Efficient Synthesis of Arylenedioxy-Bridged Porphyrin Dimers through Catalyst-Free Nucleophilic Aromatic Substitution

Article abstract of DOI:10.1002/cplu.201900670

A series of porphyrin dimers bridged by one or two rigid arylenedioxy linkers was successfully synthesized by catalyst-free meso-aryloxylation involving nucleophilic aromatic substitution. The orientational freedom and conformation of the two porphyrin macrocycles in the mono-bridged dimers depended on the steric hindrance between the macrocycles and substituents on the arylenedioxy linkers. On the other hand, the bis-bridged dimers exhibited a highly rigid cofacial conformation with a distinct interplanar distance. The fluorescence quantum yields of the bis-bridged dimers (Φ_fl=0.094 and 0.096) were quite similar to those of the monomers (Φ_fl=0.13). Owing to their high rigidities, the nonradiative deactivation of the photoexcited states associated with dimerization, which are observed for reported dimers, are mostly suppressed, thus suggesting that those dimers have highest rigidities among the cofacial porphyrin dimers exploring emission properties. Cyclic voltammetry revealed the electronic communication between the porphyrin macrocycles in the closely stacked bis-bridged dimer.

Full text of DOI:10.1002/cplu.201900670

Accepted Article
Title: Efficient Synthesis of Arylenedioxy-Bridged Porphyrin Dimers
through Catalyst-Free Nucleophilic Aromatic Substitution
Authors: Ken-ichi Yamashita, Narumi Kuramochi, Hang Pham Qui Van,
Kazuhiro Furutani, Takuji Ogawa, and Ken-ichi Sugiura
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Efficient Synthesis of Arylenedioxy-Bridged Porphyrin Dimers
through Catalyst-Free Nucleophilic Aromatic Substitution
Ken-ichi Yamashita,*[a,b] Narumi Kuramochi, Hang Pham Qui Van, Kazuhiro Furutani, Takuji
[a]
[a]
[b]
[
b]
[a]
Ogawa, and Ken-ichi Sugiura*
Abstract: A series of porphyrin dimers bridged by one or two rigid
arylenedioxy linkers was successfully synthesized by catalyst-free
meso-aryloxylation involving nucleophilic aromatic substitution. The
orientational freedom and conformation of the two porphyrin
macrocycles in the mono-bridged dimers depended on the steric
hindrance between the macrocycles and substituents on the
arylenedioxy linkers. On the other hand, the bis-bridged dimers
exhibited a highly rigid cofacial conformation with a distinct interplanar
distance. The fluorescence quantum yields of the bis-bridged dimers
can bind guests of various size by changing the orientation of the
porphyrin macrocycles.[7] This orientational change has been
occasionally applied to amplify the circular dichroism signals of
chiral guest molecules during the determination of their
chirality.[
6,8]
On the other hand, orientational rigidity is typically
increased to enhance the size selectivity of the dimers for guest
molecules.
To date, although various synthetic methods have been
reported, the exploration of cofacial porphyrin dimers, especially
closely stacked rigid dimers, remains challenging. Their
syntheses typically require complicated multi-step reactions that
(

fl = 0.094 and 0.096) were quite similar to those of the monomers
fl = 0.13). Owing to their high rigidities, the nonradiative deactivation
(
[
2d,9]
of the photoexcited states associated with dimerization, which are
observed for reported dimers, are mostly suppressed, suggesting that
those dimers have highest rigidities among the cofacial porphyrin
dimers exploring emission properties. Cyclic voltammetry revealed
the electronic communication between the porphyrin macrocycles in
the closely stacked bis-bridged dimer.
result in low total yields for porphyrin formation
or palladium-
catalyzed coupling reactions.[
2f,2g,10]
Recently, dimers have been
effectively prepared through self-assembly driven by labile
coordination or hydrogen bonding.[11] However, the lability of the
bonding causes structural instability upon environmental change.
Introduction
Cofacial porphyrin dimers, whose porphyrin units are bridged by
one or more linker units, have attracted considerable attention
owing to their unique potentials, which depend on the orientation
of the porphyrin units and, especially, the interplanar distance.[1]
For example, closely stacked dimers have been used as artificial
[
2]
reaction centers in a photosystem, the synthetic analogs of
diheme centers,[
3,4]
or catalysts for the activation of small
, O , or N
.[5] On the other hand, a dimer
molecules, such as H
2
2
2
with a considerably large cavity surrounded by two porphyrin
macrocycles can bind guest molecules or anions of suitable
molecular size in the cavity through axial coordination to the metal
center and/or - or CH- interaction.[6] Such functions are greatly
affected by not only the orientation of the two porphyrin
macrocycles, but also their orientational flexibility. Flexible dimers
Scheme 1. Schematically representing the construction of arylenedioxy-bridged
porphyrin dimers in this work.
[
a]
Dr. K. Yamashita, N. Kuramochi, H. Pham Qui Van, Prof. Dr. K.
Sugiura
Department of Chemistry, Graduate School of Science and
Engineering
Tokyo Metropolitan University
Our group[12] and others[13] have recently developed facile
synthetic methods for the preparation of meso-functionalized
porphyrins (e.g., meso-aryloxyporphyrins) via the catalyst-free
nucleophilic aromatic substitution (S Ar) of meso-halo- or meso-
N
nitroporphyrins. These methods do not require expensive or
1-1 Minami-Osawa, Hachioji, Tokyo 192-0397 (Japan)
E-mail: yamashita-k@chem.sci.osaka-u.ac.jp, sugiura@porphyrin.jp
Dr. K. Yamashita, K. Furutani, Prof. Dr. T. Ogawa
Department of Chemistry, Graduate School of Science
Osaka University
[
b]
1-1 Machikaneyama, Toyonaka, Osaka 560-0043 (Japan)
unstable reagents, and the starting materials, i.e., meso-
Supporting information for this article is given via a link at the end of
the document.
[14]
bromoporphyrins, are readily available. Moreover, the product
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yields are typically quite high. Herein, we report the application of
these reactions to the facile synthesis of various covalently
bridged porphyrin dimers, especially cofacial dimers. As
described below, dihydroxyarenes, such as resorcinols (i.e., 1,3-
hydroxyphenols) or 2,7-dihydroxynaphthalene, were adopted as
the nucleophiles and, consequently, the linker units in the dimer
(
Scheme 1).
