl
EtOH
Zn
A
A'
A
A'
NH
N
Ph
17Zn
Ph
23H2
Scheme 5. Acidic cleavage of aminal protective groups of polyazamacrocycle-appended porphyrins
was detected in the reaction mixture by MALDI-TOF
analysis. However, a significant signal broading was
observed in the 1H NMR spectra of the product recorded
in different organic solvents. These data confirm the
absence of a bisaminal protective group but a complete
structural determination was not possible. Unfortunately,
our attempts to grow single crystals for X-ray diffraction
analysis were unsuccessful.
formation of sandwich-type polytopic receptors, we have
investigated their interaction with DABCO upon variation
of the temperature. Metalloporphyrins are known to form
stable complexes with DABCO. The axial ligation of
the metalloporphyrin by a DABCO molecule may lead
to the formation of a 1:1 complex or a dimer bridged
by a DABCO molecule, depending on the ratio of the
two compounds [39–41]. It is well-established that this
reaction can be studied by 1H NMR spectroscopy because
ligated DABCO shows characteristic a proton signals for
each species and quantitative information on the reaction
To better understand in the influence of steric factors
induced by polyaza-fragments on the assembling of
the newly synthesized tricyclic ligand and the potential
Copyright © 2014 World Scientific Publishing Company
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42
J. MICHALAK ET AL.
Fig. 2. VT-NMR titration of 20Zn with DABCO in CDCl3 at (a) 303 K and (b) 203 K
N
N
Ph
N
N
N
N
N
N
N
N
N
Zn
N
N
N
Ph
Ph
N
N
N
N
N
Zn
N
N
N
Ph
N
N
N
N
Ph
20Zn x DABCO
N
N
N
N
N
N
Zn
N
N
N
N
N
N
Ph
[20Zn]2 x DABCO
N
N
Fig. 3. Monomeric and dimeric associates of 20Zn and DABCO
stoechiometry can be readily calculated from spectral
data. The most sterically hindered bisaminal protected
compound 20Zn was taken as a model compound for the
investigation of DABCO-induced dimerization using a
variable temperature 1H NMR titration (Fig. 2). The spectra
of a 8.7 × 10-3 M solution of 20Zn containing a gradually
increasing amount of DABCO was monitored from 303
K to 203 K to detect the formation of the monomeric (M)
and dimeric (D) porphyrin complexes (Fig. 3).
The assembling process leading to the formation of
porphyrin dimers D results in characteristic upfield shift
of the DABCO NMR signals to the region of -5 ppm as
a result of the influence of magnetic anisotropy of two
porphyrin aromatic p-systems. In contrast, in the case
of a 1:1 monomeric complex, two types of protons are
present in the molecule of DABCO, showing two different
resonances or a smaller upfield shift of one signal when
the complex is labile. Indeed, both expected changes
in the position of the DABCO signals were observed
as shown in Fig. 2, indicating that sterically hindered
porphyrin 20Zn formed expected complexes with
DABCO depending on the ratio between the reagents.
Both complexes are clearly observed at 203 K in the
aromatic and up-field region of the spectrum. However,
an increase of the temperature leads to a broadening of the
aromatic signals and a collapse of the DABCO protons,
indicating the labile character of the studied complexes
in CDCl3 solution.
EXPERIMENTAL
General
All reactions were performed in oven-dried glassware
under a slight positive pressure of nitrogen. All chemicals
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 42–48

SYNTHESIS OF PORPHYRIN-BIS(POLYAZAMACROCYCLE) TRIADS VIA SUZUKI COUPLING REACTION
43
used were of analytical grade and were purchased from
ppm 1.16 (s, 6H, CH3-aminal), 1.51 (s, 6H, CH3-aminal),
1.96–2.16 (m, 2H, CH2N), 2.24–2.38 (m, 2H, CH2N),
2.46–2.72 (m, 12H, CH2N), 2.85–2.98 (m, 4H, CH2N),
2.99–3.12 (m, 2H, CH2N), 3.13–3.20 (m, 4H, CH2N,
CH2-Ar), 3.38 (d, 1H, J = 15.3 Hz, CH2-Ar), 3.43 (d, 1H,
J = 15.3 Hz, CH2-Ar), 4.17 (d, 1H, J = 15.3 Hz, CH2-Ar),
4.18 (d, 1H, J = 15.3 Hz, CH2-Ar), 4.47 (d, 1H, J = 15.3
Hz, CH2-Ar), 4.49 (d, 1H, J = 15.3 Hz, CH2-Ar), 6.85
(d, 1H, J = 8.1 Hz, HAr), 6.95 (d, 1H, J = 8.1 Hz, HAr),
7.12 (d, 1H, J = 2.1 Hz, HAr), 7.17 (d, 2H, J = 8.1 Hz,
HAr), 7.24 (d, 1H, J = 2.1 Hz, HAr). 13C NMR (75 MHz,
CDCl3) (mixture of two diastereomers in 1:1 ratio): d,
ppm 12.1 (1C, CH3), 12.2 (1C, CH3) 13.6 (2C, CH3), 45.4
(2C, CH2), 45.8 (2C, CH2), 46.8 (2C, CH2), 50.5 (2C,
CH2), 50.7 (2C, CH2), 51.9 (1C, CH2), 52.0 (1C, CH2),
53.6 (1C, CH2), 53.8 (1C, CH2), 58.1 (2C, CH2), 77.2
(1C, C), 77.3 (1C, C), 80.3 (2C, C), 120.3 (1C, C), 120.6
(1C, C), 129.5 (1C, CH), 129.6 (1C, CH), 130.0 (1C,
CH), 131.0 (1C, CH), 131.6 (1C, CH), 132.8 (1C, CH),
137.2 (1C, C), 139.2 (1C, C), 140.4 (1C, C), 142.7 (1C,
C). ESI-HRMS: m/z 377.1306 [MH]+; calcd. 377.1341.
Elemental analysis: C, 56.98; H, 6.28; N, 14.72; calcd.
for C18H25N4Br: C, 57.30; H, 6.68; N, 14.85.
Acros and Aldrich Co. unless stated otherwise. Solvents
were dried using standard reported procedures [42].
Pyrrole was freshly distilled under nitrogen. Silica gel
(0.04–0.063 mm, 230-400 mesh ASTM, Merck) and
Alumina 90 neutral (0.063–0.200 mm, 70-230 mesh
ASTM, Merck) were used for column chromatography.
