Covalent Linking of Coordination-Organized Slipped Cofacial Porphyrin Dimers

Article abstract of DOI:10.1246/bcsj.77.365

Coordination-organized porphyrin dimers of 5,15-bis[2-(allyloxycarbonyl)ethyl]- and bis[3-(allyloxy)propyl]-20-(1-methyl-2-imidazolyl)porphyrinatozinc were covalently linked by an intramolecular olefin metathesis reaction in excellent yields (93-98%). It was found that the yields of the intramolecular metathesis reaction depended strongly on the molecular length of the substituent at the 5 and 15 positions. Introducing longer 3-(allyloxycarbonyl)propyl and 4-(allyloxycarbonyl)butyl substituents decreased sharply the yields of the covalent linking reaction to 26% and 16%, respectively. The covalently linked dimers maintained their coordination structures even when dissolved in as polar a solvent as pyridine.

Full text of DOI:10.1246/bcsj.77.365

ꢀ 2004 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 77, 365–374 (2004)
365
Covalent Linking of Coordination-Organized Slipped Cofacial
Porphyrin Dimers
ꢀ;1;2
Atsushi Ohashi,2 Akiharu Satake,1 and Yoshiaki Kobuke
1Graduate School of Materials Science, Nara Institute of Science and Technology,
8916-5 Takayama, Ikoma, Nara 630-0192
2CREST, Japan Science and Technology Corporation (JST)
Received September 3, 2003; E-mail: kobuke@ms.aist-nara.ac.jp
Coordination-organized porphyrin dimers of 5,15-bis[2-(allyloxycarbonyl)ethyl]- and bis[3-(allyloxy)propyl]-20-
(1-methyl-2-imidazolyl)porphyrinatozinc were covalently linked by an intramolecular olefin metathesis reaction in excel-
lent yields (93–98%). It was found that the yields of the intramolecular metathesis reaction depended strongly on the mo-
lecular length of the substituent at the 5 and 15 positions. Introducing longer 3-(allyloxycarbonyl)propyl and 4-(allyloxy-
carbonyl)butyl substituents decreased sharply the yields of the covalent linking reaction to 26% and 16%, respectively.
The covalently linked dimers maintained their coordination structures even when dissolved in as polar a solvent as pyr-
idine.
Ultrafast energy, hole, and electron transfers in multi-por-
phyrin arrays make these materials attractive for possible use
as biomimetic materials and for possible applications in nano-
meter-scale optical and electronic devices.1 Recently, it was
demonstrated that multi-porphyrin systems based on a slipped
co-facial dimer of imidazolylporphyrinatozincs2 exhibited ex-
cellent properties as third order non-linear optics materials3
and light-harvesting antenna complexes.4 These multi-porphy-
rins are readily prepared by self-coordination. Special struc-
tures, such as large rings,4 linear oligomers with specific termi-
nal porphyrins,2b and vectorial growth on a gold surface5 were
manipulated by self-assembly. These supramolecular systems
have many advantages from the viewpoint of organic synthesis.
The binding constant of complementary coordination of imida-
zolyl-to-Zn in chloroform is as large as 1010 Mꢁ1, but the coor-
dination structure tends to dissociate in the presence of polar
solvents, such as methanol or pyridine, and undergoes ex-
change reactions. These properties enabled re-organization of
the structures once formed,4,5 but at the same time made it dif-
ficult to maintain the systems in polar media. With these factors
in mind, the linkage of self-assembled structures of porphyrin
oligomers and polymers was explored. An effective method
of covalently linking self-assembled porphyrin dimers using a
ring-closing metathesis reaction6 is reported.
mentarily organized porphyrin dimers were close to each other
(Fig. 1). Based on this, unsaturated moieties of suitable lengths
were introduced at these positions. First, porphyrin dimer D-5a,
which had 2-(allyloxycarbonyl)ethyl groups at the 5,50,15,150-
positions, was designed as a precursor for dimer 7a. An ester
moiety was employed for versatile functional transformations
such as trans-esterification and hydrolysis. Since 7a has two in-
ternal olefins, all three isomers, (E,E), (Z,Z), and (E,Z), were
expected. Structures predicted by molecular mechanics calcula-
tions for (Z,Z)- and (E,E)-7a are shown in Figs. 1(a), (b) and
(c), (d), respectively. The size of each ring composed of the
5,50- or 15,150-substituents was similar to an 18 membered ring.
The designed porphyrin dimer 5a was synthesized according
to Fig. 2. Porphyrin 2a was prepared by condensation of dipyr-
romethane 1a, 1-methylimidazole-2-carbaldehyde, and octanal
in 6% yield. Then, two allyl moieties were introduced into the 5
and 15-positions by trans-esterification under neutral condi-
tions in the presence of the distannoxane catalyst 3.8 Treatment
of Zn(OAc)2 with 4a gave the zinc porphyrin complex 5a,
which automatically converted to the complementary dimer
D-5a in CHCl3. The dimer structure was maintained in CHCl3
even at concentrations below 1 mM.
The key olefin metathesis reaction on D-5a was carried out
in dilute conditions in CHCl3 (5 mM) in the presence of a 1st
generation Grubbs catalyst (10 mol%). The progress of the re-
action was monitored by MALDI-TOF mass spectroscopy. In
the case of precursor D-5a, the dimer structure predominated
in CHCl3 solution, with the major peaks in the mass spectra
corresponding to monomeric 5a. As the reaction proceeded,
the peak at m=z ¼ 1497, corresponding to covalently linked
dimer 7a, appeared and became dominant after 2 h. The crude
material was purified by SiO2 chromatography to give 7a in ex-
cellent yield (95%). Mass spectroscopy of the isolated 7a indi-
cated the complete formation of two linkages at the 5,50- and
15,150-positions. The 1H NMR spectrum of 7a showed no signs
Results and Discussion
Metathesis Reaction.
Olefin metathesis is a powerful
method of C–C bond-formation because most functional
groups except olefins are inert.6 In addition, the metathesis re-
action proceeds in non-coordinative solvents, such as CHCl3
and CH2Cl2, without the presence of any organic base. This re-
action was applied to the covalent linkage of self-assembled
porphyrin complexes. On the basis of molecular modeling us-
ing the Cerius 2 software,7 it was predicated that two pairs of
substituents at the 5,50 and 15,150-meso positions of comple-
Published on the web February 10, 2004; DOI 10.1246/bcsj.77.365

366 Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
Covalent Linking of Porphyrin Dimers
(a)
(c)
(e)
N
N
N
N
O
O
H
H
N
N
N
N
O
O
Zn
(d)
(b)
Fig. 1. Molecular modeling using the Cerius27 software: (a) top view of (Z,Z)-7a, (b) front view of (Z,Z)-7a, (c) top view of (E,E)-
7a, (d) front view of (E,E)-7a, and (e) illustration of (c) using ChemDraw. Heptyl groups are omitted for clarity.
MeO
O
O
n-Bu n-Bu
Cl
Sn O Sn Cl
Cl Sn O Sn
O
CO2Me
n-Bu
n-Bu
n-Bu
n-Bu
1a
NH HN
+
Cl
N
HN
N
n-Bu n-Bu
1-2 mol%
HO
N
N
N
N
N
N
N
N
CF3CO2H
CHCl3
; Chloranil
C7H15
C7H15
M
3
NH
N
CHO
4a M = 2H
5a M = Zn
N
+
6%
Zn(OAc)2
quant
toluene
reflux
2a
90%
O
O
n-C7H15CHO
MeO
O
O
O
O
O
O
Cy3P
O
N
N
N
N
N
N
N
O
O
C7H15
Ph
C7H15
Zn
Zn
in CHCl3
Cl
Cl
Ru
N
N
N
N
N
5a
6
Cy3P
in pyridine
N
N
N
N
N
N
N
N
N
O
O
C7H15
C7H15
Zn
Zn
N
O
O
95%
N
N
O
7a
O
D-5a
O
O
Fig. 2. Synthetic scheme for covalently-linked porphyrin dimer 7a.
of the terminal olefin, but instead the existence of the E and Z
isomers (with respect to the olefinic moiety). In these isomers,
two kinds of peaks were observed for each region of ꢀ protons
of the porphyrin ring, olefinic and allylic methylenic protons.
The ratio of the major and minor peaks was ca. 4:1, although
the absolute geometry of each peak could not be determined
by NMR. Since formation of the macrocyclic ring (>14 mem-
ber rings) by ring-closing metathesis generally gave an (E)-rich
mixture,9 the major peak observed in the NMR may have cor-
responded to the (E)-form. TLC and GPC analysis of the isolat-
ed 7a gave only a single spot and peak, respectively. This mix-
ture was used for the measurement of electronic spectra de-
scribed later. The metathesis reaction proceeded smoothly
when the concentration of the porphyrin dimer D-5a was 2–
10 mM, producing 7a in around 95% yield. However, when
the free base porphyrin 4a was used as the substrate under
the same conditions, no dimer was obtained, and almost
100% of 4a was recovered.
The design of precursor D-5a resulted in excellent yields of
the covalent linking reaction by olefin metathesis. To examine

A. Ohashi et al.
Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
367
X
n
X
O
PCy3
O
n
Ph
Cl
Cl
Ru
PCy3
O
N
N
N
N
O
N
6
N
N
N
X
R
N
Zn
X
R
Zn
N
N
n
N
N
n
a:X=O, R=n-C H -, n=2
7
15
N
N
N
n
N
N
N
N
R
b:X=O, R=n-C H -, n=3
Zn
n
7
15
R
Zn
N
N
X
c:X=O, R=n-C H -, n=4
N
O
7 15
N
X
O
d:X=O, R=Ph-, n=2
e:X=O, R=TMSCC-, n=2
f:X=2H, R=Ph-, n=2
n
n
O
D-5
O
7
X
X
Fig. 3. Ring-closing metathesis of D-5.
Table 1. Covalent Linkage of Porphyrin Dimer D-5 Shown in Fig. 3 by Ring-Closing Metathesis
Run
Substrate
Product
X
R
n
Cat.
/mol%
Time
/h
Temp
/ꢂC
Yield
/%a)
1
2
3
4
5
6
D-5a
D-5b
D-5c
D-5d
D-5e
D-5f
7a
7b
7c
7d
7e
7f
O
O
O
O
O
2H
n-C7H15–
n-C7H15–
n-C7H15–
Ph–
TMSCC–
Ph–
2
3
4
2
2
2
10
2
36
36
2
2
2
25
0b)
0b)
25
25
25
95%
26%c)
16%c)
95%
93%
98%
50b)
50b)
10
10
10
a) Iꢂsolated yield. b) Rate of conversion was very slow under standard conditions (cat.: 10 mol%, temp.:
25 C). c) No starting material was recovered.
the scope and the limitations of the metathesis reaction, precur-
sors D-5b–D-5f were also prepared. In porphyrin dimers D-5b
and D-5c, 3-(allyloxycarbonyl)propyl and 4-(allyloxycarbon-
yl)butyl groups were introduced instead of the 2-(allyloxycar-
bonyl)ethyl group to evaluate the ideal length of the side chain.
In D-5d and D-5e, phenyl and trimethylsilylethynyl groups
were introduced at the 10-meso position. A 3-(allyloxy)propyl
group was also introduced in dimer D-5f. These porphyrin di-
mers D-5b–D-5f were prepared by a similar method as that
of D-5a (Fig. 2). The results of the olefin metathesis reactions
are summarized in Fig. 3 and Table 1.