Results and Discussion
Molecular design
One of the important targets of this study is the synthesis of a rigid
cofacial porphyrin dimer. Considering their ready availability and
handling ease, dihydroxyarenes were selected as the
nucleophiles in the developed
N
S Ar reactions to produce
arylenedioxy-bridged porphyrin dimers (Scheme 1). To realize a
nearly cofacial conformation for the two porphyrin macrocycles
without structural strain, 1,3-phenylenedioxy or 2,7-
Scheme 2. Equilibrium among the three possible conformations of the mono-
bridged dimers, namely, open (A), intermediate (B), and cofacial (C).
naphthylenedioxy linker was adopted among
a series of
arylenedioxy linkers (Figure 1). The orientations of the two
porphyrin macrocycles are expected to be affected by both the
number of linker units in the structure and the neighboring
substituents on the resorcinol. For mono-bridged dimers, three
types of conformation are expected: open (A), intermediate (B),
and cofacial (C) (Scheme 2). If there are neighboring substituents
on the resorcinol (R and R ), the conformation is expected to be
regulated because of steric repulsion between the porphyrin
macrocycles and substituents. A rigid cofacial mono-bridged
dimer can be obtained using a 4,6-substituted resorcinol as the
nucleophile. Undoubtedly, the introduction of two or more linkers
into the dimer is expected to produce a more rigid cofacial
structure regardless of the presence of neighboring substituents
on the resorcinol. The interplanar distance between the two
porphyrin macrocycles is determined by the core arene (i.e., the
O···O distance in the linker unit).
Synthesis of monoarylenedioxy-bridged porphyrin dimers
Initially, we investigated the synthesis of monoarylenedioxy-
bridged porphyrin dimers 1a–e by the S
N
Ar reaction of meso-
bromodiarylporphyrin with the corresponding resorcinol
2
derivatives 3a–e. Typically, 4 equivalents of 2 were treated with 3
2
3
n
and a base (K
2
CO
3
or K
3
PO
4
) in refluxing butyronitrile ( PrCN).
Except for 1c and 1e, the desired dimers were obtained in good
yields (69–84%, Table 1). The reactions of 4,6-diethylresorcinol
(3c) and 2-methylresolcinol (3d) were slower than those of the
others because of steric hindrance (entries 3 and 5). Their
reaction times were improved using K PO instead of K CO
3 4 2 3
(entries 4 and 6). The reaction of 3e did not afford any products
because of the larger steric hindrance posed by the 2-acetyl group
(entry 7). Similarly, the reaction of
2
with 2,7-
dihydroxynaththalene (4) gave dimer 5 in 72% yield (entry 8).
Notably, reacting 3b–d in N,N-dimethylformamide (DMF) or
N,N-dimethylacetamide (DMA), which were used as solvents in a
previous study,[12d] resulted in significantly lower yields of 1b–d,
along with the formation of the debrominated by-product of 2.
These side reactions were not observed during the reaction of
acetyl-substituted resorcinols 3a and 3e. Therefore,
debromination results from the electron transfer reaction of 2 with
electron-rich nucleophiles, which was also observed in a previous
study.[
12d]
Figure 1. Selection of favorable arylenedioxy linker units for cofacial porphyrin
dimers. The red arrows indicate possible porphyrin macrocycle directions.
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Table 1. Synthesis of monoarylenedioxy-bridged porphyrin dimers.[a]
dihydroxynaphthalene (4) to produce cyclic porphyrin dimer 7 or
8, respectively (Scheme 3). Both dimers were obtained in
considerably high yields (61% and 69% for 7 and 8, respectively)
under the optimized conditions. Notably, their syntheses did not
require highly dilute condition ([6] was ca. 5–6 mM).
Scheme 3. Synthesis of bis(arylenedioxy)-bridged cyclic porphyrin dimers 7 and
8.
X-ray crystallography
Entry
1
3 or 4
Base
Time (h)
21
Product
1a
Yield (%)[b]
81
To gain information on the conformations of the prepared dimers
in the solid state, we attempted to produce single crystals for X-
ray diffractometry. Among the mono-bridged dimers, only 1b and
3a
3b
3c
3c
3d
3d
3e
4
K
K
K
K
K
K
K
K
2
2
2
3
2
3
2
2
CO
CO
CO
3
3
3
2
25
1b
84
5
afforded suitable single crystals. Although these structures were
3[c]
37[d]
not able to be solved completely due to poor diffraction data, the
preliminary structures (Figure S3) reveal that both 1b and 5 adopt
conformation B (Scheme 2) in the solid state. The distances
between the two porphyrin centers of 1b and 5 are 11.1 and 13.3
Å, respectively.
94
1c
19[d]
69
4
5
6
7
8
PO
CO
PO
3
22.5
46
1c
3
1d
4
6
1d
71
The successful X-ray diffraction studies of bis-bridged dimers
7
and 8 unambiguously confirm the adoption of the cofacial
0[d]
72
CO
3
3
24
1e
conformation in the solid state (Figure 2). As expected, the two
porphyrin macrocycles are almost parallel with small planar
angles [1.31(4)° and 0.00(3)° for 7 and 8, respectively]. The
distances between the centers of the porphyrin macrocycles of 7
and 8 are 4.759 and 7.541 Å, respectively. These distances are
quite similar to those between the two oxygen atoms in the
arylenedioxy linkers (ca. 4.84 and 7.30 Å for 7 and 8, respectively).
The planar angle between each porphyrin macrocycle and the
phenyl ring in the arylenedioxy linker units range between 76.4°
and 79.7° for 7 and 88.2° for 8. These orthogonal orientations are
due to steric repulsion between the -protons on the porphyrin
macrocycles and the protons on the arylenedioxy linkers. Thus,
the interplanar distance and size of the internal cavity are mostly
determined by the length of the arylenedioxy linker, as we
expected.
CO
24
5
[
a] Reaction conditions: 2, 0.080 mmol; 3 or 4, 0.020 mmol; base, 0.10
n
mmol; PrCN 2 mL; refluxed under N
and 20 equiv. of K
formed. [d] No products were afforded.
2
. [b] Isolated yield. [c] 3 equiv. of 2,
2
CO
3
was used. [d] Debrominated byproduct was also
Synthesis of bis(arylenedioxy)-bridged cyclic porphyrin
dimers
There have been quite limited reports on syntheses of the closely-
stacked bis-bridged dimers with covalent linker, and they provide
low yield of products or require high-dilution condition in the
cyclization step.[9a, 9c] Therefore, we investigated the S
of meso-dibromodiarylporphyrin 6 with resorcinol 3b or 2,7-
N
Ar reaction
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There are no residual electron density peaks within the cavity
3
of 7 (volume: 109 Å ), confirming its emptiness (Figure S6a,b). On
3
the other hand, 8 has larger cavity (volume: 274 Å ). Within the
cavity, residual electron density peaks derived from the severely
disordered solvent molecules (probably THF) are found (Figure
S8c,d). This suggests the guest-inclusion ability of 8.