Analytical thin-layer chromatography (TLC) was carried
out using Merck silica gel 60 plates (precoated sheets,
0.2 mm thick, with fluorescence indicator F254).
4-Bromo-1,2-bis(bromomethyl)benzene [43], 4,5-
dibromo-1,2-bis(bromomethyl)benzene [44], 4-(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)-benzaldehyde [13],
5,10-dibromo-15,20-diphenyl-porphyrin 3H2 and 3Zn
[45], 5,15-dimesityl-10,20-bis(4-bromophenyl)-porphyrin
5H2 [46] and 5Zn [47], 5,15-diphenyl-10,20-bis(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)-porphyrin 6Zn [22],
5,15-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-
phenyl)-porphyrin 7H2 [15, 18, 36] and 5,15-dimesityl-
10,20-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-
2-yl)phenyl)-porphyrin 8H2 [10, 17], were prepared
1
according to literature procedures. H and 13C spectra
were recorded on a Bruker Avance III 300 and a Bruker
Avance III 600. All chemical shifts are given in ppm,
referenced on the d scale using residual solvent peak as
Compound 2. A solution of N1,N1′-(propane-1,3-diyl)-
bis(ethane-1,2-diamine) (1.162 g, 7.3 mmol) in 35 mL of
CH3CN was cooled to -10°C and 0.64 mL of butadione
(7.3 mmol) were added dropwise. The reaction mixture
was stirred for 4.5 h and then warmed to rt. Then K2CO3
(5.04 g, 5 equiv.) and 4-bromo-1,2-bis(bromomethyl)-
benzene (2.5 g, 7.3 mmol) in 35 mL of acetonitrile were
added to this solution and the reaction mixture was heated
to 65°C. After 18 h, the suspension was filtered and the
precipitate was washed with CH3CN (3 × 20 mL). The
volatiles were removed under vacuum and the residue was
purified by column chromatography on alumina using
CH2Cl2 as eluent. The product was obtained as colourless
solid (1.5 g, 53%). 1H NMR (300 MHz, CDCl3) (mixture
of two diastereomers in 1:1 ratio): d, ppm 1.05 (dd, 2H,
J = 12.9 Hz, J = 2.7 Hz, CH2), 1.30 (s, 6H, CH3-aminal),
1.38 (s, 6H, CH3-aminal), 1.80 (dt, 2H, J = 12 Hz, J = 2.7
Hz, CH2), 2.17–2.28 (m, 6H, CH2N), 2.29–2.42 (m, 2H,
CH2N), 2.51–2.57 (m, 6H, CH2N), 2.58–2.68 (m, 4H,
CH2N), 2.73–2.81 (m, 2H, CH2N), 3.12 (d, 1H, J = 14.7
Hz, CH2-Ar), 2.25–3.20 (m, 2H, CH2N), 3.17 (d, 1H, J =
14.7 Hz, CH2-Ar), 3.40 (d, 1H, J = 14.7 Hz, CH2-Ar),
3.42 (d, 1H, J = 14.7 Hz, CH2-Ar), 3.72–4.25 (m, 2H,
CH2N), 4.01 (d, 1H, J = 14.7 Hz, CH2-Ar), 4.06 (d, 1H,
J = 14.7 Hz, CH2-Ar), 4.45 (d, 1H, J = 14.7 Hz, CH2-Ar),
4.50 (d, 1H, J = 14.7 Hz, CH2-Ar), 6.82 (d, 1H, J = 8.1
Hz, HAr), 6.95 (d, 1H, J = 8.1 Hz, HAr), 7.09 (d, 1H, J =
4.1 Hz, HAr), 7.17 (dd, 1H, J = 8.1 Hz, J = 4.1 Hz, HAr),
7.18 (dd, 1H, J = 8.1 Hz, J = 4.1 Hz, HAr), 7.23 (d, 1H,
J = 4.1 Hz, HAr). 13C NMR (75 MHz, CDCl3) (mixture of
two diastereomers in 1:1 ratio): d, ppm 11.1 (1C, CH3),
11.2 (1C, CH3) 11.4 (2C, CH3), 17.9 (2C, CH2), 44.6 (2C,
CH2), 45.2 (2C, CH2), 46.9 (2C, CH2), 49.5 (2C, CH2),
50.5 (2C, CH2), 52.0 (1C, CH2), 52.1 (1C, CH2), 54.1
1
internal standard for H and 13C. UV-Vis spectra were
recorded with a Varian Cary 100 spectrophotometer.
Mass spectra were obtained in linear mode with a Bruker
Ultraflex II LRF 2000 MALDI-TOF mass spectrometer
usingdithranolasmatrixandaccuratemassmeasurements
(HRMS) using an Orbitrap ESI-TOF mass spectrometer.
Elemental analysis were obtained using a EA1112 CHNS
Thermo Electron Flash analyser. The measurements were
made at the “Pôle Chimie Moléculaire”, the technological
platform for chemical analysis and molecular synthesis
(http://www.wpcm.fr) which relies on the Institute of
the Molecular Chemistry of University of Burgundy and
WelienceTM, a Burgundy University private subsidiary.
Synthesis
Compound 1. A solution of N1,N1′-(ethane-1,2-diyl)-
bis(ethane-1,2-diamine) (1.66g, 78mmol) in 20mL of
CH3CN was cooled to -7°C. Then 2,3-butanedione
(0.68 mL, 7.8 mmol) was added dropwise. The reaction
mixture was stirred for 3.5 h at -7°C and warmed to rt.
After addition of K2CO3 (5.38 g, 39 mmol), a solution of
o,o′-dibromomethylbenzene (2.055 g, 7.8 mol) in 15 mL
of acetonitrile was slowly (1 h) introduced in the reaction
mixture and stirring was continued for an additional
24 h. The suspension was filtered and the precipitate was
washed with CH3CN (4 × 15 mL). The organic layer and
the filtrate were evaporated to dryness under vacuum. The
residue was chromatographed on alumina using CH2Cl2
and CH2Cl2/methanol (1%). The product was obtained as
1
a colourless solid (1.558 g, 37%). H NMR (300 MHz,
CDCl3) (mixture of two diastereomers in 1:1 ratio): d,
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 43–48

44
J. MICHALAK ET AL.
(1C, CH2), 54.4 (1C, CH2), 58.5 (2C, CH2), 75.5 (2C, C),
78.5 (1C, C), 78.6 (1C, C), 120.0 (1C, C), 120.6 (1C,
C), 129.5 (1C, CH), 129.7 (1C, CH), 129.9 (1C, CH),
130.7 (1C, CH), 131.6 (1C, CH), 132.7 (1C, CH), 137.2
(1C, C), 139.2 (1C, C), 140.4 (1C, C), 142.7 (1C, C).