When the reactions of D-5b and D-5c were carried out in the
presence of 10 mol% Grubbs catalyst at room temperature, the
conversion was very slow. Covalently linked compounds 7b
and 7c were obtained by the addition of 50 mol% Grubbs cata-
lyst at 0 ꢂC in 26% and 16% yields, respectively. This was ac-
companied by the formation of significant amounts of the oligo-
meric species (Runs 2 and 3). Longer substituent groups ap-
peared to decrease the reactivity of the metathesis reaction.
On the other hand, D-5d and D-5e, which contain 2-(allyloxy-
carbonyl)ethyl groups, gave the corresponding products, 7d and
7e, in good yields of 95% and 93%, respectively. Dimer D-5f,
which had an ether-type unsaturated 3-(allyloxy)propyl group,
gave 7f in 98% yield. These results indicate that the length of
the side chain at the 5 and 15-positions is critical, and that 2-(al-
lyloxycarbonyl)ethyl and 3-(allyloxy)propyl groups give the
best results. The substituent groups at the 10-position can be
freely selected. Generally, yields of ring-closing metathesis
are heavily influenced by the size of ring to be produced. Five
to seven membered rings were obtained naturally in good
yields, whereas larger membered rings usually were obtained
only in moderate or low yields.10 The excellent yields obtained
in the cases of 5a and 5d–5f suggests that the two olefinic moi-
eties at the 5,50- and 15,150-positions were brought sufficiently
close together by coordination to favor the metathesis reaction.
UV–Vis Spectra. The UV–vis spectra (2.6 mM solution)
before and after the ring-closing metathesis (D-5a and 7a) were
compared in chloroform and pyridine (Fig. 4). As was reported
previously,2 the complementarily coordinated dimer, like D-5a,
was very stable even in a highly diluted chloroform solution
(<10ꢁ9 M). It gave characteristically split Soret bands, which
arise from blue and red shifts by face-to-face and head-to-tail
interactions of the transition moments, respectively. However,
the dimer D-5a was completely dissociated into 5a in pyridine
by competitive coordination (Fig. 4(A)). After the metathesis,
however, the UV–vis spectra of 7a in chloroform and in pyri-
dine were almost identical, showing characteristically split
Soret bands (Fig. 4(B)). The intramolecular coordination of
imidazolyl to Zn was, therefore, maintained even in as highly
coordinating a solvent as pyridine (2:4 ꢃ 106-fold excess). At
the same time, the spectra of D-5a and 7a in CHCl3 were also
identical, suggesting that none of the electronic states of the
porphyrins were perturbed and, therefore, no strain was induced
by the covalent linking.
Conclusion
Coordination-organized porphyrin pairs were successfully
linked covalently by template-assisted ring-closing metathesis
reactions in excellent yields. The resulting pairs retained their
coordination structures even in highly coordinating solvents

368 Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
Covalent Linking of Porphyrin Dimers
OMe, propanol), 3.66 (t, J ¼ 5:94 Hz, 2H, CH2O, propanol),
2.67 (brs, 1H, OH, propanol), 2.53–2.43 (m, 2.65H, CH2C(O),
propanol + lactone), 2.30–2.24 (m, 0.65H, CH2, lactone), 1.94–
1.84 (m, 2H, CH2, propanol).
0.6
(A)
0.6
5a
5a
0.5
0.4
0.4
0.2
0.0
Methyl 4-oxobutanoate;11 A solution of oxalyl chloride (5 mL,
58.7 mmol) in CHCl3 (200 mL) was cooled at ꢁ60 ꢂC. DMSO (8.3
mL, 117 mmol) was added to the solution, and then a crude mixture
of methyl 4-hydroxybutanoate and ꢁ-butyrolactone (6.4 g) was
added to the mixture. The mixture was stirred for 15 min at ꢁ60
ꢂC. Et3N (37 mL, 267 mmol) was then added to the mixture, fol-
lowed by stirring at rt for 10 h. Water (80 mL) was then added
to the mixture, followed by extraction with CHCl3. The organic
layer was washed with 0.1 M HCl, saturated NaHCO3, and brine.
The organic layer was dried over anhydrous Na2SO4 and evaporat-
ed under reduced pressure to give a mixture of methyl 4-oxobuta-
noate and ꢁ-butyrolactone (total 4.38 g, molar ratio 2.4:1 deter-
mined by 1H NMR) as a yellow oil. The mixture was directly used
for the next step without further purification. 1H NMR (270 MHz,
CDCl3) ꢂ 9.81 (s, 1H, CHO, oxobutanoate), 4.35 (t, J ¼ 7:0 Hz,
0.9H, lactone), 3.70 (s, 3H, OMe, oxobutanoate), 2.81 (t, J ¼ 6:2
Hz, 2H, oxobutanoate), 2.64 (t, J ¼ 6:2 Hz, 2H, oxobutanoate),
2.50 (t, J ¼ 7:5 Hz, 0.9H, lactone), 2.30–2.24 (m, 0.9H, lactone).
Trifluoroacetic acid (0.29 mL, 3.7 mmol) was added to a mix-
ture of crude 4-oxobutanoate (4.3 g, 28.8 mmol for net aldehyde)
and pyrrole (103 mL, 1.48 mol) in deoxygenated CHCl3. After stir-
ring for 12 h at rt, the mixture was diluted with CHCl3 and washed
with 0.1 M NaOH solution and water. The organic layer was dried
over Na2SO4, followed by the evaporation of CHCl3 under reduced
pressure. Excess pyrrole was then recovered by distillation under
reduced pressure. The brown residue was purified by SiO2 column
chromatography (EtOAc/hexane 1/2) to give dipyrromethane 1a
D-5a
0.3
0.2
0.1
0.0
D-5a
nm
480
360
400
440
350 400 450 500 550 600 650 700 750 800
nm
(B)
7a
0.4
0.2
0.0
7a
0.40
0.30
0.20
0.10
0.00
nm
480
360
400
440
350 400 450 500 550 600 650 700 750 800
nm
Fig. 4. UV–vis spectra of (A) 5a (2.6 mM as monomer unit)
and (B) 7a (2.6 mM as dimer) in chloroform (solid line) and
pyridine (dotted line). Inset: enlarged spectra.
such as pyridine. The excellent yields of the linked products
may be applied to systems of porphyrin oligomers and poly-
mers composed of multiple complementary dimer units. In par-
ticular, we may now use this method for stabilization of macro-
ring systems and immobilization of meso–meso linked porphy-
rin oligomers on a gold surface.
1
(3.92 g, 3 steps 27%). H NMR (270 MHz, CDCl3) ꢂ 7.76 (brs,
2H, NH), 6.59–6.55 (m, 2H, pyrrole ꢀ), 6.14–6.09 (m, 2H, pyrrole
ꢃ), 6.06–6.02 (m, 2H, pyrrole ꢃ), 3.97 (t, J ¼ 7:3 Hz, 1H, CH),
3.62 (s, 3H, OMe), 2.32–2.17 (m, 4H, CH2). 13C NMR (67.7
MHz, CDCl3) ꢂ 173.78, 132.26, 117.27, 107.93, 105.74, 51.59,
ꢂ
36.89, 31.93, 29.53. mp 49 ꢄ 1 C. Anal: calcd for C13H16N2O2;
C, 67.22; H, 6.94; N, 12.06%; found C, 67.09; H, 6.85; N, 11.88%.
meso-[3-(Methoxycarbonyl)propyl]dipyrromethane 1b: Di-
pyrromethane 1b (1.1 g, 50%) was synthesized from methyl 5-ox-
opentanoate11 (1.1 g, 8.5 mmol) and pyrrole in a similar manner as
for the preparation of 1a. 1H NMR (270 MHz, CDCl3) ꢂ 7.94 (brs,
2H, NH), 6.66 (s, 2H, pyrrole CH ), 6.145 (s, 2H, pyrrole CH ),
Experimental
General Methods. 1H NMR and 13C NMR spectra were re-
corded on a JEOL ECP-600 (600 MHz NMR) or a EX-270 (270
MHz) spectrometer using TMS (0 ppm) or the residual resonance
(7.26 ppm (1H) or 77.0 ppm (13C) for CHCl3) of the solvent as the
internal standard. UV–vis spectra were obtained from a Shimadzu
UV-3100PC instrument. Fluorescence spectra were obtained with
a Hitachi F-4500 spectrometer. MALDI-TOF mass spectra were
measured with a Perseptive Biosystems Voyager DE-STR appara-
tus. Dithranol purchased from SIGMA was used as a matrix in the
MALDI-TOF mass spectrometric measurements. Chromatography
was performed using silica gel 60 N (KANTO chemical Co., 63–
210 mm). Thin-layer chromatography was performed on Merck
silica gel 60F254 plates. All chemicals obtained from commercial
sources were used without further purification.
Synthesis of Dipyrromethane. meso-[2-(Methoxycarbony)-
ethyl]dipyrromethane 1a: Methyl 4-hydroxybutanoate;11 ꢁ-Bu-
tyrolactone (5 g, 58 mmol) and triethylamine (48 mL, 348 mmol)
were dissolved in MeOH (100 mL) and stirred for 12 h at rt. Tri-
ethylamine and methanol were evaporated to give a mixture of
methyl 4-hydroxybutanoate and ꢁ-butyrolactone (total 6.4 g, mo-
lar ratio 3:1 determined by 1H NMR). The mixture was directly
used for the next step without purification. 1H NMR (270 MHz,
CDCl3) ꢂ 4.36 (t, J ¼ 6:75 Hz, 0.65H, lactone), 3.68 (s, 3H,
ꢃ
ꢀ
6.065 (s, 2H, pyrrole CH ), 4.12 (t, J ¼ 7:3 Hz, 1H, CH), 3.66
ꢃ
(s, 3H, OMe), 2.33 (t, J ¼ 7:3 Hz, 2H, CH2C(O)), 2.02–1.97 (m,
2H, CH2), 1.69–1.62 (m, 2H, CH2).
meso-[4-(Methoxycarbonyl)butyl]dipyrromethane 1c: Di-
pyrromethane 1c (5.9 g, 46%) was synthesized from methyl 6-ox-
ohexanoate11 (7.5 g, 52 mmol) and pyrrole in a similar manner as
for the preparation of 1a. 1H NMR (600 MHz, CDCl3) ꢂ 7.86 (brs,
2H, NH), 6.64 (s, 2H, pyrrole CH ), 6.14 (s, 2H, pyrrole CH ),
ꢃ
ꢀ
6.05 (s, 2H, pyrrole CH ), 3.99 (t, J ¼ 7:32 Hz, 1H, CH), 3.65
ꢃ
(s, 3H, OMe), 2.29 (t, J ¼ 6:0 Hz, 2H, CH2C(O)), 1.99–1.93 (m,
2H, CH2), 1.68–1.62 (m, 2H, CH2), 1.37–1.31 (m, 2H, CH2).
meso-(3-Allyloxypropyl)dipyrromethane 1d: Dipyrrometh-
ane 1d (4.26 g, 40%) was synthesized from 4-allyloxybutanal12
(5.6 g, 43.6 mmol) and pyrrole in a similar manner as for the prep-
1
aration of 1a. H NMR (270 MHz, CDCl3) ꢂ 7.76 (brs, 2H, NH),
6.60–6.50 (m, 2H, pyrrole H5), 6.14–6.10 (m, 2H, pyrrole H4),
6.05–6.01 (m, 2H, pyrrole H3), 5.90 (ddt, J ¼ 17:3, 10.4, 5.4 Hz,
1H, CH=CH2), 5.25 (ddt, J ¼ 17:3, 3.5, 1.6 Hz, 1H, CH=CH2),
5.15 (ddt, J ¼ 10:4, 4.3, 1.6 Hz, 1H, CH=CH2), 3.96 (t, J ¼ 7:8

A. Ohashi et al.
Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
369
Hz, 1H, CH), 3.93 (dt, J ¼ 5:4, 1.6 Hz, 2H, CH2–CH=CH2), 3.42
(t, J ¼ 6:21 Hz, 2H), 2.05–1.94 (m, 2H, CH2), 1.63–1.52 (m, 2H,
CH2). 13C NMR (67.70 MHz, CDCl3) ꢂ 134.76, 133.24, 116.94,
116.75, 107.84, 105.45, 71.76, 70.13, 37.36, 31.35, 27.66. mp <
25 ꢂC. Anal: calcd for C15H20N2O; C, 73.74; H, 8.25; N,
11.47%, found C, 73.52; H, 8.32; N, 11.21%.
by broadening; UV–vis (CHCl3): 417 (Abs.; 0.4774), 518 (0.0225),
552 (0.0095), 593 (0.0070), 650 (0.0050) nm; Fluorescence (Ex =
417 nm, CHCl3): 654, 721 nm; MALDI-TOF Mass of C41H48N6O4
Calcd: 688.3; Found: 689.1 (M + H)þ.