The porphyrin planes in both crystals 7 and 8 are oriented in
almost the same direction (Figure 3). Furthermore, the molecules
of 8 are arranged in -stacked columns.
Figure 3. Packing structures of (a, b) 7 and (c, d) 8. (C = gray, N = blue, and O
=
red). The aryl groups, hydrogen atoms, and solvent molecules are omitted for
clarity.
Conformational analysis of the dimers by 1H NMR
spectroscopy
The orientations of the two porphyrin macrocycles of the prepared
1
dimers in solution were analyzed by H NMR spectroscopy. As
discussed above, this orientation is expected to be regulated by
Figure 2. (a, c) Top and (b, d) side views of the crystal structures of 7 and 8,
respectively (C = gray, H = white, N = blue, and O = red). Substituents on the
aryl groups and solvent molecules are omitted for clarity. The two inner NH
protons of each porphyrin macrocycle of 7 were statistically disordered over the
four N atoms.
2
the neighboring substituents on the arylenedioxy linker (R and
3
R ) of mono-bridged dimer 1. The conformational differences are
1
reflected in the H NMR spectra of dimers 1a–d (Table 2, Figures
S1 and S2). The chemical shifts of the porphyrin proton signals

(Hmeso, H , and inner NH) of 1a and 1b are quite similar to those
[
12d]
of monomer 9 (Figure 4),
freedom of 1a and 1b.
confirming the high conformational
On the other hand, the chemical shifts of the porphyrin proton
signals of 1c are considerably upfield relative to those of the other
compounds; for example, the (NH) values of 1c and 9, are −3.82
and −2.77 ppm ( = −1.05 ppm), respectively. In addition, the
singlet signal of the proton on position 2 of the phenylenedioxy
linker (HL1) of 1c, observed at 5.59 ppm, is considerably upfield
shifted. These upfield shifts are characteristic of a cofacial
conformation and are attributed to the shielding effect caused by
aromatic ring current interactions between the closely associated
porphyrin macrocycles. Moreover, the proton signals of the two
ortho protons and two alkoxy substituents in the Ar groups of 1c
are broadened and/or inequivalently observed (Figure 5b). These
results also indicate a cofacial conformation for 1c because the
split peaks are assignable to endo and exo protons on the basis
of the roughly orthogonal orientations of the aryl rings and
porphyrin macrocycles (Figure 5e) and the rotational-motion
restriction of the aryl rings at room temperature on the NMR
timescale due to steric hindrance. The chemical shifts of the
porphyrin proton signals of 1d are slightly downfield relative to
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those of 1a and 1b. Moreover, compared to the chemical shifts of
2
-methyl-1,3-dimethoxybenzene,[15] the signal for the L2 proton is
upfield shifted ( = −0.84 ppm) while that of the methyl protons
on the linker units is considerably downfield shifted ( = −1.74
ppm). These shifts are the result of the diatropic ring current
associated with the 18 aromatic porphyrin macrocycle, and
suggests that 1d has a fixed open conformation (A).
Understandably, bis-bridged dimers 7 and 8 are strictly fixed
in a cofacial conformation. The chemical shifts of the porphyrin
proton signals of 7 and 8 are upfield relative to those of the
corresponding monomer (i.e., 10) and mono-bridged dimers (i.e.,
1
and 5 for 7 and 8, respectively). Moreover, the degree of the
shift for 7 is larger than that for 8; for example, the (NH) values
of 7 and 8 are −4.25 and −3.10 ppm, respectively, which reflects
the difference in the interplanar distances revealed by the
crystallographic studies. As was observed for 1c, the signals for
the two ortho protons and the two alkoxy substituents in the Ar
groups of 7 and 8 are observed to be completely inequivalent
1
Figure 5. Partial H NMR spectra of (a) 1a, (b) 1c, (c) 7, and (d) 8 representing
(
Figure 5c,d). This reflects the completely fixed cofacial
i
the terminal methyl signals of the OAm (3-methylbutoxy) substituents (500 MHz,
conformations of the bis-bridged dimers, in contrast to the certain
amount of conformational freedom observed for the mono-
bridged cofacial dimer 1c.
3
CDCl ). (e) Schematic representation of the regiochemistry of the aryl proton of
the cofacial porphyrin dimers (1c, 7, and 8).
Spectroscopic comparison
Table 2. Selected 1H NMR data for the prepared compounds (500 MHz,
CDCl ).
3
Solution-conformation information was also obtained by UV/vis
absorption studies. The Soret band region of the spectra is shown
in Figure 6, with the entire spectra shown in Figures S9 and S10.
Among the mono-bridged dimers, 1c exhibits the largest blue-shift
of the Soret band (414 nm) with respect to that of reference
monomer 9 (417 nm[12d]). In addition, its Soret band is significantly
broadened. These spectroscopic features are characteristic of
cofacial porphyrin dimers and can be explained well by exciton
coupling.[16] Therefore, these results, as well as those of the H
1

/ ppm
NMR study, strongly indicate that 1c adopts a cofacial
conformation in solution.
H
meso
H
4
H
1
H
2
H
3
H
L1
H
L2
NH
1
1
1
1
5
9
7
8
a
b
c
d
10.14
10.12
9.59
9.38
9.46
8.95
9.58
9.24
9.38
8.77
8.94
9.29
9.29
9.28
8.88
9.29
9.20
9.26
9.12
9.11
8.73
9.12
9.02
9.10
9.06
9.06
8.56
9.10
8.86
8.98
8.53
8.58
8.90
7.59
7.54
5.59
6.92
6.31
-
−2.80
−2.78
−3.82
−2.72
−2.94
−2.77
−4.25
−3.10
−2.49
[
b]
[
b]
10.12
10.03
10.10
-
5.74
6.64
7.32
[
a]
[b]
[b]
-
-
[
[
[
b]
b]
b]
[c]
[d]
-
-
-
=
=
=
=
4.00
4.54
8.16
7.92
[c]
[d]
[c]
[d]
[b]
[b]
=
=
-
-
1
0[a]
[
a] Data from ref. 12d. [b] No proton available. [c] Equivalent to H4. [d]
Equivalent to H3
.