ESI-HRMS: m/z 391.1467 [MH]+; calcd. 391.1497.
Elemental analysis: C, 55.21; H, 7.09; N, 12.00; calcd.
for C19H27N4Br·H2O: C, 55.75; H, 7.14; N, 13.69.
5,15-Diphenyl-10,20-bis(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)-porphyrin 6H2. 5,15-Dibromo-
10,20-diphenylporphyrin 3H2 (50.0 mg, 0.08 mmol)
and Pd(Ph3P)2Cl2 (3 mg, 3 mol.%) were flushed with
argon. Later freshly distilled dichloroethane (6 mL),
triethylamine (0.28 mL) and pinacolborane (0.24 mL,
1.6 mmol) were added and the mixture was refluxed
for 21 h. The reaction mixture was cooled to ambient
temperature, quenched with saturated aqueous solution
of NaCl. The organic layer was separated, dried over
MgSO4 and evaporated. The residue was purified by
column chromatography on silica gel using CH2Cl2 as an
eluent. Evaporation of the fraction produced the desired
porphyrin as a red solid (14 mg, 23%). The spectral data
of the isolated compound were in good agreement with
the literature data [48].
5,15-Dimesityl-10,20-bis(4-(4,4,5,5-tetramethyl-
1,3,2-dioxaborolan-2-yl)phenyl)-porphyrin 8H2.
5-Mesityldipyrromethane (1.052g, 3.98mmol) and 4-(4,-
4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzald-
ehyde (0.956 g, 4.01 mmol) were dissolved in CH2Cl2
(500 mL). BF3·(OEt)2 (210 mL, 1.95 × 10-3 mmol) was
added to the reaction mixture upon intense stirring. DDQ
(1.360 g, 5.99 mmol) was added after 1 h. The mixture
was kept for additional 1 h before it was neutralized with
1 mL of NEt3 and filtered through silica gel using CHCl3
(1.5 L) as eluent. The volume of the fraction was reduced
and the compound was purified at silica gel with CH2Cl2/
C5H12 (85:15) mixture as eluent. The evaporation of the
fraction produced 8H2 as a violet solid (496.4 mg, 27%).
1H NMR (300 MHz, CDCl3): d, ppm -2.71 (s, 2H, NH),
1.43 (s, 24H, CH3-pinacol), 1.76 (s, 12H, o-CH3), 2.55 (s,
6H, p-CH3), 7.20 (s, 4H, HMes), 8.08 (d, 4H, J = 7.8 Hz,
HPh), 8.16 (d, 4H, J = 7.8 Hz, HPh), 8.60 (d, 4H, J = 4.7
Hz, Hpyr), 8.71 (d, 4H, J = 4.7 Hz, Hpyr).
5,15-Dimesityl-10,20-bis(4-(4,4,5,5-tetramethyl-
1,3,2-dioxaborolan-2-yl)phenyl)-porphyrinato zinc
8Zn. Route 1. Zn(OAc)2 (57.7 mg, 0.263 mmole)
was added to the solution of 5,15-dimesityl-10,20-
bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)
phenyl)-porphyrin 8H2 (50.0 mg, 0.052 mmol) in
CH2Cl2/MeOH mixture (3:1, 20 mL). The mixture was
kept for 6 h at ambient temperature and diluted with
CH2Cl2 (30 mL). The solution was washed with water
(5 × 15 mL), dried over MgSO4. The evaporation of the
fraction produced 8Zn as a pink solid (51.3 mg, 97%).
Route 2. 5,15-Dimesityl-10,20-bis(4-bromophenyl)-
porphyrinato zinc 5Zn (50.0 mg, 0.054 mmol) was
added to a solution of 4,4,4′,4′,5,5,5′,5′-octamethyl-
2,2′-bi(1,3,2-dioxaborolane) (30.3 mg, 0.120 mmol)
in 3 mL of distilled DMSO. PdCl2(dppf) (4.4 mg,
0.005 mmol) and KOAc (16.0 mg, 0.163 mmol) were
added and the mixture was refluxed overnight. After
complete conversion, controlled by MALDI-TOF MS,
the product was extracted with toluene and washed
with a large excess of water. The organic phase was
dried over MgSO4 and the product was purified by
column chromatography on silica gel using CH2Cl2 as
eluent. The evaporation of the fraction produced the
desired zinc porphyrin as a pink solid (38.9 mg, 71%).
1H NMR (300 MHz, CDCl3): d, ppm 1.42 (s, 24H, CH3-
Pin), 1.74 (s, 12H, o-CH3), 2.54 (s, 6H, p-CH3), 7.19 (s,
4H, HMes), 8.10 (d, 4H, J = 7.8 Hz, HPh), 8.18 (d, 4H,
J = 7.8 Hz, HPh), 8.68 (d, 4H, J = 4.6 Hz, Hpyr), 8.80 (d,
4H, J = 4.6 Hz, Hpyr).
5,15-Bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxa-
borolan-2-yl)phenyl)-porphyrin 7H2. BF3·(OEt)2 (103
mL,0.811mmol)wasaddedtoasolutionofdipyrromethane
(395 mg, 2.70 mmol) and 4-(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)-benzaldehyde (627 mg, 2.70 mmol)
in 250 mL of CH2Cl2. The reaction mixture was kept for
1 h before DDQ (920 mg, 4.05 mmol) was added. After
1 h, the reaction mixture was neutralized with 1 mL of
triethylamine and filtered through silica gel with CHCl3
(500 mL) containing 1% of NEt3. After evaporation the
compound was purified on silica gel using CH2Cl2 as
eluent. The evaporation of the fraction produced 7H2
1
as a pink solid (171.3 mg, 18%). H NMR (300 MHz,
CDCl3): d, ppm -2.66 (s, 2H, NH), 1.54 (s, 24H, CH3-
pinacol), 8.36 (d, 4H, J = 7.6 Hz, HPh), 8.46 (d, 4H, J =
7.9 Hz, HPh), 9.15 (d, 4H, J = 4.7 Hz, Hpyr), 9.50 (d, 4H,
J = 4.7 Hz, Hpyr), 10.47 (s, 2H, Hmeso).