5,15-Bis[4-(methoxycarbonyl)butyl]-10-heptyl-20-(1-meth-
yl-2-imidazolyl)porphyrin (2c): In a similar manner as for the
preparation of 2a, porphyrin 2c was synthesized by condensation
of 2-formyl-1-methylimidazole (440 mg, 4.0 mmol), octanal
(512 mg, 4 mmol), and meso-[4-(methoxycarbonyl)butyl]dipyrro-
methane 1c (2 g, 8.1 mmol) in the presence of TFA (2.3 mL,
16.3 mmol) in CHCl3 (1 L) followed by oxidation with p-chloranil
(3 g, 12.2 mmol). Purification was performed using a silica gel col-
Synthesis of Porphyrin. 5,15-Bis[2-(methoxycarbonyl)eth-
yl]-10-heptyl-20-(1-methyl-2-imidazolyl)porphyrin (2a): A 2
L round-bottom flask was charged with 2-formyl-1-methylimida-
zole (240 mg, 2.2 mmol), octanal (280 mg, 2.2 mmol), meso-[2-
(methoxycarbonyl)ethyl]dipyrromethane 1a (1 g, 4.3 mmol), and
chloroform (1 L). After bubbling with a N2 stream for 5 min, tri-
fluoroacetic acid (TFA) (1.2 mL, 8.6 mmol) was added to the mix-
ture, and the mixture was stirred at rt in the dark for 4 h. p-Chlor-
anil (1.6 g, 6.5 mmol) was then added, and the reaction mixture
was again stirred for 10 h. A saturated NaHCO3 solution was added
to the mixture, and the mixture was then extracted with CHCl3.
The organic layer was washed with brine, dried over anhydrous
Na2SO4, and concentrated under reduced pressure. The residue
was loaded on a silica gel column and eluted with CHCl3/acetone
(10:1) to give 2a (82 mg, 6%). 1H NMR (600 MHz, CDCl3) ꢂ 9.56
(d, J ¼ 4:2 Hz, 2H, Porꢀ), 9.51 (d, J ¼ 4:2 Hz, 2H, Porꢀ), 9.44 (d,
J ¼ 4:2 Hz, 2H, Porꢀ), 8.74 (d, J ¼ 4:2 Hz, 2H, Porꢀ), 7.67 (br.s,
1H, imidazole CH), 7.45 (br.s, 1H, Im CH), 5.30–5.23 (m, 4H, es-
ter ꢀCH2), 5.00–4.98 (m, 2H, heptyl-C1), 3.75 (s, 6H, COOMe),
3.52–3.45 (m, 4H, ester ꢃCH2), 3.38 (s, 3H, NCH3), 2.55–2.45
(m, 2H, heptyl-C2), 1.80–1.78 (m, 2H, heptyl-C3), 1.54–1.52 (m,
2H, heptyl-C4), 1.36–1.34 (m, 4H, heptyl-C5, C6), 0.91 (t, J ¼ 7
Hz, 3H, heptyl-C7), ꢁ2:71 (s, 2H, NH); 13C NMR (150 MHz,
CDCl3) ꢂ 173.2 (C=O), 148.7 (Im N=C–N), 128.5 (imidazole
ring), 132–126 (br, 4 carbons (Porꢀ)), 122.1 (Im CH), 121.5
(meso), 116.9 (meso), 104.0 (meso), 52.0 (COOMe), 41.8 (ester
ꢃ), 39.1 (heptyl-C1), 36.1 (heptyl-C2), 34.6 (NCH3), 32.0 (hep-
tyl-C5), 30.7 (heptyl-C3), 30.5 (ester ꢀ), 29.6 (heptyl-C4), 22.8
(heptyl-C6), 14.2 (heptyl-C7). The other 4 carbons (Porꢃ) could
not be observed by broadening; UV–vis (CHCl3): 418 (Abs.;
1.3949), 516 (0.0856), 551 (0.0366), 594 (0.0260), 652 (0.0188)
nm; Fluorescence (Ex = 418 nm, CHCl3): 620, 723 nm; MAL-
DI-TOF Mass of C39H44N6O4 Calcd: 660.3; Found: 661.9 (M +
H)þ.
5,15-Bis[3-(methoxycarbonyl)propyl]-10-heptyl-20-(1-meth-
yl-2-imidazolyl)porphyrin (2b): In a similar manner as for the
preparation of 2a, porphyrin 2b was synthesized by condensation
of 2-formyl-1-methylimidazole (440 mg, 4.0 mmol), octanal
(512 mg, 4 mmol), and meso-[3-(methoxycarbonyl)propyl]dipyr-
romethane 1b (2 g, 8.1 mmol) in the presence of TFA (2.3 mL,
16.3 mmol) in CHCl3 (1 L) followed by oxidation with p-chloranil
(3 g, 12.2 mmol). Purification was performed using a silica gel col-
umn (CHCl3/acetone (10:1)) to give 2b (300 mg, 10%). 1H NMR
(600 MHz, CDCl3) ꢂ 9.34 (m, 6H, Porꢀ), 8.67 (m, 2H, Porꢀ), 7.62
(br.s, 1H, Im CH), 7.31 (br.s, 1H, Im CH), 4.76–4.74 (m, 6H, hep-
tyl-C1, ester ꢁ), 3.73 (s, 6H, COOMe), 3.32 (s, 3H, NCH3), 2.71–
2.67 (m, 4H, ester ꢀ), 2.62–2.58 (m, 4H, ester ꢃ), 2.42–2.38 (m,
2H, heptyl-C2), 1.72–1.68 (m, 2H, heptyl-C3), 1.48–1.42 (m, 2H,
heptyl-C4), 1.33–1.30 (m, 4H, heptyl-C5, C6), 0.89 (t, J ¼ 7 Hz,
3H, heptyl-C7), ꢁ2:86 (s, 2H, NH); 13C NMR (150 MHz, CDCl3)
ꢂ 174.1 (C=O), 148.9 (Im N=C–N), 128.2 (Im CH), 132–126 (br,
4 carbons (Porꢀ)), 121.7 (Im CH), 121.5 (meso), 118.2 (meso),
103.4 (meso), 51.8 (COOMe), 39.1 (heptyl-C2), 35.9 (heptyl-C1),
34.5 (NCH3), 34.3 (ester ꢁ), 34.0 (ester ꢀ), 32.8 (ester ꢃ), 32.0
(heptyl-C5), 30.7 (heptyl-C3), 29.5 (heptyl-C4), 22.8 (heptyl-C6),
14.3 (heptyl-C7). The other 4 carbons (Porꢃ) could not be observed
1
umn (CHCl3/acetone (10:1)) to give 2c (202 mg, 7%). H NMR
(600 MHz, CDCl3) ꢂ 9.52 (d, J ¼ 4:4 Hz, 2H, Porꢀ), 9.43 (d, J ¼
4:4 Hz, 2H, Porꢀ), 9.37 (d, J ¼ 4:4 Hz, 2H, Porꢀ), 8.72 (d, J ¼ 4:4
Hz, 2H, Porꢀ), 7.67 (br.s, 1H, Im CH), 7.44 (br.s, 1H, Im CH), 4.97
(t, J ¼ 7 Hz, 2H, heptyl-C1), 4.91 (t, J ¼ 7 Hz, 4H, ester ꢂ), 3.66
(s, 6H, COOMe), 3.37 (s, 3H, NCH3), 2.52–2.50 (m, 2H, heptyl-
C2), 2.49–2.45 (m, 8H, ester ꢀ, ꢁ), 2.10 (m, 4H, ester ꢃ), 1.81
(m, 2H, heptyl-C3), 1.54 (m, 2H, heptyl-C4), 1.36–1.34 (m, 4H,
heptyl-C5, C6), 0.90 (t, J ¼ 7 Hz, 3H, heptyl-C7), ꢁ2:79 (s, 2H,
NH); 13C NMR (150 MHz, CDCl3) ꢂ 174.1 (C=O), 148.9 (Im
N=C–N), 128.4 (Im CH), 132–126 (br, 4 carbons (Porꢀ)), 121.7
(Im CH), 121.4 (meso), 118.9 (meso), 103.4 (meso), 51.7
(COOMe), 39.1 (heptyl-C2), 37.8 (ester ꢁ), 36.1 (NCH3), 34.9 (es-
ter ꢂ), 34.5 (heptyl-C1), 34.1 (ester ꢀ), 32.0 (heptyl-C5), 30.7 (hep-
tyl-C3), 29.5 (heptyl-C4), 25.8 (ester ꢃ), 22.8 (heptyl-C6), 14.2
(heptyl-C7). The other 4 carbons (Porꢃ) could not be observed
by broadening; UV–vis (CHCl3): 418 (Abs.; 0.2271), 518
(0.0100), 555 (0.0042), 591 (0.0031), 649 (0.0021) nm; Fluores-
cence (Ex = 418 nm, CHCl3): 651, 716 nm; MALDI-TOF Mass
of C43H52N6O4 Calcd: 716.4; Found: 717.3 (M + H)þ.