Figure 6. Soret bands in the UV/vis absorption spectra of the prepared
compounds in toluene. The extinction coefficients of monomers 9 and 10 have
been doubled.
Figure 4. Chemical structures of the reference monomers.[12d]
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The Soret bands of both bis-bridged dimers are considerably
blue-shifted, with 7 exhibiting the greatest shift. This suggests that
the structures of the bis-bridged dimers obtained by X-ray
diffractometry are essentially retained, even in solution.
Dimerization was found to have quite a small effect on the
positions of the longest wavelength bands, which are determined
only by the number of meso substituents.
reduction potentials of 1a, 7, 8, as well as those of previously
reported 9 and 10, are summarized in Table S2, with the cyclic
voltammograms of 1a, 7, and 8 shown in Figure 7. The potentials
of the dimers are almost the same as those of the reference
monomers. It is noteworthy that the first reduction wave of 7 is
+
split (−1.64 and −1.74 V vs. Fc/Fc ) and the second reduction
wave is irreversible, which indicates that the two porphyrin
moieties in 7 are reduced in a stepwise manner due to the
electronic communication between them. On the other hand, no
splitting is observed for the first reduction wave of 8, rather its
second reduction wave is split, which indicates that electronic
communication between the more separated porphyrin moieties
in 8 is weaker than that in 7, but is not negligible.
Fluorescence data for 1a, 7, 8, 9, and 10 are summarized in
Table 3, and the spectra are shown in Figure S11. As was
observed for the positions of the longest-wavelength UV/vis
absorption bands, the positions of the emission peaks and
spectral shapes are primarily determined by the number of meso
substituents. The fluorescence quantum yields (fl) of both mono-
and bis-bridged dimers are slightly lower than those of the
reference monomers. Notably, the dependence of the interplanar
distance on the spectral shape and fl is very small based on the
data for 7 and 8. This small dependence is uncommon because
the reported cofacial dimers, mainly mono-bridged dimers, have
considerably low fl values with strong distance-dependence;[
2a-
d,5d,9d]
for example, the fl values of a mono-anthracene- and
biphenylene-bridged dimers are 0.22 and 0.04, respectively,
relative to the corresponding monomer.[2c,2d] The decrease in fl
due to dimerization have been explained by the strong -orbital
overlap in face-to-face dimers leading to non-fluorescence decay
processes.[2a,2b] However, our results do not fit this explanation;
instead, we suggest that -orbital overlap is not the main factor
governing the decrease in fl. The major difference between the
previously reported dimer and the dimer reported herein lies in
structural rigidities; i.e., various intramolecular motions, such as
slipping and pacman-like motion, are structurally allowed in
mono-bridged dimers bridged even by rigid linkers, while those,
especially the pacman-like motion, are significantly hindered in
our dimers. The high structural rigidities of the bis-bridged dimers
prevent the nonradiative deactivation associated with
dimerization. These observations suggest that 7 and 8 have the
highest rigidities among the cofacial porphyrin dimers exploring
emission properties.
Table 3. Fluorescence data for the prepared compounds in toluene excited
at 520 nm.
Figure 7. Cyclic voltammograms of (a) 1a, (b) 7, and (c) 8 in CH
0.1 M TBAPF
2 2
Cl containing
fl / nm[a]

[b]

fl
6
.
1
9
7
8
1
a
648, 714
649, 715
664, 735
663, 733
664, 733
0.077 (0.93)
0.083
0.094 (0.72)
0.096 (0.74)
0.130
Conclusions
0
[
a] Wavelengths of the emission maxima. [b] Fluorescence quantum yield.
We have reported a practical and efficient procedure for the
synthesis of arylenedioxy-bridged porphyrin dimers via catalyst-
free nucleophilic substitution. In most cases, the product yields
were considerably high. The orientations of the two porphyrin
macrocycles and degree of orientational freedom are controlled
by both the number of linker units in the structure and the
neighboring substituents on the resorcinol. In particular, the highly
rigid cofacial structures of the bis-bridged dimers were revealed
by X-ray diffraction and spectroscopic studies. Owing to the high
rigidities of the bis-bridged dimers, the nonradiative deactivation
of the photoexcited states associated with dimerization, which are
The values in parentheses are relative ones to the corresponding
monomers.
Electrochemistry
To obtain further insight into the electronic communication
between the two porphyrin macrocycles of the dimers, 1a, 7, and
were subjected to cyclic voltammetry. The effect of stacking was
clearly observed in the reduction events. The oxidation and
8
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typically observed for reported dimers, are mostly suppressed,
suggesting that 7 and 8 have highest rigidities among the cofacial
porphyrin dimers exploring emission properties. For the closely
stacked bis-bridged dimer, electronic communication between the
porphyrin macrocycles was observed in the electrochemical study.
The small dimer 7 has a small empty cavity while the larger dimer
The resultant mixture was stirred at room temperature for 1.5 hours. The
unreacted zinc powder was removed by filtration, and the filtrate was
diluted with water (300 mL). The product was extracted with Et
organic layer was washed with aqueous NaHCO and brine, and dried over
MgSO . Solvent was removed under the reduced pressure. The crude
2
O. The
3
4
product was purified by flash column chromatography (silica gel,
toluene/EtOAc = 10:1, then 5:1) to give 3c as a pink waxy solid (1.181 g,
8
has a cavity that can encapsulate small molecules. Our
.11 mmol, 71%). 1H NMR data were consistent with the previously
7
reported one.[19] 1H NMR (500 MHz, CDCl
)  = 6.85 (s, 1H), 6.28 (s, 1H),
preliminary experiments suggest that several linear alkane
molecules can be encapsulated within the cavity of 8. We
anticipate that the synthesis method developed herein will
contribute to the further development of the chemistry of cofacial
porphyrin dimers. We also anticipate that these bis-bridged
dimers are some of the most rigid dimers reported to date, and
thus exhibit significant selectivities and/or affinities during
molecular recognition or catalysis. We are currently developing
this chemistry, the results of which will be reported in due course.
3
4.98 (brs, 2H), 2.54 (q, J = 7.6 Hz, 4H), 1.19 ppm (t, J = 7.6 Hz, 6H).