5,15-Bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxabo-
rolan-2-yl)phenyl)-porphyrinato zinc 7Zn. Zn(OAc)2
(709.9 mg, 3.235 mmol) was added to a solution of
porphyrin 7H2 (192.5 mg, 0.270 mmol) in CH2Cl2/
MeOH (3:1, 120 mL). The mixture was stirred at ambient
temperature and monitored by MALDI-TOF MS until
completeconversionofstartingmaterial.Thenthemixture
was diluted with 50 mL of CH2Cl2, washed with water
(3 × 70 mL), dried over MgSO4 and evaporated. The solid
residue was purified by column chromatography on silica
with CH2Cl2/MeOH (10:1) as eluent. The evaporation of
the fractions produced 7Zn as a red powder (61.3 mg,
33%). 1H NMR (300 MHz, CDCl3): d, ppm 1.51 (s, 24H,
CH3-pinacol), 8.23 (d, 4H, J = 7.9 Hz, HPh), 8.27 (d, 4H,
J = 7.9 Hz, HPh), 9.12 (d, 4H, J = 4.7 Hz, Hpyr), 9.43
(d, 4H, J = 4.7 Hz, Hpyr), 10.32 (s, 2H, Hmeso).
5,15-Dimesityl-10,20-di(biphenyl)porphyrin 9H2.
Pd(OAc)2 (2.4 mg, 0.010 mmol) and PPh3 (5.9 mg, 0.020
mmol) were dissolved in 20 mL of distilled THF. The
solution of Na2CO3 in water (211.0 mg, 2 mmol, 4 mL
H2O), 5,15-dimesityl-10,20-bis(4-(4,4,5,5-tetramethyl-
1,3,2-dioxaborolan-2-yl)phenyl)-porphyrin 8H2 (47.0
mg, 0.050 mmol) and C6H5Br (16 ml, 0.150 mmol) were
added successively. The mixture was refluxed for 5 h.
Copyright © 2014 World Scientific Publishing Company
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SYNTHESIS OF PORPHYRIN-BIS(POLYAZAMACROCYCLE) TRIADS VIA SUZUKI COUPLING REACTION
45
The reaction mixture was cooled to room temperature,
125.3 (CH), 125.4 (CH), 125.6 (CH), 125.7 (CH), 127.2
(CH), 127.8 (CH), 129.1 (CH), 129.3 (CH), 129.5 (br
s, CHpyr), 130.8 (CH), 131.5 (br s, CHpyr), 135.1 (CH),
137.7 (C), 138.6 (C), 138.9 (C), 139.3 (C), 139.4 (C),
139.6 (C), 140.0 (C), 140.4 (C), 140.9 (C), 141.0 (C).
UV-vis (CH2Cl2): lmax, nm (log e) 420 (5.61), 516 (4.28),
552 (3.99), 592 (3.76), 649 (3.69). MALDI-TOF MS:
m/z 1289.70. ESI-HRMS: m/z 1291.75302 [MH]+; calcd.
1291.74842.
diluted with 30 mL of CH2Cl2, and washed with water
(3 × 10 mL). After evaporation, the residue was purified
on silica with CH2Cl2 as eluent. The evaporation of the
fractions produced the porphyrin as violet powder (30.0
1
mg, 71%). H NMR (300 MHz, CDCl3): d, ppm -2.64
(s, 2H, NH), 1.78 (s, 12H, CH3-Mes), 2.56 (s, 6H, CH3-
Mes), 7.28 (s, 4H, HMes), 7.46 (t, 2H, J = 7.9 Hz, HAr),
7.59 (t, 4H, J = 7.9 Hz, HAr), 7.91 (d, 4H, J = 7.9 Hz,
HAr), 7.97 (d, 4H, J = 8.1 Hz, HAr), 8.29 (d, 4H, J = 8.1
Hz, HAr), 8.70 (d, 4H, J = 4.6 Hz, Hpyr), 8.87 (d, 4H, J =
4.6 Hz, Hpyr). MALDI-TOF MS: m/z 851.65 [M + H]+.
Coupling of 5,15-dimesityl-10,20-bis(4-(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-
porphyrin(8H2)with1toform10H2 and11H2. Basefree
porphyrin 8H2 (100.0 mg, 0.100 mmol), Pd(OAc)2 (4.8
mg, 0.020 mmol), 1,1′-bis(diphenylphosphino)ferrocene
(dppf) (12.6 mg, 0.020 mmol) and Cs2CO3 (137.0
mg, 0.400 mmol) were mixed as solids. The reaction
vessel was evacuated and purged with N2 three times.
Subsequently, toluene (6 mL) and polyazacycloalcane
1 (119.0 mg, 0.300 mmol) were added and the reaction
mixture heated to reflux. After complete conversion,
monitored by MALDI-TOF MS, the solvents were
evaporated and the residue was separated at silica with
CH2Cl2/CH3OH (10:2) (fractions containing 11H2) and
CH2Cl2/CH3OH/NEt3 (20:8:1) (fractions containing
10H2). After evaporation, compound 10H2 was purified
on Sephadex LH-20 resin with CH2Cl2 as eluent. The
evaporation of the fractions afforded 10H2 as a violet
The fraction containing 11H2 was evaporated and
purified on Sephadex LH-20 resin with CH2Cl2 as
eluent. The evaporation of fractions produced the desired
1
porphyrin as a violet powder (13.7 mg, 52%). H NMR
(300 MHz, CDCl3) (mixture of two diastereomers in
1:1 ratio): d, ppm -2.62 (s, 4H, NH), 1.17 (s, 6H, CH3-
aminal), 1.48 (s, 6H, CH3-aminal), 1.77 (s, 24H, CH3-
Mes), 2.16–2.22 (m, 4H, CH2N), 2.54 (s, 12H, CH3-Mes),
2.55–2.90 (m, 8H, CH2N), 3.18–3.40 (m, 8H, CH2N),
3.40–3.50 (m, 8H, CH2N, CH2-Ar), 3.53 (d, 1H, J = 15.1
Hz, CH2-Ar), 3.68 (d, 1H, J = 15.1 Hz, CH2-Ar), 4.42
(d, 1H, J = 14.3 Hz, CH2-Ar), 4.44 (d, 1H, J = 14.3 Hz,
CH2-Ar), 4.68 (d, 1H, J = 15.2 Hz, CH2-Ar), 4.71 (d, 1H,
J = 15.2 Hz, CH2-Ar), 7.20 (br s, 8H, CH-Mes), 7.42 (d,
2H, J = 8.1 Hz, Harom), 7.41 (t, 2H, J = 7.9 Hz, HPh), 7.51
(t, 4H, J = 7.9 Hz, HPh), 7.65 (m, 4H, Harom), 7.78–7.93
(m, 12H, HAr and HPh), 8.20 (d, 8H, J = 7.5 Hz, HAr), 8.21
(d, 8H, J = 4.5 Hz, Hpyr), 8.79 (d, 4H, J = 4.5 Hz, Hpyr),
8.81 (d, 4H, J = 4.5 Hz, Hpyr). UV-vis (CH2Cl2): lmax, nm
(log e) 420 (5.52), 516 (4.17), 551 (3.88), 592 (3.63), 648
(3.57). MALDI-TOF MS: m/z 1069.40.