5,15-Bis[2-(methoxycarbonyl)ethyl]-20-(1-methyl-2-imida-
zolyl)-10-phenylporphyrin (2d): In a similar manner as for the
preparation of 2a, porphyrin 2d was synthesized by condensation
of 2-formyl-1-methylimidazole (220 mg, 2 mmol), benzaldehyde
(0.2 mL, 2 mmol), and meso-[2-(methoxycarbonyl)ethyl]dipyrro-
methane 1a (1.03 g, 4 mmol) in the presence of TFA (0.9 mL, 6
mmol) in CHCl3 (1 L) followed by oxidation with p-chloranil
(1.5 g, 6 mmol). Purification was performed using a silica gel col-
umn (CHCl3/acetone (20:1)) to give 2d (73 mg, 6%). 1H NMR
(600 MHz, CDCl3) ꢂ 9.49 (d, J ¼ 4:2 Hz, 2H, Porꢀ), 9.43 (d, J ¼
4:2 Hz, 2H, Porꢀ), 8.89 (d, J ¼ 4:2 Hz, 2H, Porꢀ), 8.81 (d, J ¼ 4:2
Hz, 2H, Porꢀ), 8.22 (d, J ¼ 7 Hz, 1H, Ph), 8.10 (d, J ¼ 7 Hz, 1H,
Ph), 7.82–7.74 (m, 3H, Ph), 7.68 (s, 1H, Im CH), 7.48 (s, 1H, Im
CH), 5.32 (t, J ¼ 7:4 Hz, 4H, ester ꢀ), 3.75 (s, 6H, COOMe),
3.50 (t, J ¼ 7:4 Hz, 4H, ester ꢃ), 3.40 (s, 3H, NCH3), ꢁ2:73 (s,
2H, NH); 13C NMR (150 MHz, CDCl3) ꢂ 173.1 (C=O), 148.7
(Im N=C–N), 144.2–149.5 (br, 4 carbons (Porꢃ)), 142.3 (Ph),
134.4 (Ph), 132.7 (Porꢀ), 131.1 (Porꢀ), 128.9 (Porꢀ), 128.5 (C;
Ph), 128.0 (Im CH), 127.4 (Porꢀ), 126.73 (Ph), 126.66 (Ph),
121.5 (Im CH), 121.3 (meso), 117.5 (meso), 104.8 (meso), 52.0
(COOMe), 41.8 (ester ꢃ), 34.6 (NCH3), 30.4 (ester ꢀ); UV–vis
(CHCl3): 417 (Abs.; 1.9670), 515 (0.1159), 548 (0.0415), 590
(0.0384), 647 (0.0224) nm; Fluorescence (Ex = 417 nm, CHCl3):
652, 717 nm; MALDI-TOF Mass of C38H34N6O4 Calcd: 638.26;
Found: 639.8 (M + H)þ.
5,15-Bis[2-(methoxycarbonyl)ethyl]-20-(1-methyl-2-imida-
zolyl)-10-(trimethylsilylethynyl)porphyrin (2e): In a similar
manner as for the preparation of 2a, porphyrin 2e was synthesized
by condensation of 2-formyl-1-methylimidazole (1.1 g, 10 mmol),
3-trimethylsilylpropynal (0.632 g, 5 mmol), and meso-[2-(methoxy-

370 Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
Covalent Linking of Porphyrin Dimers
carbonyl)ethyl]dipyrromethane 1a (2.32 g, 10 mmol) in the pres-
ence of TFA (1.16 mL, 15 mmol) in CHCl3 (1 L) followed by ox-
idation with p-chloranil (3.68 g, 15 mmol). Purification was per-
formed using a silica gel column (CHCl3/MeOH (9:1)) to give
103.8 (meso), 65.6 (–OCH2), 41.9 (ester ꢃ), 39.1 (heptyl-C1),
36.0 (heptyl-C2), 34.6 (NCH3), 32.0 (heptyl-C5), 30.7 (ester ꢀ),
30.4 (heptyl-C3), 29.4 (heptyl-C4), 22.8 (heptyl-C6), 14.2 (hep-
tyl-C7). The other 4 carbons (Porꢃ) could not be observed by
broadening; UV (CHCl3): 417 (Abs.; 0.1438), 517 (0.0100), 553
(0.0051), 589 (0.0035), 647 (0.0024) nm; Fluorescence (Ex =
417 nm, CHCl3) : 655, 722 nm; MALDI-TOF Mass of
C43H48N6O4 Calcd: 712.37; Found: 713.6 (M + H)þ.
1
2e (208 mg, 6.3%). H NMR (600 MHz, CDCl3) ꢂ 9.70 (d, J ¼
4:2 Hz, 2H, Porꢀ), 9.41 (d, J ¼ 4:2 Hz, 2H, Porꢀ), 9.34 (d, J ¼
4:2 Hz, 2H, Porꢀ), 8.71 (d, J ¼ 4:2 Hz, 2H, Porꢀ), 7.70 (br.s,
1H, Im CH), 7.46 (br.s, 1H, Im CH), 5.19–5.17 (m, 4H, ester ꢀ),
3.7 (s, 6H, COOMe), 3.43 (t, J ¼ 7:2 Hz, 4H, ester ꢃ), 3.33 (s,
3H, NCH3), 0.67 (s, 9H, TMS), ꢁ2:78 (s, 2H, inner proton);
13C NMR (150 MHz, CDCl3) ꢂ 173.0 (C=O), 148.4 (Im N=C–
N), 147–144 (br, 4 carbons (Porꢃ)), 131.9 (Porꢀ), 131.2 (Porꢀ),
128.4 (Porꢀ), 128.3 (Im CH), 128.2 (Porꢀ), 121.7 (Im CH),
118.3 (meso), 107.1 (TMS–CꢅC–), 106.4 (meso), 102.5 (meso),
100.1 (TMS–CꢅC–), 52.0 (COOMe), 41.7 (ester ꢃ), 34.6 (NCH3),
30.2 (ester ꢀ), 0.4 (TMS); UV–vis (nm, CHCl3): 427 (Abs.;
2.3982), 527 (0.1086), 566 (0.1405), 608 (0.0553), 665 (0.0651);
Fluorescence (Ex = 427 nm, CHCl3): 668, 740 nm; MALDI-
TOF Mass of C37H38N6O4Si Calcd: 658.2; Found: 659.2 (M +
H)þ.
5,15-Bis[3-(allyloxycarbonyl)propyl]-10-heptyl-20-(1-meth-
yl-2-imidazolyl)porphyrin (4b): In a similar manner as for the
preparation of 4a, the transesterification of 2b (116 mg, 1.7 mmol)
1
was carried out to give 4d (110 mg, 88%). H NMR (600 MHz,
CDCl3) ꢂ 9.52 (m, 2H, Porꢀ), 9.50 (m, 2H, Porꢀ), 9.34 (m, 2H,
Porꢀ), 8.63 (m, 2H, Porꢀ), 7.69 (s, 1H, Im CH), 7.46 (s, 1H, Im
CH), 6.00 (ddt, J ¼ 5:9, 11.0, 17.4 Hz, 2H, CH=CH2), 5.34 (d,
J ¼ 17:4 Hz, 2H, CH=CH2), 5.26 (t, J ¼ 7 Hz, 4H, ester ꢀ),
5.25 (d, J ¼ 11:0 Hz, 2H, CH=CH2), 4.98 (t, J ¼ 7 Hz, 2H, hep-
tyl-C1), 4.89–4.86 (m, 4H, ester ꢁ), 4.57 (dd, J ¼ 5:9 Hz, 4H,
–OCH2), 3.31 (s, 3H, NCH3), 2.88–2.77 (m, 4 H, ester ꢀ), 2.76–
2.65 (m, 4H, ester ꢃ), 2.52 (m, 2H, heptyl-C2), 1.68 (m, 2H, hep-
tyl-C3), 1.57–1.51 (m, 2H, heptyl-C4), 1.39–1.34 (m, 4H, heptyl-
C5, C6), 0.91 (t, J ¼ 7 Hz, 3H, heptyl-C7), ꢁ2:87 (s, 2H, NH);
13C NMR (150 MHz, CDCl3) ꢂ 173.3 (C=O), 148.6 (Im N=C–
N), 132.3 (allyl ꢀ), 127.8 (Im CH), 132–127 (br, 4 carbons (Porꢀ),
121.9 (Im CH), 121.6 (meso), 118.6 (CH=CH2), 118.3 (meso),
102.6 (meso), 65.4 (–OCH2), 39.1 (heptyl-C2), 36.1 (heptyl-C1),
34.6 (NCH3), 34.3 (ester ꢁ), 34.2 (ester ꢃ), 32.7 (ester ꢀ), 32.0
(heptyl-C5), 30.7 (heptyl-C3), 29.4 (heptyl-C4), 22.8 (heptyl-C6),
14.2 (heptyl-C7). The other 4 carbons (Porꢃ) could not be observed
by broadening; UV (nm, CHCl3): 417 (Abs.; 0.5504), 518
(0.0168), 552 (0.0039), 593 (0.0028), 649 (0.0029); Fluorescence
(Ex = 417 nm, CHCl3): 654, 721 nm; MALDI-TOF Mass of
C45H52N6O4 Calcd: 740.4; Found: 741.7 (M + H)þ.
5,15-Bis[4-(allyloxycarbonyl)butyl]-10-heptyl-20-(1-methyl-
2-imidazolyl)porphyrin (4c): In a similar manner as for the prep-
aration of 4a, the transesterification of 2c (116 mg, 1.7 mmol) was
carried out to give 4c (151 mg, 78%). 1H NMR (600 MHz, CDCl3)
ꢂ 9.49 (d, J ¼ 4 Hz, 2H, Porꢀ), 9.41 (d, J ¼ 4 Hz, 2H, Porꢀ), 9.36
(d, J ¼ 4 Hz, 2H, Porꢀ), 8.70 (d, J ¼ 4 Hz, 2H, Porꢀ), 7.66 (s, 1H,
imidazole ring), 7.43 (s, 1H, imidazole ring), 5.88 (ddt, J ¼ 4:4,
11.0, 16.8 Hz, 2H, CH=CH2), 5.30 (d, J ¼ 16:8 Hz, 2H,
CH=CH2), 5.17 (d, J ¼ 11:0 Hz, 2H, CH=CH2), 4.94 (t, J ¼ 7
Hz, 2H, heptyl-C1), 4.89 (t, J ¼ 7 Hz, 4H, ester ꢂ), 4.58 (d, J ¼
4:4 Hz, 4H, –OCH2), 3.34 (s, 3H, NCH3), 2.52–2.46 (m, 10H, hep-
tyl-C2, ester ꢀ, ꢁ), 2.14–2.08 (m, 4H, ester ꢃ), 1.80 (m, 2H, heptyl-
C3), 1.53–1.51 (m, 2H, heptyl-C4), 1.35–1.34 (m, 4H, heptyl-C5,
C6), 0.92–0.89 (m, 3H, heptyl-C7), ꢁ2:70 (s, 2H, NH); 13C NMR
(150 MHz, CDCl3) ꢂ 173.3 (C=O), 148.9 (Im N=C–N), 132.3
(CH=CH2), 128.3 (Im CH), 132–127 (br.s, 4 carbons (Porꢀ),
122.8 (Im CH), 121.4 (meso), 118.9 (meso), 118.6 (CH=CH2),
103.3 (meso), 65.2 (–OCH2), 39.1 (CH2), 37.7 (CH2), 36.1
(CH2), 34.9 (CH2), 34.6 (NCH3), 34.2 (CH2), 32.0 (CH2), 30.7
(CH2), 29.4 (CH2), 25.8 (CH2), 22.8 (CH2), 14.2 (CH3). The other
4 carbons (Porꢃ) could not be observed by broadening; UV–vis
(nm, CHCl3): 418 (Abs.; 1.0357), 517 (0.0439), 552 (0.0179),
594 (0.0118), 651 (0.0103); Fluorescence (Ex = 418 nm, CHCl3):
655, 722 nm; MALDI-TOF Mass of C47H56N6O4 Calcd: 768.44;
Found: 769.9 (M + H)þ.