General procedure for the synthesis of 1,3-phenylenedioxy-bridged
porphyrin dimer 1
5
-Bromo-10,20-bis[3,5-bis(3-methylbutoxy)phenyl]porphyrin (2) (0.080
mmol), resorcinol derivative 3 (0.020 mmol), and K CO (0.10 mmol) were
mixed in dry butyronitrile (2 mL). The mixture was purged with N and
2
3
2
refluxed with stirring while protected against exposure to light. The reaction
was monitored by TLC. After the reaction was complete, the reaction
2 3
mixture was filtrated to remove K CO , and then solvent was evaporated
Experimental Section
under reduced pressure. The crude product was purified by flash column
chromatography (silica gel) to give 1.
Instrumentation and Materials
Mono-(5-acetyl-1,3-phenylenedioxy)-bridged porphyrin dimer 1a
5
-Bromo-10,20-bis[3,5-bis(3-methylbutoxy)phenyl]porphyrin (2)[17] 5,15-
dibromo-10,20-bis[3,5-bis(3-methylbutoxy)phenyl]porphyrin (6)[17b]
and
the reference monomers (9 and 10)[12d] were synthesized by previously
,
reported
procedures.
N,N-Dimethylformamide
(DMF),
N,N-
n
dimethylacetamide (DMA), butyronitrile ( PrCN), and toluene were distilled
from CaH
any further purification. CDCl
Analytical thin layer chromatography (TLC) was performed on silica gel 60
254 plates. Flash column chromatography was performed using silica gel
0N (spherical, neutral, 40–50 m). All NMR spectral data were recorded
2
. All other chemicals were of reagent grade and used without
3
was acquired from Acros Organics.
2
was reacted with 5-acetylresorcinol (3a) for 21 h according to the general
procedure. The crude product was purified by flash column
chromatography (silica gel, hexane/toluene 1:2) to give 1a as a purple solid
F
6
(
81%). Analytically pure sample was obtained by recrystallization from hot
toluene/hexane as a purple powder. R = 0.55 (toluene); m.p. 280−281 ºC;
1H NMR (500 MHz, CDCl
)  = 10.14 (s, 2H, H ), 9.38 (d, J = 4.7 Hz, 4H,
), 9.29 (d, J = 4.7 Hz, 4H, H ), 9.12 (d, J = 4.6 Hz, 4H, H ), 9.06 (d, J =
.7 Hz, 4H, H ), 7.59 (t, J = 2.3 Hz, 1H, H ), 7.40 (d, J = 2.2 Hz, 8H, H ),
.01 (d, J = 2.4 Hz, 2H, H ), 6.92 (t, J = 2.2 Hz, 4H, H ), 4.18 (t, J = 6.7 Hz,
6H, H), 1.90 (m, J = 6.6 Hz, 8H, H ), 1.82 (s, 3H, H ), 1.80 (q, J = 6.7 Hz,
6H, H), 0.99 (d, J = 6.6 Hz, 48H, H), −2.80 ppm (s, 4H, H
); 13C NMR
)  = 196.9 (Cq), 167.0 (Cq), 158.6 (Cq), 147.2 (Cq),
46.7 (Cq), 146.4 (Cq), 142.9 (Cq), 141.7 (Cq), 139.6 (Cq), 131.7 (CH),
31.5 (CH), 131.3 (Cq), 131.2 (CH), 127.4 (CH), 119.8 (Cq), 114.5 (CH),
09.7 (2×CH), 104.8 (CH), 101.1 (CH), 66.8 (CH ), 38.1 (CH ), 26.5 (CH ),
); IR (ATR): ν˜ = 3297, 2954, 2928, 2869, 1690,
on a 500 MHz spectrometer at ambient temperature (25 °C) unless
otherwise noted. 1H NMR spectra were referenced internally to
f
13
3
b
tetramethylsilane as the standard. C NMR spectra were referenced
H
f
c
d
internally to solvent signals ( = 77.0 ppm for CDCl ). APCI HRMS data
3
4
7
1
1
e
m
g
were measured on a Bruker micrOTOF II equipped with the DirectProbe
assembly. ESI HRMS data were measured on a Bruker micrOTOF QIII. IR
n
h
i
k
o
spectral data were recorded on
a PerkinElmer Spectrum Two
j
l
a
spectrometer equipped with an ATR unit. UV/vis spectral data were
recorded on Shimadzu UV-3600 or UV-3150 spectrometers. Fluorescence
(125 MHz, CDCl
3
1
1
1
spectral data were recorded on
a JASCO FP-8200 fluorescence
spectrometer. Measurements were performed without deaeration of the
sample solution. The fluorescence quantum yields were estimated by
taking tetraphenylporphyrin in toluene as the standard (fl = 0.11).[18]
Melting points were determined on a Yanaco MP-S3 melting point
apparatus. Cyclic voltammetry (CV) measurements were carried out using
2
2
3
25.1 (CH), 22.7 ppm (CH
587, 1430, 1406, 1331, 1291, 1152, 1055, 923, 848, 791, 727, 691 cm ;
UV/Vis (toluene): max (Log) = 415 (5.78), 510 (4.58), 544 (4.08), 586
3
-
1
1
(4.02), 643 nm (3.73); HRMS(APCI): m/z calcd for
112 129 8 11
C H N O :
ALS 650C electrochemical analyzer in argon-saturated CH
2 2
Cl solutions
+
1762.9808 ([M+H] ); found 1762.9792; elemental analysis calcd (%) for
containing 0.1 tetrabutylammonium hexafluorophosphate as
M
a
C
112 128
H N
8
O11: C, 76.33; H, 7.32; N, 6.36; found: C, 76.06; H, 7.30; N, 6.18.
supporting electrolyte at ambient temperature (298 K). A conventional
three-electrode cell was used with a glassy carbon working electrode, a
platinum wire counter electrode, and an Ag/AgCl reference electrode.
Ferrocene was used as the internal standard in all electrochemical
experiments.
Mono-(1,3-phenylenedioxy)-bridged porphyrin dimer 1b
Synthesis of 4,6-diethylresorcinol (3c)[19]
This compound was synthesized in a similar manner to the synthesis of
the related compounds.[20] To a suspension of 4,6-diacetylresorcinol
2
was reacted with resorcinol (3b) for 25 h according to the general
(1.942 g, 10 mmol) and Zn powder (13.078 g, 200 mmol) in ethanol (200
procedure. The crude product was purified by flash column
chromatography (silica gel, hexane/toluene 1:1, then 1:1.5) to give 1b as
mL) at 0 °C, concentrated hydrochloric acid (50 mL) was added dropwise.