1
powder (40.1 mg, 30%). H NMR (600 MHz, CDCl3)
Coupling of 5,15-dimesityl-10,20-bis(4-(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-
porphyrin (8H2) with 2 to form 14H2. Base free
porphyrin 8H2 (150.0 mg, 0.150 mmol), Pd(OAc)2 (7.2
mg, 0.030 mmol), Cs2CO3 (207.4 mg, 0.600 mmol)
and dppf (19.2 mg, 0.030 mmol) were mixed as solids.
The reaction vessel was evacuated and purged with N2
three times. Subsequently, toluene (14 mL) and 2 (187.4
mg, 0.450 mmol) were added and the reaction mixture
heated to reflux. After complete conversion (monitored
by MALDI-TOF MS), the solvents were evaporated and
the residue was separated by column chromatography
on silica with CH2Cl2/CH3OH (10:2) to CH2Cl2/CH3OH/
NEt3 (20:8:1) mixtures. After evaporation the porphyrin
was purified on Bio-Beads® S-X resin with CH2Cl2 as
eluent. The evaporation of the fractions produced the
(mixture of two diastereomers in 1:1 ratio): d, ppm -2.52
(s, 4H, NH), 1.27 (s, 12H, CH3-aminal), 1.65 (s, 6H,
CH3-aminal), 1.66 (s, 6H, CH3-aminal), 1.89 (s, 24H,
CH3-Mes), 2.22 (d, 2H, J = 10.6 Hz, CH2N), 2.29 (d, 2H,
J = 10.6 Hz, CH2N), 2.41 (br s, 4H, CH2N), 2.65 (s, 12H,
CH3-Mes), 2.78 (m, 12H, CH2N), 2.78–2.90 (m, 10H,
CH2N), 3.01–3.15 (m, 10H, CH2N), 3.18–3.27 (m, 4H,
CH2N), 3.27–3.35 (m, 4H, CH2N), 3.45 (d, 2H, J = 14.4
Hz, CH2-Ar), 3.52 (d, 2H, J = 14.4 Hz, CH2-Ar), 3.66
(d, 2H, J = 15.1 Hz, CH2-Ar), 3.74 (d, 2H, J = 15.1 Hz,
CH2-Ar), 4.41 (d, 2H, J = 14.3 Hz, CH2-Ar), 4.46 (d, 2H,
J = 14.3 Hz, CH2-Ar), 4.74 (d, 2H, J = 15.2 Hz, CH2-Ar),
4.79 (d, 2H, J = 15.2 Hz, CH2-Ar), 7.26 (d, 2H, J = 7.1
Hz, CHarom), 7.31 (s, 8H, CHMes), 7.38 (d, 2H, J = 7.1 Hz,
CHarom), 7.64 (s, 2H, CHarom), 7.68 (d, 2H, J = 6.9 Hz,
CHarom), 7.70 (d, 2H, J = 6.9 Hz, CHarom), 7.74 (s, 2H,
CHarom), 7.94 (d, 4H, J = 7.0 Hz, HAr), 7.97 (d, 4H, J = 7.0
Hz, HAr), 8.29 (d, 8H, J = 7.0 Hz, HAr), 8.72 (d, 4H, J =
4.5 Hz, Hpyr), 8.74 (d, 4H, J = 4.5 Hz, Hpyr), 8.90 (br d,
4H, J = 4.5 Hz, Hpyr), 8.91 (br d, 4H, J = 4.5 Hz, Hpyr). 13C
NMR (150 MHz, CDCl3) (mixture of two diastereomers
in 1:1 ratio): d, ppm 12.2 (CH3), 12.3 (CH3), 13.7 (CH3),
21.5 (CH3), 21.7 (CH3), 45.6 (CH2), 45.9 (CH2), 46.0
(CH2), 46.9 (CH2), 50.7 (CH2), 50.9 (CH2), 52.1 (CH2),
52.2 (CH2), 54.0 (CH2), 54.6 (CH2), 58.5 (CH2), 59.0
(CH2), 77.5 (C), 80.5 (C), 118.4 (C), 119.1 (C), 119.2 (C),
1
porphyrin as a violet powder (46.3 mg, 24%). H NMR
(600 MHz, CDCl3) (mixture of two diastereomers in 1:1
ratio): d, ppm -2.62 (s, 4H, NH), 1.15 (br s, 4H, CH2),
1.40 (s, 12H, CH3-aminal), 1.48 (s, 12H, CH3-aminal),
1.77 (s, 24H, CH3-Mes), 1.92–1.98 (m, 2H, CH2), 2.01–
2.05 (m, 2H, CH2), 2.29 (br s, 12H, CH2N), 2.48 (br s,
4H, CH2N), 2.53 (m, 24H, CH3-Mes, CH2N), 2.77 (br s,
8H, CH2N), 2.87 (br s, 4H, CH2N), 3.15–3.56 (m, 4H,
CH2N), CH2-Ar), 3.66 (d, 2H, J = 14.7 Hz, CH2-Ar), 3.68
(d, 2H, J = 15.6 Hz, CH2-Ar), 3.85 (br s, 4H, CH2N), 4.21
(d, 2H, J = 14.6 Hz, CH2-Ar), 4.26 (d, 2H, J = 14.6 Hz,
Copyright © 2014 World Scientific Publishing Company
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J. MICHALAK ET AL.