5,15-Bis(3-allyloxypropyl)-20-(1-methyl-2-imidazolyl)-10-
phenylporphyrin (4f): In a similar manner as for the preparation
of 2a, porphyrin 4f was synthesized by condensation of 2-formyl-
1-methylimidazole (0.23 g, 2.1 mmol), benzaldehyde (0.22 g, 2.1
mmol), and meso-(3-allyloxypropyl)dipyrromethane 1d (0.96 g,
3.9 mmol) in the presence of TFA (0.9 mL, 5.3 mmol) in CHCl3
(1 L) followed by oxidation with p-chloranil (1.6 g, 6.5 mmol). Pu-
rification was performed using a silica gel column (CHCl3/acetone
(9:1)) to give 4f (90 mg, 6.5%). 1H NMR (270 MHz, CDCl3) ꢂ 9.54
(d, J ¼ 4:8 Hz, 2H, Porꢀ), 9.48 (d, J ¼ 4:8 Hz, 2H, Porꢀ), 8.87 (d,
J ¼ 4:8 Hz, 2H, Porꢀ), 8.79 (d, J ¼ 4:8 Hz, 2H, Porꢀ), 8.25 (d,
J ¼ 5:3 Hz, 1H, o-Ph), 7.84–7.68 (m, 3H, m- and p-Ph), 7.68 (d,
J ¼ 1:0 Hz, 1H, Im), 7.48 (d, J ¼ 1:0 Hz, 1H, Im), 6.16–6.00
(m, 2H, CH=CH2), 5.42 (d, J ¼ 17:3 Hz, 2H, CH=CH2), 5.26
(d, J ¼ 10:2 Hz, 2H, CH=CH2), 5.11 (t, J ¼ 7:3 Hz, 4H, Por-
CH2), 4.07 (d, J ¼ 5:4 Hz, 4H, CH2–CH=CH2), 3.66 (t, J ¼ 5:8
Hz, 4H, CH2–O–), 3.40 (s, 3H, N–Me), 2.85–2.74 (m, 4H,
–CH2–CH2–CH2), ꢁ2:66 (s, 2H, NH).
5,15-Bis[2-(allyloxycarbonyl)ethyl)-10-heptyl-20-(1-methyl-
2-imidazolyl)porphyrin (4a): A mixture of porphyrin 2a (100
mg, 0.15 mmol) and allyl alchol (0.2 mL, 3 mmol) was refluxed
in toluene (3 mL) in the presence of distannoxane catalyst 3 (1
mg, 2 mmol). The reaction was monitored by MALDI-TOF mass
spectra. Normally, the transesterification was completed within 4
h. The mixture was cooled to rt, and water was added to the mix-
ture. The mixture was then extracted with CHCl3. The organic lay-
er was washed with brine, dried over Na2SO4, and evaporated un-
der reduced pressure. The residue was loaded on a silica gel col-
umn and eluted with CHCl3/MeOH (10:1) to give 4a (90 mg,
90%). 1H NMR (600 MHz, CDCl3) ꢂ 9.51 (d, J ¼ 4 Hz, 2H, Porꢀ),
9.47 (d, J ¼ 4 Hz, 2H, Porꢀ), 9.41 (d, J ¼ 4 Hz, 2H, Porꢀ), 8.73
(d, J ¼ 4 Hz, 2H, Porꢀ), 7.68 (s, 1H, Im CH), 7.45 (s, 1H, Im CH),
5.92 (ddt, J ¼ 5:9, 11.0, 17.4 Hz, 2H, CH=CH2), 5.32 (d, J ¼ 17:4
Hz, 2H, CH=CH2), 5.26 (t, J ¼ 7 Hz, 4H, ester ꢀ), 5.21 (d, J ¼
11:0 Hz, 2H, CH=CH2), 4.93 (t, J ¼ 7 Hz, 2H, heptyl-C1), 4.68
(d, J ¼ 5:9 Hz, 4H, –OCH2), 3.50 (t, J ¼ 7 Hz, 4H, ester ꢃ),
3.34 (s, 3H, NCH3), 2.49 (m, 2H, heptyl-C2), 1.78 (m, 2H, hep-
tyl-C3), 1.53–1.51 (m, 2H, heptyl-C4), 1.35–1.34 (m, 4H, heptyl-
C5, C6), 0.92–0.89 (m, 3H, heptyl-C7), ꢁ2:81 (s, 2H, NH);
13C NMR (150 MHz, CDCl3) ꢂ 172.4 (C=O), 148.7 (Im N=C–
N), 132.2 (CH=CH2), 128.3 (Im CH), 129.5–126.3 (br, 4 Porꢀ),
122.1 (Im CH), 121.6 (meso), 118.6 (CH=CH2), 116.9 (meso),
5,15-Bis[2-(allyloxycarbonyl)ethyl]-10-phenyl-20-(1-methyl-
2-imidazolyl)porphyrin (4d): In a similar manner as for the
preparation of 4a, the transesterification of 2d (60 mg, 94 mmol)
was carried out to give 4d (55 mg, 85%). 1H NMR (600 MHz,

A. Ohashi et al.
Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
371
CDCl3) ꢂ 9.50 (d, J ¼ 4:8 Hz, 2H, Porꢀ), 9.44 (d, J ¼ 4:8 Hz, 2H,
Porꢀ), 8.89 (d, J ¼ 4:8 Hz, 2H, Porꢀ), 8.81 (d, J ¼ 4:8 Hz, 2H,
Porꢀ), 8.21 (d, J ¼ 7 Hz, 1H, Ph), 8.11 (d, J ¼ 7 Hz, 1H, Ph),
7.82–7.73 (m, 3H, Ph), 7.68 (s, 1H, Im CH), 7.47 (s, 1H, Im
CH), 5.90 (ddt, J ¼ 6, 10, 16 Hz, 4H, CH=CH2), 5.32 (d, J ¼
16 Hz, 2H, CH=CH2), 5.30 (t, J ¼ 8 Hz, 4H, ester ꢀ), 5.19 (d, J ¼
10 Hz, 2H, CH=CH2), 4.69 (d, J ¼ 6 Hz, 4H, –OCH2), 3.53 (t, J ¼
8 Hz, 4H, ester ꢃ), 3.39 (s, 3H, NCH3), ꢁ2:73 (s, 2H, NH);
13C NMR (150 MHz, CDCl3) ꢂ 172.2 (C=O), 148.6 (Im N=C–
N), 149.2–144.4 (4 carbons (Porꢃ)), 142.2 (Ph), 134.3 (Ph),
132.7 (Porꢀ), 132.1 (CH=CH2), 131.1 (Porꢀ), 128.9 (Porꢀ),
128.5 (Ph), 128.0 (Im CH), 127.5 (Porꢀ), 126.7 (Ph), 126.6 (Ph),
121.5 (Im CH), 121.2 (meso), 118.5 (CH=CH2), 117.4 (meso),
104.8 (meso), 65.6 (–OCH2), 41.9 (ester ꢀ), 34.6 (NCH3), 30.4 (es-
ter ꢃ); UV–vis (nm, CHCl3): 417 (Abs.; 2.0850), 515 (0.1201), 549
(0.0424), 590 (0.0392), 647 (0.0230); Fluorescence (Ex = 417 nm,
CHCl3): 652, 718 nm; MALDI-TOF Mass of C42H38N6O4 Calcd:
690.30; Found: 691.2 (M + H)þ.
5,15-Bis[2-(allyloxycarbonyl)ethyl)-20-(1-methyl-2-imida-
zolyl)-10-(trimethylsilylethynyl)porphyrin (4e): In a similar
manner as for the preparation of 4a, the transesterification of 2e
(70 mg, 0.1 mmol) was carried out to give 4e (62 mg, 88%).
1H NMR (600 MHz, CDCl3) ꢂ 9.71 (d, J ¼ 4:2 Hz, 2H, Porꢀ),
9.44 (d, J ¼ 4:2 Hz, 2H, Porꢀ), 9.39 (d, J ¼ 4:2 Hz, 2H, Porꢀ),
8.74 (d, J ¼ 4:2 Hz, 2H, Porꢀ), 7.68 (s, 1H, Im CH), 7.45 (s,
1H, Im CH), 5.89 (ddt, J ¼ 6, 11, 19 Hz, 2H, CH=CH2), 5.30
(d, J ¼ 19 Hz, 2H, CH=CH2), 5.24 (t, J ¼ 8 Hz, 2H, ester ꢀ),
5.19 (d, J ¼ 11 Hz, 2H, CH=CH2), 4.67 (d, J ¼ 6 Hz, 4H,
–OCH2–), 3.48 (t, J ¼ 7 Hz, 4H, ester ꢃ), 3.35 (s, 3H, NCH3),
0.66 (s, 9H, TMS), ꢁ2:67 (s, 2H, NH); 13C NMR (150 MHz,
CDCl3) ꢂ 172.3 (C=O), 148.5 (Im N=C–N), 148.2–144.5 (4 car-
bons (Porꢃ)), 132.1 (CH=CH2), 131.8 (Porꢀ), 131.3 (Porꢀ),
128.5 (Porꢀ), 128.4 (Im CH), 128.3 (Porꢀ), 121.6 (Im CH),
118.6 (CH=CH2), 118.3 (meso), 107.1 (TMS–CꢅC–), 106.7
(meso), 102.5 (meso), 100.1 (TMS–CꢅC–), 65.6 (–OCH2–), 41.8
(ester ꢃ), 34.5 (NCH3), 30.2 (ester ꢀ), 0.44 (TMS); UV–vis (nm,
CHCl3): 427 (Abs.; 2.3423), 527 (0.1030), 565 (0.1344), 607
(0.0452), 665 (0.0633); Fluorescence (Ex = 427 nm, CHCl3):
668, 740 nm; MALDI-TOF Mass of C41H42N6O4Si Calcd:
710.3; Found: 711.0 (M + H)þ.