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a
purple solid (84%). Analytically pure sample was obtained by
purified by flash column chromatography (silica gel, hexane/toluene 1:1,
recrystallization from hot octane as
a
purple powder.
R
f
=
0.15
)  =
then 1:1.5) to give 1d as a purple solid (71%). Analytically pure sample
1
(hexane/toluene 1:1); m.p.: 263−264 ºC; H NMR (500 MHz, CDCl
3
was obtained by recrystallization from hot octane as a purple powder. R
f
1
1
9
0.12 (s, 2H, H
.11 (d, J = 4.6 Hz, 4H, H
), 7.40 (d, J = 2.2 Hz, 8H, H
t, J = 8.5 Hz, 1H, H
b
), 9.46 (d, J = 4.8 Hz, 4H, H
f
), 9.28 (d, J = 4.7 Hz, 4H, H
c
),
= 0.28 (hexane/toluene 1:1); m.p.: 162−163 ºC; H NMR (500 MHz, CDCl
3
)
d
), 9.06 (d, J = 4.7 Hz, 4H, H
e
), 7.54 (t, J = 2.4
 = 10.12 (s, 2H, H
), 9.12 (d, J = 4.6 Hz, 4H, H
2.2 Hz, 8H, H ), 6.93 (t, J = 2.2 Hz, 4H, H
5.74 (d, J = 8.4 Hz, 2H, H ), 4.20 (t, J = 6.7 Hz, 16H, H
1.91 (m, J = 6.7 Hz, 8H, H ), 1.81 (q, J = 6.6 Hz, 16H, H
Hz, 48H, H), −2.72 ppm (s, 4H, H
); 13C NMR (125 MHz, CDCl
3
b
), 9.58 (d, J = 4.7 Hz, 4H, H
), 9.10 (d, J = 4.7 Hz, 4H, H
), 6.20 (t, J = 8.4 Hz, 1H, H
), 3.86 (s, 3H, H
m
f
), 9.29 (d, J = 4.6 Hz, 4H,
Hz, 1H, H
m
g
), 6.91 (t, J = 2.2 Hz, 4H, H
h
), 6.81
H
c
d
e
), 7.41 (d, J =
(
6
1
o
), 6.31 (dd, J = 6.1 and 2.3 Hz, 2H, H
), 1.90 (m, J = 6.7 Hz, 8H, H ), 1.81 (q, J = 6.8 Hz, 16H, H
.00 (d, J = 6.7 Hz, 48H, H), −2.78 ppm (s, 4H, H
); 13C NMR (125 MHz,
)  = 167.2 (Cq), 158.6 (Cq), 147.1 (Cq), 146.6 (Cq), 146.3 (Cq),
43.0 (Cq), 142.1 (Cq), 132.0 (Cq), 131.7 (CH), 131.4 (CH), 131.1 (CH),
30.0 (CH), 127.8 (CH), 119.7 (Cq), 114.5 (CH), 110.2 (CH), 105.6 (CH),
04.6 (CH), 101.1 (CH), 66.8 (CH ), 38.2 (CH ), 25.1 (CH), 22.7 ppm
); IR (ATR): ν˜ = 3294, 2954, 2926, 2869, 1588, 1429, 1332, 1245,
n
), 4.18 (t, J =
g
h
o
),
.7 Hz, 16H, H
i
k
j
),
n
i
),
l
a
k
j
), 1.00 (d, J = 6.5
CDCl
3
l
a
)  = 165.4
1
1
1
(Cq), 158.6 (Cq), 147.0 (Cq), 146.6 (Cq), 146.4 (Cq), 143.0 (Cq), 142.2
(Cq), 132.9 (Cq), 131.7 (CH), 131.4 (CH), 131.0 (CH), 127.8 (CH), 126.2
(CH), 119.7 (Cq), 114.5 (CH), 113.8 (Cq), 110.0 (CH), 104.5 (CH), 101.1
2
2
(
CH
3
2 2 3 3
(CH), 66.8 (CH ), 38.2 (CH ), 25.1 (CH), 22.7 (CH ), 10.0 ppm (CH ); IR
-
1
1158, 1130, 1062, 965, 924, 848, 794, 780, 732, 691 cm ; UV/Vis
(ATR): ν˜ = 3300, 2954, 2923, 2869, 1587, 1461, 1430, 1383, 1336, 1233,
-
1
(toluene): max (Log) = 415 (5.79), 510 (4.59), 544 (4.10), 586 (4.02), 643
1149, 1117, 1059, 964, 922, 846, 796, 733, 692 cm ; UV/Vis (toluene):
+
nm (3.75); HRMS(APCI): m/z calcd for C110
found 1720.9647; elemental analysis calcd (%) for C110
6.80; H, 7.38; N, 6.51; found: C, 76.53; H, 7.28; N, 6.30.
127 8
H N O10: 1720.9702 ([M+H] ),

max (Log) = 417 (5.81), 480 (3.85), 510 (4.61), 545 (4.14), 586 (4.04),
+
H
126
N
8
O
10: C,
643 nm (3.81); MS(APCI): m/z calcd for C111
129 8
H N O10: 1733.97 ([M+H] ),
7
128 8
found 1733.95; elemental analysis calcd (%) for C111H N O10: C, 76.87;
H, 7.44; N, 6.46; found: C, 76.61; H, 7.39; N, 6.27.
Mono-(4,6-diethyl-1,3-phenylenedioxy)-bridged porphyrin dimer 1c
Mono-(2,7-naphthylenedioxy)-bridged porphyrin dimer 5
2
was reacted with 4,6-diethylresorcinol (3c) for 94 h according to the
2
was reacted with 2,7-dihydroxynaphthalene (4) instead of 3 for 24 h
general procedure, but 3 equiv. of 2 and 20 equiv. of K CO was used. The
2
3
according to the general procedure. The crude product was purified by
flash column chromatography (silica gel, hexane/toluene 1:1, then 1:1.5)
to give 5 as a purple solid (72%). Analytically pure sample was obtained
crude product was purified by flash column chromatography (silica gel,
hexane/toluene 1:1, then 1:1.5) to give 1c as a purple solid (37%).
Analytically pure sample was obtained by recrystallization from hot octane
by recrystallization from hot octane as a purple powder. R
f
= 0.33
)  =
as
a
purple powder.