CH2-Ar), 4.65 (d, 2H, J = 15.2 Hz, CH2-Ar), 4.69 (d, 2H,
J = 15.2 Hz, CH2-Ar), 7.16 (d, 2H, J = 7.1 Hz, CHarom),
7.18 (s, 8H, CHMes), 7.32 (d, 2H, J = 7.1 Hz, CHarom), 7.53
(s, 2H, CHarom), 7.61 (d, 2H, J = 6.7 Hz, CHarom), 7.63 (d,
2H, J = 6.7 Hz, CHarom), 7.66 (s, 2H, CHarom), 7.86 (d,
4H, J = 7.0 Hz, HAr), 7.89 (d, 4H, J = 7.0 Hz, HAr), 8.20
(br s, 8H, HAr), 8.63 (br s, 8H, Hpyr), 8.80 (br s, 8H, Hpyr).
13C NMR (150 MHz, CDCl3 + CD3OD) (mixture of two
diastereomers in 1:1 ratio)‡: d, ppm 11.3 (CH3), 17.4
(CH2), 21.3 (CH3), 21.5 (CH3), 44.5 (CH2), 44.9 (CH2),
46.6 (CH2), 50.5 (CH2), 51.6 (CH2), 54.3 (CH2), 54.9
(CH2), 58.7 (CH2), 59.2 (CH2), 77.0 (br s, C), 79.5 (C),
118.3 (C), 119.0 (C), 119.1 (C), 125.1 (CH), 125.2 (CH),
125.6 (CH), 125.9 (CH), 126.9 (CH), 127.7 (CH), 128.8
(CH), 129.0 (CH), 130.6 (CH), 135.0 (CH), 137.7 (C),
138.3 (C), 139.3 (C), 139.5 (C), 139.8 (C), 140.8 (C),
140.9 (C). MALDI-TOF MS: m/z 1317.82. ESI-HRMS:
m/z 1319.78274 [MH]+; calcd. 1319.77972.
127.2 (CH), 128.7 (CH), 129.1 (CH), 130.4 (CH), 131.5,
132.0, 135.2 (CH), 136.9 (C), 138.9 (C), 139.3 (C), 139.5
(C), 139.6 (C), 140.5 (C), 140.4 (C), 142.3 (C), 149.47
(C), 149.89 (C). UV-vis (CH2Cl2): lmax, nm (log e) 413
(5.61), 540 (4.29). MALDI-TOF MS: m/z 1115.44. ESI-
HRMS: m/z 1117.51074 [MH]+; calcd. 1117.50541.
After evaporation of the fraction containing 16Zn, the
residue (26.4 mg) was purified at Bio-Beads® S-X resin
with CH2Cl2 eluent. The evaporation of the fractions
produced the desired porphyrin as a violet powder (17.9
mg, 25%). 1H NMR (300 MHz, CDCl3) (mixture of two
diastereomers in 1:1 ratio, 80% purity): d, ppm 1.23 (s,
6H, CH3-aminal), 1.51 (s, 6H, CH3-aminal), 2.03–2.08
(m, 8H, CH2N), 2.21–2.60 (m, 8H, CH2N), 3.44–3.68
(m, 10H, CH2N, CH2-Ar), 4.18–4.25 (m, 2H, CH2-Ar),
4.48–4.54 (m, 2H, CH2-Ar), 4.70–4.73 (m, 2H, CH2-Ar),
7.27–7.40 (m, 4H, CHarom, HPh), 7.60–7.63 (m, 2H, HPh),
7.71–7.74 (m, 2H, CHarom), 7.77–7.78 (m, 2H, HPh), 7.95–
7.96 (m, 4H, HAr), 8.29–8.30 (m, 8H, HAr), 9.16–9.20 (m,
8H, Hpyr), 9.40–9.43 (m, 8H, Hpyr), 10.28 (br s, 4H, Hmeso).
MALDI-TOF MS: m/z 895.09.
Coupling of 5,15-diphenyl-10,20-bis(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)-porphyrinato
zinc 6Zn with 1 to form 17Zn. 6Zn (400 mg, 0.51 mmol),
1 (576 mg, 1.53 mmol), Pd(OAc)2 (23 mg, 0.103 mmol),
dppf (56 mg, 0.103 mmol) and Cs2CO3 (665 mg, 2.04
mmol) were flushed with N2. (The reaction vessel was
evacuated and purged with N2 three times). Subsequently,
toluene (32 mL) was added and the reaction mixture
was refluxed for 13 h until complete conversion of the
starting material. After cooling the mixture was diluted
with CH2Cl2 and washed with water. Organic layer was
evaporated and the residue was purified on silica with
CH2Cl2/CH3OH (1:1) mixture. The residue was dissolved
in CH2Cl2 and subjected to Bio-Beads SX-1 gel column
with CH2Cl2 eluent to produce 17Zn with 80% yield. 1H
NMR (600 MHz, CDCl3) (mixture of two diastereomers
in 1:1.6 ratio): d, ppm 1.26 (6H, CH3-aminal, isomer A),
1.32 (s, 6H, CH3-aminal, isomer B), 1.70 (s, 6H, CH3-
aminal, both isomers), 2.36–2.48 (m, 12H, CH2N, both
isomers), 2.52–2.75 (m, 16H, CH2N, both isomers),
2.76–2.86 (m, 4H, CH2N, both isomers), 2.90–3.00 (m,
4H, CH2N), 3.00–3.10 (m, 4H, CH2N, both isomers),
3.10–3.24 (m, 8H, CH2N, both isomers), 3.32–3.38 (m,
4H, CH2N, both isomers), 3.53 (d, 2H, J = 14.2 Hz,
CH2-Ar, isomer A), 3.63 (d, 2H, J = 14.2 Hz, CH2-Ar,
isomer B), 3.70 (d, 2H, J = 15.1 Hz, CH2-Ar, isomer B),