Synthesis of Zinc Complex. 5,15-Bis[2-(allyloxycarbonyl)-
ethyl]-10-heptyl-20-(1-methyl-2-imidazolyl)porphyrinatozinc
(5a): A saturated solution of zinc acetate in MeOH (5 mL) was
added to a solution of 4a (80 mg, 0.12 mmol) in CHCl3 (15
mL). After stirring for 1 h at rt, the mixture was diluted with CHCl3
and washed with water. The organic layer was washed with brine,
dried over anhydrous Na2SO4, and evaporated under reduced pres-
sure to give 5a (88 mg, quant). D-5a: 1H NMR (600 MHz, CDCl3)
ꢂ 9.73 (d, J ¼ 4, 2 Hz, 2H, Porꢀ), 9.66 (d, J ¼ 4:2 Hz, 2H, Porꢀ),
8.87 (d, J ¼ 4:2 Hz, 2H, Porꢀ3), 6.07 (ddt, J ¼ 5:9, 10.8, 16.2 Hz,
4H, CH=CH2), 5.47 (d, J ¼ 16:2 Hz, 2H, CH=CH2), 5.46 (d, J ¼
1:8 Hz, 1H, Im H4), 5.50–5.40 (m, 4H, ester ꢀ), 5.40 (d, J ¼ 4:2
Hz, 2H, Porꢀ4), 5.32 (dd, J ¼ 1:8, 10.2 Hz, 2H, CH=CH2), 5.25
(t, J ¼ 7 Hz, 2H, heptyl-C1), 4.88 (dd, J ¼ 13:8, 5.9 Hz, 2H,
–OCH2), 4.82 (dd, J ¼ 13:8, 5.9 Hz, 2H, –OCH2), 3.86–3.80 (m,
2H, ester ꢃ), 3.75–3.64 (m, 2H, ester ꢃ), 2.75 (t.t, J ¼ 7, 7 Hz,
2H, heptyl-C2), 2.00 (t.t, J ¼ 7, 7 Hz, 2H, hepty-C3), 1.97 (d, J ¼
1:8 Hz, 1H, Im H5), 1.67 (t.t, J ¼ 7, 7 Hz, 2H, heptyl-C4), 1.64 (s,
3H, NCH3), 1.48–1.43 (m, 4H, heptyl-C5, C6), 0.98 (t, J ¼ 7 Hz,
3H, heptyl-C7); 13C NMR (150 MHz, CDCl3) ꢂ 172.9 (C=O),
150.1 (Porꢃ), 149.5 (Porꢃ), 149.2 (Porꢃ), 148.6 (Porꢃ), 146.1
(Im N=C–N), 132.6 (CH=CH2), 129.5 (Porꢀ2), 128.9 (Porꢀ3),
128.3 (Porꢀ1), 127.2 (Porꢀ4), 122.8 (Im CH), 121.6 (meso),
118.4 (Im CH), 117.8 (CH=CH2), 116.8 (meso), 95.8 (meso),
65.5 (–OCH2), 42.7 (ester ꢃ), 39.8 (heptyl-C2), 36.3 (heptyl-C1),
32.7 (NCH3), 32.2 (heptyl-C3), 30.9 (ester ꢀ), 29.7 (heptyl-C4),
22.9 (heptyl-C6), 14.3 (heptyl-C7); D-5a: UV–vis (CHCl3): 416
(Abs.; 0.1052), 434 (0.1165), 568 (0.0104), 616 (0.0044) nm; 5a
(monomer): UV–vis (pyridine): 426, 566, 610 nm; Fluorescence
(Ex = 416 nm, CHCl3) : 619, 673 nm; MALDI-TOF Mass of
C43H46N6O4Zn Calcd: 774.3; Found: 775.4 (M + H)þ.
5,15-Bis[3-(allyloxycarbonyl)propyl]-10-heptyl-20-(1-meth-
yl-2-imidazolyl)porphyrinatozinc (5b): In a similar manner as
for the preparation of 5a, the introduction of zinc ion into 4b
(75.4 mg, 102 mmol) was carried out to give 5b (82 mg, quant).
D-5b: 1H NMR (600 MHz, CDCl3) ꢂ 9.72 (d, J ¼ 4 Hz, 2H, Porꢀ),
9.66 (d, J ¼ 4 Hz, 2H, Porꢀ), 8.92 (d, J ¼ 4 Hz, 2H, Porꢀ3), 6.09
(m, 2H, CH=CH2), 5.47 (s, 1H, Im H5), 5.46 (d, J ¼ 16:2 Hz, 2H,
CH=CH2), 5.32 (d, J ¼ 10:8 Hz, 2H, CH=CH2), 5.31 (d, J ¼ 4
Hz, 2H, Porꢀ4), 5.28–5.23 (m, 4H, heptyl-C1), 5.14–4.98 (m,
4H, ester ꢁ), 4.83 (d, J ¼ 6 Hz, 4H, –OCH2), 3.27–3.23 (m, 2H,
ester ꢀ), 3.10–3.00 (m, 4H, ester ꢀ,ꢃ), 2.98–2.94 (m, 2H, ester
ꢃ), 2.76 (t.t, J ¼ 7, 7 Hz, 2H, heptyl-C2), 2.01 (t.t, J ¼ 7, 7 Hz,
2H, heptyl-C3), 1.98 (d, J ¼ 2 Hz, 1H, Im H4), 1.70–1.66 (m,
2H, heptyl-C4), 1.64 (s, 3H, NCH3), 1.49–1.41 (m, 4H, heptyl-
C5, C6), 0.99 (t, J ¼ 7 Hz, 3H, heptyl-C7); 13C NMR (150 MHz,
CDCl3) ꢂ 173.8 (C=O), 150.4 (Porꢃ), 149.5 (Porꢃ), 149.2 (Porꢃ),
148.4 (Porꢃ), 146.3 (Im N=C–N), 132.6 (CH=CH2), 129.3
(Porꢀ3), 129.1 (Porꢀ2), 128.4 (Porꢀ1), 127.0 (Porꢀ4), 122.3
(meso), 121.6 (Im CH), 118.5 (CH=CH2), 118.0 (Im CH), 117.6
(meso), 95.5 (meso), 65.4 (–OCH2), 39.7 (heptyl-C2), 36.3 (hep-
tyl-C1), 35.0 (ester ꢁ), 34.9 (ester ꢃ), 33.5 (ester ꢀ), 32.6 (NCH3),
32.2 (heptyl-C5), 31.0 (heptyl-C3), 29.7 (heptyl-C4), 22.9 (heptyl-
C6), 14.3 (heptyl-C7); UV–vis (CHCl3): 416 (Abs.; 0.0726), 434
(0.0840), 568 (0.0014), 618 (ꢁ0:0008) nm; Fluorescence (Ex =
416 nm, CHCl3): 621, 674 nm; MALDI-TOF Mass of
C45H50N6O4Zn Calcd: 802.32; Found: 803.62 (M + H)þ.
5,15-Bis[4-(allyloxycarbonyl)butyl]-10-heptyl-20-(1-methyl-
2-imidazolyl)porphyrinatozinc (5c): In a similar manner as for
the preparation of 5a, the introduction of zinc ion into 4c (105 mg,
137 mmol) was carried out to give 5c (113 mg, quant). D-5c:
1H NMR (600 MHz, CDCl3) ꢂ 9.71 (d, J ¼ 4 Hz, 2H, Porꢀ),
9.60 (d, J ¼ 4 Hz, 2H, Porꢀ), 8.82 (d, J ¼ 4 Hz, 2H, Porꢀ3),
5.96 (ddt, J ¼ 5, 11, 16 Hz, 2H, CH=CH2), 5.43 (s, 1H, Im H5),
5.32 (d, J ¼ 4 Hz, 2H, Porꢀ4), 5.25 (dd, J ¼ 16 Hz, 2H,
CH=CH2), 5.20 (dd, J ¼ 11 Hz, 2H, CH=CH2), 5.27–5.20 (m,
4H, heptyl-C1), 5.14–5.00 (m, 4H, ester ꢂ), 4.67 (d, J ¼ 5 Hz,
4H, –OCH2), 2.90 (t.t, J ¼ 7, 7 Hz, 2H, heptyl-C2), 2.77–2.73
(m, 8H, ester ꢃ,ꢁ), 2.55–2.33 (m, 4H, ester ꢀ), 2.00 (t.t, J ¼ 7, 7
Hz, 2H, heptyl-C3), 1.98 (d, J ¼ 1:8 Hz, 1H, Im H4), 1.69 (t.t,
J ¼ 7, 7 Hz, 2H, heptyl-C4), 1.62 (s, 3H, NCH3), 1.48–1.43 (m,
4H, heptyl-C5, C6), 0.99 (t, J ¼ 7 Hz, 3H, heptyl-C7); 13C NMR
(150 MHz, CDCl3) ꢂ 173.6 (C=O), 150.4 (Porꢃ), 149.4 (Porꢃ),
149.0 (Porꢃ), 148.4 (Porꢃ), 146.2 (Im N=C–N), 132.5
(CH=CH2), 129.1 (Porꢀ1), 129.0 (Porꢀ3), 128.3 (Porꢀ2), 127.0
(Porꢀ4), 122.3 (meso), 121.6 (Im CH), 118.8 (meso), 118.3
(CH=CH2), 117.7 (Im CH), 95.5 (meso), 65.2 (–OCH2), 39.8 (es-
ter ꢃ), 38.6 (heptyl-C2), 36.4 (ester ꢂ), 35.6 (heptyl-C1), 34.7 (ester
ꢁ), 32.7 (NCH3), 32.2 (heptyl-C5), 31.0 (heptyl-C3), 29.7 (heptyl-
C4), 26.7 (ester ꢀ), 22.9 (heptyl-C6), 14.3 (heptyl-C7); UV–vis
(CHCl3): 415 (Abs.; 0.6215), 435 (0.7064), 531 (0.0085), 568
(0.0544), 618 (0.0294) nm; Fluorescence (Ex = 415 nm, CHCl3):
622, 677 nm; MALDI-TOF Mass of C47H54N6O4Zn Calcd:
830.35; Found: 831.32 (M + H)þ.

372 Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
Covalent Linking of Porphyrin Dimers
5,15-Bis[2-(allyloxycarbonyl)ethyl]-20-(1-methyl-2-imida-
zolyl)-10-phenylporphyrinatozinc (5d): In a similar manner as
for the preparation of 5a, the introduction of zinc ion into 4d (530
mg, 43 mmol) was carried out to give 5d (33 mg, quant). D-5d:
1H NMR (600 MHz, CDCl3) ꢂ 9.61 (d, J ¼ 4:2 Hz, 2H, Porꢀ2),
9.06 (d, J ¼ 4:2 Hz, 2H, Porꢀ1), 8.94 (d, J ¼ 4:2 Hz, 2H, Porꢀ3),
8.67 (d, J ¼ 6:6 Hz, 1H, Ph), 8.13 (d, J ¼ 7:8 Hz, 1H, Ph), 7.94
(dd, J ¼ 7:8, 8.4 Hz, 1H, Ph), 7.87 (t, J ¼ 8:4 Hz, 1H, Ph), 7.77
(dd, J ¼ 6:6, 8.4 Hz, 1H, Ph), 6.06 (ddt, J ¼ 6, 10.2, 16.2 Hz,
2H, CH=CH2), 5.53 (d, J ¼ 2 Hz, 1H, Im H5), 5.51–5.46 (m,
4H, ester ꢀ), 5.47 (d, J ¼ 4:2 Hz, 2H, Porꢀ4), 5.46 (dd, J ¼ 1:8,
16.2 Hz, 2H, CH=CH2), 5.31 (dd, J ¼ 1:8, 10.2 Hz, 2H,
CH=CH2), 4.87 (ddt, J ¼ 1:2, 6, 12 Hz, 2H, –OCH2), 4.84 (ddt,
J ¼ 1:2, 6, 12 Hz, 2H, –OCH2), 3.88–3.81 (m, 2H, ester ꢃ),
3.75–3.68 (m, 2H, ester ꢃ), 2.13 (d, J ¼ 2 Hz, 1H, Im H4), 1.67
(s, 3H, NCH3); 13C NMR (150 MHz, CDCl3) ꢂ 172.8 (C=O),
150.7 (Porꢃ), 149.6 (Porꢃ), 149.5 (Porꢃ), 148.3 (Porꢃ), 146.0
(Im N=C–N), 134.8 (Ph), 134.7 (Ph), 132.7 (Porꢀ2), 132.5
(CH=CH2), 128.9 (Porꢀ1), 128.1 (Porꢀ3), 127.6 (Porꢀ4), 127.4
(Ph), 126.5 (Ph), 126.3 (Ph), 122.0 (meso), 121.5 (Im CH), 118.4
(Im CH), 118.0 (CH=CH2), 117.5 (meso), 96.4 (meso), 65.6
(–OCH2), 42.7 (ester ꢃ), 32.7 (NCH3), 30.9 (ester ꢀ); UV–vis
(CHCl3): 413 (Abs.; 0.1400), 435 (0.1510), 565 (0.0198), 616
(0.0107) nm; Fluorescence (Ex = 413 nm, CHCl3): 619, 674
nm; MALDI-TOF Mass of C42H36N6O4Zn Calcd: 752.21; Found:
753.4 (M + H)þ.