R
f
=
0.15 (hexane/toluene 1:1);
R
f
=
0.15
)  =
hexane/toluene 1:1); m.p.: 270−272 ºC; 1H NMR (500 MHz, CDCl
(
3
1
(hexane/toluene 1:1); m.p.: 208−210 ºC; H NMR (500 MHz, CDCl
3
1
9
0.03 (s, 2H, H
.02 (d, J = 4.5 Hz, 4H, H
), 7.32 (dd, J = 7.5, 2.2 Hz, 2H, H
.85 (t, J = 2.2 Hz, 4H, H
6H, H), 1.86 (m, J = 6.7 Hz, 8H, H
), −2.94 ppm (s, 4H, H
b
), 9.24 (d, J = 4.7 Hz, 4H, H
f
), 9.20 (d, J = 4.6 Hz, 4H, H
c
),
9
8
6
4
H
−
.59 (s, 2H, H
.73 (d, J = 4.5 Hz, 4H, H
.96 (brs, 8H, H and H
.02 (m, 16H, H and H′), 3.33 (q, J = 7.4 Hz, 4H, H
, H, H ′, H′ and H ), 1.02 (brs, 24H, H or H′), 0.94 (brs, 24H, H
3.82 ppm (s, 4H, H )  = 162.7 (Cq), 158.4
); 13C NMR (125 MHz, CDCl
b
), 8.95 (d, J = 4.7 Hz, 4H, H
f
), 8.88 (d, J = 4.5 Hz, 4H, H
c
),
),
),
d e
), 8.86 (d, J = 4.7 Hz, 4H, H ), 7.76 (d, J = 9.1
d
), 8.56 (d, J = 4.7 Hz, 4H, H
e
), 7.62 (s, 1H, H
n
Hz, 2H, H
6
1
o
m
), 7.27 (d, J = 2.2 Hz, 8H, H
g
),
g
g
′), 6.79 (t, J = 2.2 Hz, 4H, H
), 5.59 (s, 1H, H
h m
h
), 6.64 (d, J = 1.9 Hz, 2H, H
), 1.76 (q, J = 6.7 Hz, 16H, H
); 13C NMR (125 MHz, CDCl
3
)
n
), 4.12 (t, J = 6.7 Hz,
i
i
o
), 2.00–1.68 (m, 30H,
i
k
j
), 1.00
k
j
k
j
p
l
l
l
or H′),
l
(d, J = 6.6 Hz, 48H, H
l
a
a
3

1
1
1
2
1
= 164.6 (Cq), 158.5 (Cq), 146.9 (Cq), 146.4 (Cq), 146.2 (Cq), 142.8 (Cq),
41.9 (Cq), 135.6 (Cq), 132.0 (Cq), 131.5 (CH), 131.3 (CH), 130.9 (CH),
29.6 (CH), 127.6 (CH), 125.1 (Cq), 119.6 (Cq), 116.5 (CH), 114.4 (CH),
11.6 (CH), 104.5 (CH), 101.0 (CH), 66.7 (CH ), 38.1 (CH ), 25.1 (CH),
2 2
2.7 ppm (CH
(
(
Cq), 142.7 (Cq), 132.9 (Cq), 131.1 (CH), 130.6 (CH), 130.3 (CH), 129.8
CH), 126.9 (CH), 125.4 (Cq), 118.8 (Cq), 114.4 (br, CH), 106.8 (CH),
103.4 (CH), 100.6 (CH), 66.6 (CH
2 2 2
), 38.1 (CH ), 25.1 (CH), 23.6 (CH ),
22.7 (CH ), 15.1 ppm (CH ) (four signals corresponding to the pyrrole α
3
3
3
); IR (ATR): ν˜ = 3297, 2954, 2927, 2869, 1588, 1429, 1384,
carbons were not observed due to severe exchange broadening through
NH tautomerism); IR (ATR): ν˜ = 3295, 2956, 2928, 2870, 1587, 1464,
-1
336, 1243, 1151, 1057, 965, 922, 845, 833, 792, 725, 691 cm ; UV/Vis
(toluene): max (Log) = 416 (5.81), 510 (4.59), 545 (4.11), 586 (4.02), 643
1432, 1407, 1383, 1346, 1283, 1243, 1164, 1116, 1056, 965, 923, 846,
+
nm (3.78); HRMS(APCI): m/z calcd for C114
found 1770.9839; elemental analysis calcd (%) for C114
7.34; H, 7.29; N, 6.33; found: C, 77.13; H, 7.52; N, 6.19.
H
129
N
8
O
10: 1770.9859 ([M+H] ),
-
1
833, 789, 729, 689 cm ; UV/Vis (toluene): max (Log) = 414 (5.69), 513
128 8
H N O10: C,
(4.45), 549 (4.09), 590 (3.90), 647 nm (3.78); HRMS(APCI): m/z calcd for
7
+
C
114 135
H N
8
O
10: 1777.0328 ([M+H] ), found 1777.0289; elemental analysis
calcd (%) for C114
134 8
H N O10: C, 77.08; H, 7.60; N, 6.31; found: C, 77.04; H,
Bis-(5-acetyl-1,3-phenylenedioxy)-bridged porphyrin dimer 7
7.61; N, 6.13.
Mono-(2-methyl-1,3-phenylenedioxy)-bridged porphyrin dimer 1d
5
,15-Dibromo-10,20-bis[3,5-bis(3-methylbutoxy)phenyl]porphyrin (6) (200
mg, 0.207 mmol), 5-acetylresolcinol (3a) (31.56 mg, 0.207 mmol), and
CO (143.27 mg, 1.03 mmol) were mixed in dry DMA (40 mL). The
mixture was purged with N and stirred at 120 C for 5 h while protected
2
was reacted with 2-methylresorcinol (3d) for 6 h according to the general
K
2
3
procedure, but K PO was used instead of K CO . The crude product was
3
4
2
3
2
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+
against exposure to light. The reaction mixture was diluted with toluene,
1927.0070 ([M+H] ), found 1927.0089; elemental analysis calcd (%) for
124 132 8
C H N O12: C, 77.31; H, 6.91; N, 5.82; found: C, 76.95; H, 6.87; N, 5.69.
washed with water (9  50 mL), dried over MgSO
reduced pressure. The crude product was purified by flash column
chromatography (silica gel, toluene, then CHCl ) to give 7 as a purple solid
121.2 mg, 0.063 mmol, 61%). Analytically pure sample was obtained by
recrystallization from EtOAc/EtOH as a purple powder. R = 0.45 (toluene);
4
, and concentrated under
3
X-Ray crystal structure determinations
(
f
Purple crystals of 1b were grown by the slow diffusion of methanol vapor
into a toluene solution of 1b. Purple crystals of 5 were grown by the slow
diffusion of hexane vapor into a 4-chlorotoluene solution of 5. Purple
crystals of 7 were grown by the slow diffusion of hexane vapor into a
toluene solution of 7. Purple crystals of 8 were grown by the slow diffusion
of methanol vapor into a THF solution of 8. Single-crystal X-ray diffraction
data were collected on a Rigaku XtaLab P200 diffractometer using
graphite-monochromated Cu K radiation ( = 1.54178 Å) for 1b and 5, a
Bruker Smart APEX CCD diffractometer using graphite-monochromated
Mo K radiation ( = 0.71073 Å) for 7, and a Rigaku XtaLab P200
diffractometer using graphite-monochromated Mo K radiation ( =
.71075 Å) for 8. The structures were solved using SHELXS or SHELXT[
programs and refined by full-matrix least-squares calculations on F2
SHELXL).[22] All non-hydrogen atoms were modeled anisotropically.