3.88 (d, 2H, J = 15.5 Hz, CH2-Ar, isomer A), 4.60 (d, 2H,
J = 15.5 Hz, CH2-Ar, isomer B), 4.65 (d, 2H, J = 14.2 Hz,
CH2-Ar, isomer A), 4.91 (d, 2H, J = 15.5 Hz, CH2-Ar,
isomer A), 4.96 (d, 2H, J = 15.5 Hz, CH2-Ar, isomer
B), 7.43 (d, 2H, J = 7.6 Hz, Harom, both isomers), 7.51
(d, 2H, J = 7.3 Hz, Harom, both isomers), 7.70–7.80 (m,
12H, HPh, both isomers), 7.88–7.93 (m, 2H, Harom, both
isomers), 7.94–7.99 (m, 2H, Harom, both isomers), 7.99–
8.04 (m, 4H, Harom, both isomers), 8.16–8.26 (m, 8H,
HPh, both isomers), 8.78–8.82 (m, 2H, HPyr, isomer A),
Coupling of 5,15-bis(4-(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)phenyl)-porphyrinato zinc 7Zn
with 1 to form 15Zn and 16Zn. Metalloporphyrin 7Zn
(61.3 mg, 0.079 mmol), Pd(OAc)2 (3.6 mg, 0.016 mmol),
Cs2CO3 (102.7 mg, 0.315 mmol) and dppf (9.6 mg, 0.016
mmol) were mixed as solids. The reaction vessel was
evacuated and purged with N2 three times. Subsequently,
toluene (4 mL) and 1 (89.2 mg, 0.236 mmol) were added
and the reaction mixture heated to reflux. After complete
conversion monitored by MALDI-TOF MS, the solvents
were evaporated and the residue was purified on silica
with CH2Cl2/CH3OH (10:2) for 16Zn and CH2Cl2/
CH3OH/NEt3 (20:8:1) for 15Zn. After evaporation 15Zn
was purified on Bio-Beads® S-X resin with CH2Cl2 as
eluent. The evaporation of fraction produced the desired
1
porphyrin as a violet powder (23.1 mg, 26%). H NMR
(600 MHz, CDCl3) (mixture of two diastereomers in 1:1
ratio): d, ppm 1.23 (s, 12H, CH3-aminal), 1.52 (s, 12H,
CH3-aminal), 2.19–2.23 (m, 4H, CH2N), 2.33–2.50 (m,
12H, CH2N), 2.63–2.72 (m, 8H, CH2N), 2.76–2.85 (m,
12H, CH2N), 2.92–3.03 (m, 8H, CH2N), 3.20–3.28 (m,
4H, CH2N), 3.39 (d, 2H, J = 15.3 Hz, CH2-Ar), 3.49
(d, 2H, J = 15.3 Hz, CH2-Ar), 3.64 (d, 2H, J = 15.3 Hz,
CH2-Ar), 3.7 (d, 2H, J = 15.3 Hz, CH2-Ar), 4.36 (d, 2H,
J = 14.2 Hz, CH2-Ar), 4.43 (d, 2H, J = 14.2 Hz, CH2-Ar),
4.71 (d, 2H, J = 14.2 Hz, CH2-Ar), 4.73 (d, 2H, J = 14.2
Hz, CH2-Ar), 7.26 (d, 2H, J = 6.2 Hz, CHarom), 7.34 (d,
2H, J = 6.2 Hz, CHarom), 7.61 (s, 2H, CHarom), 7.69 (d, 2H,
J = 6.2 Hz, CHarom), 7.71 (d, 2H, J = 6.2 Hz, CHarom), 7.72
(s, 2H, CHarom), 7.98 (d, 4H, J = 7.6 Hz, HAr), 8.00 (d, 4H,
J = 7.6 Hz, HAr), 8.31 (d, 8H, J = 7.6 Hz, HAr), 9.22 (d,
4H, J = 4.5 Hz, Hpyr), 9.23 (d, 4H, J = 4.5 Hz, Hpyr), 9.44
(br d, 4H, J = 4.5 Hz, Hpyr), 9.45 (br d, 4H, J = 4.5 Hz,
Hpyr), 10.31 (br s, 4H, Hpyr). 13C NMR (150 MHz, CDCl3)
(mixture of two diastereomers in 1:1 ratio): d, ppm 12.0
(CH3), 13.0 (CH3), 45.2 (CH2), 45.3 (CH2), 46.1 (CH2),
49.1 (CH2), 50.2 (CH2), 51.2 (CH2), 53.4 (CH2), 54.0
(CH2), 57.9 (CH2), 58.4 (CH2), 76.8 (C), 80.5 (C), 105.7
(CHpyr), 118.4 (C), 125.0 (CH), 125.6 (CH), 125.7 (CH),
Copyright © 2014 World Scientific Publishing Company
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SYNTHESIS OF PORPHYRIN-BIS(POLYAZAMACROCYCLE) TRIADS VIA SUZUKI COUPLING REACTION
47
8.82–8.92 (m, 12H, HPyr, both isomers), 8.94–9.00 (m,
J = 8.1 Hz, Harom), 77.39 (t, 2H, J = 7.9 Hz, HPh), 7.82 (d,
1H, J = 8.1 Hz, Harom), 7.88 (s, 1H, Harom), 7.91 (d, 2H, J =
7.0 Hz, HAr), 7.92 (d, 2H, J = 7.0 Hz, HAr), 8.30 (d, 4H,
J = 7.0 Hz, HAr), 8.30 (d, 2H, J = 7.5 Hz, HPh), 8.70 (d,
2H, J = 4.5 Hz, Hpyr), 8.86 (d, 2H, J = 4.5 Hz, Hpyr), 8.88
(d, 2H, J = 4.5 Hz, Hpyr). ESI-HRMS: m/z 1043.55103
[MH]+; calcd. 1043.54592.
2H, HPyr, isomer B). UV-vis (CHCl3): lmax, nm (log e) 424
(5.53), 554 (4.19), 596 (3.82). MALDI-TOF MS: m/z
1115.34 [M – 1]. ESI-HRMS: m/z 1117.50996 [MH]+;
calcd. 1117.50541.