5,15-Bis[2-(allyloxycarbonyl)ethyl]-20-(1-methyl-2-imida-
zolyl)-10-(trimethylsilylethynyl)porphyrinatozinc (5e): In a
similar manner as for the preparation of 5a, the introduction of zinc
ion into 4e (50 mg, 70 mmol) was carried out to give 5e (54 mg,
quant). D-5e: 1H NMR (600 MHz, CDCl3) ꢂ 9.92 (d, J ¼ 4:2
Hz, 2H, Porꢀ2), 9.65 (d, J ¼ 4:2 Hz, 2H, Porꢀ1), 8.86 (d, J ¼
4:2 Hz, 2H, Porꢀ3), 6.06 (ddt, J ¼ 6, 10.8, 16.2 Hz, 2H,
CH=CH2), 5.48 (d, J ¼ 16:2 Hz, 2H, CH=CH2), 5.45 (d, J ¼
4:2 Hz, 2H, Porꢀ4), 5.44 (d, J ¼ 2 Hz, 1H, Im CH), 5.31 (d, J ¼
10:8 Hz, 2H, CH=CH2), 4.86 (dd, J ¼ 6, 12.6 Hz, 2H, –OCH2),
4.80 (dd, J ¼ 6, 12.6 Hz, 2H, –OCH2), 3.85–3.77 (m, 2H, ester
ꢀ), 3.73–3.67 (m, 2H, ester ꢀ), 2.02 (d, J ¼ 2 Hz, 1H, Im CH),
1.66 (s, 3H, NCH3), 0.74 (s, 9H, TMS); 13C NMR (150 MHz,
CDCl3) ꢂ 172.7 (C=O), 152.0 (Porꢃ), 150.5 (Porꢃ), 150.0 (Porꢃ),
147.8 (Porꢃ), 145.5 (Im N=C–N), 132.5 (CH=CH2), 131.9
(Porꢀ2), 129.3 (Porꢀ3), 128.8 (Porꢀ1), 127.9 (Porꢀ4), 121.9 (Im
CH), 118.5 (meso), 118.4 (Im CH), 118.2 (CH=CH2), 109.2
(meso), 100.4 (TMS–CꢅC–), 99.9 (TMS–CꢅC–), 98.7 (meso),
65.6 (–OCH2), 42.7 (ester ꢀ), 32.7 (NCH3), 30.9 (ester ꢃ), 0.7
(TMS); UV–vis (CHCl3): 426 (Abs.; 0.7554), 445 (1.2834), 579
(0.0830), 637 (0.1747) nm; Fluorescence (Ex = 426 nm, CHCl3):
640, 698 nm; MALDI-TOF Mass of C41H40N6O4SiZn Calcd:
772.22; Found: 773.6 (M + H)þ.
CH2), 2.14 (d, J ¼ 1:7 Hz, 1H, Im H4), 1.66 (s, 3H, N–Me).
UV–vis (PhCN): 415 (Abs.; 0.47), 439 (0.49), 523 (0.051), 566
(0.056), 620 (0.056) nm; MALDI-TOF Mass of C42H40N6O2Zn
Calcd: 726.3; Found: 727.3 [(M + H)þ, 100 (relative intensity)],
1452.2 [(M2 + H)þ, 60].
Covalently Linked Dimer 7a: A mixture of D-5a (80 mg, 0.11
mmol as 5a) and Grubbs catalyst 6 (8 mg, 10 mmol) was stirred in
CHCl3 (15 mL) at rt. The time course of the reaction progress was
monitored by MALDI-TOF mass spectra. (Normally, convergent
peaks corresponding to the desired product were observed after
2–3 h.) Water was added to the mixture, and the mixture was ex-
tracted with CHCl3. The organic layer was washed with brine,
dried over Na2SO4, and evaporated under reduced pressure. The
residue was loaded on a silica gel column and eluted with
CHCl3/acetone (9:1) to give the covalently linked dimer 7a (73
mg, 95%). Split signals due to isomers with respect to two olefin
ꢀ
moieties were observed in a ca. 1:4 ratio. Asterisk ( ) and prime
(0) indicate signals of major and minor isomers, respectively. No
mark indicates that peaks of both isomers are overlapped. 1H NMR
(600 MHz, CDCl3) ꢂ 9.750 (cis; d, J ¼ 4:2 Hz, 4H ꢃ 1/5, Porꢀ2),
ꢀ
9.75 (trans; d, J ¼ 4:2 Hz, 4H ꢃ 4/5, Porꢀ2), 9.670 (cis; d, J ¼
ꢀ
4:2 Hz, 4H ꢃ 1/5, Porꢀ1), 9.63 (trans; d, J ¼ 4:2 Hz, 4H ꢃ 4/
5; Porꢀ1), 8.910 (cis; d, J ¼ 4:2 Hz, 4H ꢃ 1/5, Porꢀ3), 8.89
ꢀ
ꢀ
(trans; d, J ¼ 4:2 Hz, 4H ꢃ 4/5, Porꢀ3), 6.47–6.45 (trans; m,
J ¼ 1:2 Hz, 4H ꢃ 4/5, CH=CH), 6.400 (cis; t, J ¼ 6:0 Hz, 4H
ꢃ 1/5, CH=CH), 5.50–5.42 (trans & cis; m, 4H, ester ꢀ),
ꢀ0
ꢀ
5.43 (trans & cis; s, 2H, Im H5), 5.39 (trans; d, J ¼ 4:2 Hz,
4H ꢃ 4/5, Porꢀ4), 5.330 (cis; d, J ¼ 4:2 Hz, 4H ꢃ 1/5, Porꢀ4),
5.29–5.22 (trans & cis; m, 4H, heptyl-C1), 5.200 (cis; dd,
J ¼ 6:0, 12 Hz, 2H ꢃ 1/5, CH=CH), 5.100 (cis; dd, J ¼ 6:0, 12
ꢀ
Hz, 2H ꢃ 1/5, O–CH2), 5.06 (trans; d, J ¼ 10:2 Hz, 2H ꢃ 4/
ꢀ
5, O–CH2), 5.00 (trans; d, J ¼ 10:2 Hz, 2H ꢃ 4/5, O–CH2),
4.14–4.050 (cis; m, 4H ꢃ 1/5, ester ꢃ), 3.85–3.790 (cis; m, 4H ꢃ
ꢀ
1/5, ester ꢃ), 3.92–3.80 (trans; m, 4H ꢃ 4/5, ester ꢃ), 3.74–
ꢀ
3.60 (trans; m, 4H ꢃ 4/5, ester ꢃ), 2.77–2.70 (trans & cis; m,
4H, heptyl-C2), 2.03–1.97 (trans & cis; m, 4H, heptyl-C3), 1.94
(trans & cis; s, 2H, Im H4), 1.69–1.65 (trans & cis; m, 4H, hep-
tyl-C4), 1.64 (trans & cis; s, 6H, NCH3), 1.48–1.43 (trans & cis;
m, 8H, heptyl-C5, C6), 0.99 (trans & cis; t, J ¼ 7:2 Hz, 6H, hep-
tyl-C7); 13C NMR (150 MHz, CDCl3) ꢂ 172.90 (C=O; cis),
ꢀ
ꢀ
172.5 (C=O; trans), 150.0 (Porꢃ; trans), 149.90 (Porꢃ; cis),
149.630 (Porꢃ; cis), 149.60 (Porꢃ; trans), 149.0 (Porꢃ; trans),
ꢀ
ꢀ
148.90 (Porꢃ; cis), 148.4 (Porꢃ; trans), 148.30 (Porꢃ; cis),
ꢀ
146.00 (Im N=C–N; cis), 145.9 (Im N=C–N; trans), 130.8
ꢀ
ꢀ
(CH=CH; trans), 129.80 (CH=CH; cis), 129.6 (Porꢀ2), 128.70
ꢀ
(Porꢀ3; cis), 128.6 (Porꢀ3; trans), 128.2 (Porꢀ1), 127.37 &
127.32 (Porꢀ4), 122.8 (meso; trans), 122.70 (meso; cis), 121.65
& 121.61 (imidazole ring), 117.90 & 117.86 (imidazole ring),
ꢀ
ꢀ
ꢀ0
ꢀ
116.80 (meso; cis), 116.7 (meso; trans), 96.0 (meso), 63.4
5,15-Bis(3-allyloxypropyl)-20-(1-methyl-2-imidazolyl)-10-
phenylporphyrinatozinc (5f): In a similar manner as for the
preparation of 5a, the introduction of zinc ion into 4f (90 mg,
136 mmol) was carried out to give 5f (99 mg, quant). D-5f:
1H NMR (270 MHz, CDCl3) ꢂ 9.63 (d, J ¼ 4:8 Hz, 2H, Porꢀ1),
9.03 (d, J ¼ 4:8 Hz, 2H, Porꢀ2), 8.95 (d, J ¼ 4:8 Hz, 2H, Porꢀ3),
8.68 (d, J ¼ 7:4 Hz, 1H, o-Ph), 8.16 (d, J ¼ 7:3 Hz, 1H, o-Ph),
7.98–7.72 (m, 3H, m- and p-Ph), 6.18 (ddt, J ¼ 17:3, 10.4, 5.4
Hz, 2H, CH=CH2), 5.52 (ddt, J ¼ 17:3, 3.5, 1.6 Hz, 2H,
CH=CH2), 5.50 (d, J ¼ 1:7 Hz, 1H, Im H5), 5.41 (d, J ¼ 4:8
Hz, 2H, Porꢀ4), 5.33 (ddt, J ¼ 10:4, 4.3, 1.6 Hz, 2H, CH=CH2),
5.28–5.14 (m, 4H, Por ꢃCH2), 4.23 (dt, J ¼ 5:4, 1.6 Hz, 4H,
CH2–CH=CH2), 4.00–3.85 (m, 4H, –CH2O), 3.16–2.90 (m, 4H,
(–OCH2; trans), 58.90 (–OCH2; cis), 43.2 (ester ꢃ), 39.8 (heptyl-
C2), 36.3 (heptyl-C1), 32.7 (NCH3), 32.2 (heptyl-C5), 31.4 (ester
ꢀ), 30.9 (heptyl-C3), 29.6 (heptyl-C4), 22.9 (heptyl-C6), 14.3 (hep-
tyl-C7); UV–vis (nm, CHCl3): 416 (Abs.; 2.0287), 435 (2.2464),
570 (0.2089), 617 (0.0799), (nm, pyridine): 417 (Abs.; 0.7124),
436 (0.8064), 570 (0.712), 617 (0.0301), (nm, MeOH/CHCl3
=
100/1): 416 (Abs.; 0.1009), 431 (0.1135), 566 (0.0100), 615
(0.0045); Fluorescence (Ex = 416 nm, CHCl3): 620, 673 nm;
MALDI-TOF Mass of C82H84N12O8Zn2 Calcd: 1492.5; Found:
1493.3 (M + H)þ.