Hydrogen atoms were fixed at calculated positions and refined with a riding
model. In the crystal of 8, solvent molecules were heavily disordered, and
thus they were removed from the structure (and the corresponding F
the SQUEEZE procedure implemented in the PLATON program suite.[
1
m.p.: >300 ºC; H NMR (500 MHz, CDCl
3
)  = 8.77 (d, J = 4.7 Hz, 8H, H
), 8.16 (d, J = 2.3 Hz, 4H, H ), 7.10 (s, 4H, H
b
),
),
),
),
8
6
4
2
.53 (d, J = 4.7 Hz, 8H, H
.76 (t, J = 2.2 Hz, 4H, H
.00 (t, J = 2.3 Hz, 2H, H
.03 (m, J = 6.7 Hz, 4H, H
c
k
d
e
), 6.63 (s, 4H, Hd′), 4.04 (t, J = 6.9 Hz, 8H, H
), 3.93 (t, J = 6.7 Hz, 8H, Hf′), 3.02 (s, 6H, H
), 1.88 (q, J = 6.9 Hz, 8H, H
f
j
l
h
g
), 1.74 (m, J = 6.7
),
); 13C NMR (125 MHz,
)  = 197.8 (Cq), 166.3 (Cq), 158.6 (Cq), 158.4 (Cq), 141.5 (Cq),
Hz, 4H, Hh′), 1.63 (q, J = 6.7 Hz, 8H, Hg′), 1.18 (d, J = 6.6 Hz, 24H, H
i
0
.87 (d, J = 6.6 Hz, 24H, Hi′), −4.25 ppm (s, 4H, H
a
CDCl
3
1
1
3
39.8 (Cq), 130.6 (CH), 129.2 (Cq), 126.6 (CH), 119.6 (Cq), 115.4 (CH),
14.1 (CH), 109.8 (CH), 108.8 (CH), 100.4 (CH), 66.7 (CH ), 66.4 (CH ),
8.3 (CH ), 38.0 (CH ), 27.3 (CH ), 25.5 (CH), 25.0 (CH), 23.0 (CH ), 22.6
) (two signals corresponding to the pyrrole α carbons were not
2
2
2
2
3
3
21]
0
ppm (CH
3
observed due to severe exchange broadening through NH tautomerism);
(
IR (ATR): ν˜ = 3301, 2954, 2924, 2869, 1688, 1587, 1432, 1355, 1295,
-
1
1
274, 1166, 1126, 1060, 1007, 981, 799, 727 cm ; UV/Vis (toluene): max
(
(
Log) = 408 (5.66), 491 (3.74), 521 (4.29), 558 (4.16), 600 (3.78), 658 nm
0
) with
+
3.93); HRMS(APCI): m/z calcd for C120
133
H N
8
O14: 1910.9968 ([M+H] ),
23]
132 8 2
found 1910.9968; elemental analysis calcd (%) for C120H N O14·H O: C,
Fourier (|Fo|) and difference Fourier (|Fo|−|Fc|) maps were drawn using
the ShelXle program.[24] The crystallographic data are summarized in
74.74; H, 7.00; N, 5.81; found: C, 74.75; H, 6.91; N, 5.78.
Tables S1. For 1b and 5, we were not able to obtain sufficient data
because of the very weak diffraction. Therefore, those data are treated as
preliminary results. CCDC 1959547 (7), and 1970724 (8) contain the
supplementary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.
Bis-(2,7-naphthylenedioxy)-bridged porphyrin dimer 8
Acknowledgements
5
,15-Dibromo-10,20-bis[3,5-bis(3-methylbutoxy)phenyl]porphyrin
(6)
This work was partially supported by JSPS KAKENHI Grant
Numbers JP17K14447 and JP25110002.
(
289.7 mg, 0.300 mmol), 2,7-dihydroxynaphthalene (4) (62.7 mg, 0.391
mmol), and K CO (143.27 mg, 1.03 mmol) were mixed in dry DMF (45
mL). The mixture was purged with N and stirred at 80 C for 13 h, and
then at 120 C for 7 h while protected against exposure to light. The
reaction mixture was diluted with CHCl , washed with water (5  100 mL),
dried over Na SO , and concentrated under reduced pressure. The crude
product was purified by flash column chromatography (silica gel,
hexane/toluene 1:1), and then recrystallized from CHCl /MeOH to give 8
as a purple solid (199.1 mg, 0.103 mmol, 69%). Analytically pure sample
2
3
2
Keywords: Aromatic substitution • Host-guest systems • Pi
interactions • Porphyrinoids • Rigid dimers
3
2
4
[
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[
-
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1162, 1057, 1011, 984, 957, 920, 871, 829, 792, 717 cm ; UV/Vis
(
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3.89), 657 nm (3.98); HRMS(APCI): m/z calcd for H N O :
C
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A series of porphyrin dimers bridged
by one or two arylenedioxy linkers
was successfully synthesized in high
yields by catalyst-free nucleophilic
aromatic substitution. The
Ken-ichi Yamashita,* Narumi
Kuramochi, Hang Pham Qui Van,
Kazuhiro Furutani, Takuji Ogawa, Ken-
ichi Sugiura*
orientational freedom and
Page No. – Page No.
conformation of the two porphyrin
macrocycles in the mono-bridged
dimers were controlled by the
substituents on the arylenedioxy
linkers. Bis-bridged dimers exhibited
a highly rigid cofacial conformation.
Efficient Synthesis of Arylenedioxy-
Bridged Porphyrin Dimers through
Catalyst-Free Nucleophilic Aromatic
Substitution
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