Coupling of 5,15-diphenyl-10,20-bis(4,4,5,5-tetra-
methyl-1,3,2-dioxaborolan-2-yl)-porphyrinato zinc
6Zn with 2 to form 20Zn. 6Zn (300 mg, 0.39 mmol), 2
(450 mg, 1.15 mmol), Pd(OAc)2 (8.61 mg, 0.038 mmol),
dppf (21 mg, 0.038 mmol) and Cs2CO3 (500 mg, 1.53
mmol) were flushed with N2. The reaction vessel was
evacuated and purged with N2 three times. Subsequently,
toluene (24 mL) was added and the reaction mixture
was refluxed for 15 h until complete conversion of the
starting material. After cooling the mixture was diluted
with CH2Cl2 and washed with water. Organic layer was
evaporated and applied to column filled with silica gel
in CH2Cl2/MeOH (1:1) mixture. The column was eluted
with CH2Cl2/MeOH (1:1) and the collected fractions
were evaporated. The residue was dissolved in CH2Cl2
and subjected to Bio-Beads SX-1 gel column with
Deprotection of the aminal group of the porphyrin
10H2 to form 22H2. 10H2 (29.4 mg, 0.023 mmol) was
dissolved in HCl/EtOH mixture (HCl l0%, 1:1, 2 mL) and
kept at ambient temperature. After complete conversion
monitored by MALDI-TOF MS, Na2CO3 (15%, aqueous
solution, pH = 10) was added and the mixture was diluted
with CH2Cl2 (40 mL). The organic phase was washed
with water (4 × 20 mL) and dried over Na2SO4. The
evaporation produced the base free porphyrin 22H2 as a
violet solid (24.0 mg, 89%). 1H NMR (300 MHz, CDCl3):
d, ppm -2.57 (s, 2H, NH), 1.86 (s, 12H, CH3-Mes), 2.63
(s, 6H, CH3-Mes), 2.77 (s, 8H, CH2N), 2.89 (br s, 8H,
CH2N), 2.95 (br s, 8H, CH2N), 3.97 (s, 4H, CH2-Ar), 4.02
(s, 4H, CH2-Ar), 7.29 (s, 4H, CH-Mes), 7.54 (d, 2H, J =
7.7 Hz, CHarom), 7.81 (d, 2H, J = 7.7 Hz, CHarom), 7.89 (s,
2H, CHarom), 7.97 (d, 4H, J = 7.5 Hz, CHAr), 8.28 (d, 4H,
J = 7.5, Hz, CHAr), 8.71 (d, 4H, J = 4.5 Hz, Hpyr), 8.86 (d,
4H, J = 4.5 Hz, Hpyr). UV-vis (CHCl3): lmax, nm (log e)
420 (5.41), 516 (3.99), 552 (3.69), 592 (3.46), 648 (3.38).
1
CH2Cl2 eluent to produce 20Zn with 93% yield. H
NMR (600 MHz, CDCl3) (mixture of two diastereomers
in 1:1 ratio): d, ppm 1.17–1.23 (m, 2H, CH2), 1.45 (s,
6H, CH3-aminal), 1.52 (s, 6H, CH3-aminal), 1.64 (s, 6H,
CH3-aminal), 1.65 (s, 6H, CH3-aminal), 2.16–2.22 (m,
2H, CH2), 2.25–2.35 (m, 4H, CH2), 2.36–2.48 (m, 8H,
CH2N), 2.49–2.58 (m, 4H, CH2N), 2.62–2.78 (m, 16H,
CH2N), 2.88–2.96 (m, 4H, CH2N), 2.98–3.07 (m, 2H,
CH2N), 3.14–3.21 (m, 2H, CH2N), 3.25–3.38 (m, 6H,
CH2N, CH2-Ar), 3.53 (d, 2H, J = 15.2 Hz, CH2-Ar), 3.58–
3.64 (m, 4H, CH2N), 3.72 (d, 2H, J = 15.2 Hz, CH2-Ar),
3.87–4.02 (m, 6H, CH2N, CH2-Ar), 4.48 (d, 2H, J = 15.2
Hz, CH2-Ar), 4.55 (d, 2H, J = 15.2 Hz, CH2-Ar), 4.90
(d, 2H, J = 15.2 Hz, CH2-Ar), 4.97 (d, 2H, J = 15.2 Hz,
CH2-Ar), 7.41 (br d, 2H, J = 6.6 Hz, Harom), 7.54 (s, 2H,
Harom), 7.73–7.85 (m, 12H, HPh), 7.89 (s, 2H, Harom), 7.95–
8.02 (m, 4H, Harom), 8.06 (s, 2H, Harom), 8.18–8.32 (m,
8H, HPh), 8.84 (br d, 2H, J = 4.5 Hz, HPyr), 8.89–9.00
(m, 12H, HPyr), 9.03 (br d, 2H, J = 4.5 Hz, HPyr). UV-vis
(CHCl3): lmax, nm (log e) 424 (5.53), 554 (4.19), 596
(3.63). MALDI-TOF MS: m/z 1143.51 [M – 1].
CONCLUSION
In this paper, we have described the optimal
experimental conditions to prepare polyazamacrocycle-
substituted porphyrins using Suzuki–Miyaura cross-
couplingreactions.Thesestudiesdemonstratethatboronic
esters appended zinc porphyrins are suitable electro-
philes to react with aromatic bromides possessing a
bisaminal-protected benzannulated polyazamacrocyclic
moiety to give tricyclic architectures linked directly
or by a p-phenylene spacer. A proper choice of the
optimal catalysts, the nature of the base and the solvent
reaction mixture are key parameters to obtain a selective
transformation.
These triads represent an interesting and promising
class of mixed macrocyclic ligands with high potential for
various applications. For example these systems constitute
a remarkable platform which combines imaging and
fluorescent properties.
Deprotection of the aminal group of the porphyrin
11H2 to form 21H2. 11H2 (13.7 mg, 0.013 mmol) was
dissolved in the mixture of HCl/EtOH (HCl l0%, 1:1,
2 mL) and kept at ambient temperature. After complete
conversion monitored by MALDI-TOF MS, Na2CO3
(15%, aqueous solution, pH = 10) was added and the
mixture was diluted with CH2Cl2 (40 mL). The organic
phase was washed with water (4 × 20 mL) and dried
over Na2SO4. The evaporation produced the base free
Acknowledgements
This work was supported by the CNRS, the Russian
Foundation for Basic Research (Grant No. 12-03-93114)
and was carried out in the framework of the International
Associated French-Russian Laboratory of Macrocycle
Systems and Related Materials (LAMREM) of CNRS
and RAS. SM thanks the Conseil Régional de Bourgogne
for a post-doctoral fellowship. The authors gratefully
acknowledge support from Ministère de l’Enseignement
1
porphyrin 21H2 as a violet solid (10.8 mg, 83%). H
NMR (300 MHz, CDCl3): d, ppm -2.58 (s, 2H, NH),
1.84 (s, 12H, CH3-Mes), 2.61 (s, 6H, CH3-Mes), 2.79
(br s, 4H, CH2N), 2.93 (br s, 4H, CH2N), 2.97 (br s, 4H,
CH2N), 4.02 (s, 2H, CH2-Ar), 4.06 (s, 2H, CH2-Ar), 7.27
(s, 4H, CH-Mes), 7.46 (t, 1H, J = 7.9 Hz, HPh), 7.55 (d, 1H,
Copyright © 2014 World Scientific Publishing Company
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J. MICHALAK ET AL.
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