Covalently Linked Dimer 7b: A mixture of D-5b (82 mg, 102
mmol as 5b) and Grubbs catalyst 6 (42 mg, 51 mmol) was stirred in
CHCl3 (20 mL) at 0 ꢂC. After 36 h, water was added to the mixture,

A. Ohashi et al.
Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
373
ꢀ
followed by extraction with CHCl3. The organic layer was washed
with brine, dried over Na2SO4, and evaporated under reduced pres-
sure. The residue was loaded on a silica gel column and eluted with
CHCl3/acetone (9:1) to give the covalently linked dimer 7b (41
mg, 26%). Small peaks due to inseparable impurities were ob-
served in the 1H NMR spectra. Split signals due to isomers with re-
spect to two olefin moieties were observed in a ca. 1:3 ratio. Aster-
(cis; m, 8H ꢃ 1/3, –OCH2), 4.73–4.67 (trans; m, 8H ꢃ 2/3,
–OCH2), 2.93–2.90 (trans & cis; m, 8H, ester ꢃ), 2.77–2.72 (trans
& cis; m, 4H, heptyl-C2), 2.71–2.65 (trans & cis; m, 8H, ester ꢁ),
2.45–2.32 (trans & cis; m, 8H, ester ꢀ), 2.03–1.99 (trans & cis; m,
4H, heptyl-C3), 1.98 (trans & cis; s, 2H, Im CH), 1.72–1.67 (trans
& cis; m, 4H, heptyl-C4), 1.54 (trans & cis; s, 6H, NCH3), 1.48–
1.43 (trans & cis; m, 8H, heptyl-C5, C6), 0.99 (trans & cis; t, J ¼
7 Hz, 6H, heptyl-C7); 13C NMR (150 MHz, CDCl3) ꢂ 173.50
ꢀ
isk ( ) and prime (0) indicate signals of major and minor isomers,
ꢀ ꢀ
(C=O; cis), 173.4 (C=O; trans), 150.4 (Porꢃ; trans), 150.30
respectively. No mark indicates that peaks of both isomers are
overlapped. 1H NMR (600 MHz, CDCl3) ꢂ 9.730 (cis; d, J ¼ 4
ꢀ
(Porꢃ; cis), 149.3 (Porꢃ; trans), 149.20 (Porꢃ; cis,), 149.10 (Porꢃ;
ꢀ
ꢀ ꢀ
cis), 149.0 (Porꢃ; trans), 148.40 (Porꢃ; cis), 148.3 (Porꢃ; trans),
Hz, 4H ꢃ 1/4; Porꢀ2), 9.71 (trans; d, J ¼ 4 Hz, 4H ꢃ 3/4,
Porꢀ2), 9.59–9.54 (trans & cis; d, J ¼ 4 Hz, Porꢀ1), 8.920 (cis;
146.2 (imidazole), 129.00 (Porꢀ3; cis), 128.9 (Porꢀ3; trans),
ꢀ
ꢀ
ꢀ
d, J ¼ 4 Hz, 4H ꢃ 1/4, Porꢀ3), 8.90 (trans; d, J ¼ 4 Hz, 4H ꢃ
128.70 (CH=CH; cis), 128.4 (CH=CH; trans), 128.3 (Porꢀ2),
ꢀ
3/4, Porꢀ3), 6.23–6.17 (trans; m, 4H ꢃ 3/4, CH=CH), 5.93–
127.0 (Porꢀ4), 122.4 (meso), 121.6 (imidazole ring), 118.80 (meso;
ꢀ
cis), 118.6 (meso; trans), 117.7 (imidazole ring), 95.6 and 95.5
5.870 (cis; m, 4H ꢃ 1/4, CH=CH), 5.42 (trans & cis; s, 2H, Im
ꢀ
ꢀ
(meso), 63.3 (–OCH2; trans), 60.30 (–OCH2; cis), 39.8 (heptyl-
H5), 5.39 (trans; d, J ¼ 4 Hz, 4H ꢃ 3/4, Porꢀ4), 5.350 (cis; d, J ¼
ꢀ
C2), 38.80 (ester ꢃ; cis), 38.4 (ester ꢃ; trans), 36.3 (hepyl-C1),
4 Hz, 4H ꢃ 1/4, Porꢀ4), 5.27–5.22 (trans & cis; m, 4H, heptyl-C1),
5.16–5.07 (trans & cis; m, 8H, ester ꢁ), 5.02–4.850 (cis; m, 8H ꢃ
35.60 (ester ꢂ; cis), 35.5 (ester ꢂ; trans), 35.1 (ester ꢁ; trans),
ꢀ
ꢀ
ꢀ
1/4, –OCH2), 4.87–4.69 (trans; m, 8H ꢃ 3/4, –OCH2), 3.12–
34.90 (ester ꢁ; cis), 32.6 (NCH3), 32.2 (heptyl-C5), 31.0 (heptyl-
ꢀ
2.98 (trans & cis; m, 8H, ester ꢀ), 2.94–2.91 (trans & cis; m,
4H, ester ꢃ), 2.86–2.82 (trans & cis; m, 4H, ester ꢃ), 2.77–2.70
(trans & cis; m, 4H, heptyl-C2), 2.03–1.98 (trans & cis; m, 4H,
heptyl-C3), 1.97 (trans & cis; s, 2H, Im H4), 1.71–1.66 (trans &
cis; m, 4H, heptyl-C4), 1.62 (trans & cis; s, 6H, NCH3), 1.48–
1.42 (trans & cis; m, 8H, heptyl-C5, C6), 0.99 (trans & cis; t, J ¼
7 Hz, 6H, heptyl-C7); 13C NMR (150 MHz, CDCl3) ꢂ 173.70
C3), 29.6 (heptyl-C4), 26.7 (ester ꢀ, trans), 26.50 (ester ꢀ; cis),
22.9 (heptyl-C6), 14.3 (heptyl-C7); UV–vis (CHCl3): 416 (Abs.;
0.0771), 435 (0.0849), 570 (0.0071), 617 (0.0025), (pyridine):
417 (Abs.; 0.3506), 435 (0.4257), 569 (0.0339), 619 (0.0195),
(MeOH/CHCl3 = 100/1): 412 (Abs.; 0.0737), 430 (0.0816), 565
(0.0073), 615 (0.0043) nm; Fluorescence (Ex = 416 nm, CHCl3):
620, 674 nm; MALDI-TOF Mass of C90H100N12O8Zn2 Calcd:
1604.6; Found: 1605.5 (M + H)þ.
Covalently Linked Dimer 7d: In a similar manner as for the
preparation of 7a, the covalent linking of D-5d (30 mg, 40 mmol)
was carried out to give 7d (28 mg, 95%). Split signals due to iso-
mers with respect to two olefin moieties were observed in a ca. 1:4
ꢀ
ꢀ
(C=O; cis), 173.6 (C=O; trans), 150.4 (Porꢃ; trans), 149.90
ꢀ
(Porꢃ; cis), 149.70 (Porꢃ; cis), 149.6 (Porꢃ; trans), 149.0 (Porꢃ),
148.7 (Porꢃ), 146.2 (Im N=C–N), 129.50 (Porꢀ3; cis), 129.3
(Porꢀ3; trans), 129.0 (Porꢀ2), 128.40 (CH=CH; cis), 128.3
ꢀ
ꢀ
(CH=CH; trans), 128.1 (Porꢀ2), 127.3 (Porꢀ4; trans), 127.00
ꢀ
(Porꢀ4; cis), 122.4 (meso), 121.7 (Im CH), 118.50 (meso; cis),
ratio. Asterisk ( ) and prime (0) indicate signals of major and minor
isomers, respectively. 1H NMR (600 MHz, CDCl3) ꢂ 9.610 (cis; d,
ꢀ
ꢀ
118.1 (meso; trans), 118.0 (Im CH), 117.7 (meso), 95.4 (meso),
ꢀ
63.6 (–OCH2; trans), 60.00 (–OCH2; cis), 39.7 (heptyl-C2), 36.3
J ¼ 4:2 Hz, 4H ꢃ 1/5, Porꢀ2), 9.58 (trans; d, J ¼ 4:2 Hz, 4H ꢃ
ꢀ
(heptyl-C1), 35.2 (ester ꢁ), 35.1 (ester ꢀ; trans), 34.80 (ester ꢀ;
4/5, Porꢀ2), 9.07 (trans & cis; d, J ¼ 4:2 Hz, 4H, Porꢀ1), 8.990
ꢀ
cis), 33.70 (ester ꢃ; cis), 33.4 (ester ꢃ; trans), 32.7 (heptyl-C5),
(cis; d, J ¼ 4:2 Hz, 4H ꢃ 1/5, Porꢀ3), 8.97 (trans; d, J ¼ 4:2
ꢀ
ꢀ
32.2 (NCH3), 31.0 (heptyl-C3), 29.7 (heptyl-C4), 22.9 (heptyl-
C6), 14.3 (heptyl-C7); UV–vis (CHCl3): 416 (Abs.; 0.2307), 434
(0.2680), 568 (0.0221), 617 (0.0112), (pyridine): 417 (Abs.;
0.6572), 434 (0.8115), 568 (0.0661), 617 (0.0341) nm; Fluores-
cence (Ex = 416 nm, CHCl3): 620, 678 nm; MALDI-TOF Mass
of C86H92N12O8Zn2 Calcd: 1548.5; Found: 1549.5 (M + H)þ.
Covalently Linked Dimer 7c: A mixture of D-5c (105 mg,
126 mmol as 5c) and Grubbs catalyst 6 (52 mg, 63 mmol) was stir-
red in CHCl3 (20 mL) at 0 ꢂC. After 36 h, water was added to the
mixture, followed by extraction with CHCl3. The organic layer was
washed with brine, dried over Na2SO4, and evaporated under re-
duced pressure. The residue was loaded on a silica gel column
and eluted with CHCl3/acetone (10:1) to give the covalently linked
dimer 7c (33 mg, 16%). Split signals due to isomers with respect to
Hz, 4H ꢃ 4/5, Porꢀ3), 8.74–8.65 (trans & cis; br, 2H, Ph),
8.15–8.01 (trans & cis; br, 2H, Ph), 7.95 (trans & cis; br.t, J ¼
7:8 Hz, 2H, Ph), 7.87 (trans & cis; br.t, J ¼ 8:4 Hz, 2H, Ph),
ꢀ
7.77 (trans & cis; br.t, J ¼ 7:8 Hz, 2H, Ph), 6.47 (trans; br.s,
4H ꢃ 4/5, CH=CH), 6.400 (cis; t, J ¼ 6:0 Hz, 4H ꢃ 1/5,
CH=CH), 5.58–5.42 (trans & cis; m, 8H, ester ꢀ), 5.48 (trans &
ꢀ
cis; br, 2H, Im H5), 5.47 (trans; d, J ¼ 4:2 Hz, 4H ꢃ 4/5, Porꢀ4),
5.390 (cis; d, J ¼ 4:2 Hz, 4H ꢃ 1/5, Porꢀ4), 5.190 (cis; dd, J ¼ 6:0,
12 Hz, 4H ꢃ 1/5, –OCH2), 5.100 (cis; dd, J ¼ 6:0, 12 Hz, 4H ꢃ
ꢀ
1/5, –OCH2), 5.06 (trans; d, J ¼ 10:2 Hz, 4H ꢃ 4/5, –OCH2),
5.00 (trans; d, J ¼ 10:2 Hz, 4H ꢃ 4/5, –OCH2), 4.15–4.050
ꢀ
(cis; m, 4H ꢃ 1/5, ester ꢃ), 3.90–3.870 (cis; m, 4H ꢃ 1/5, ester
ꢀ
ꢀ
ꢃ), 3.95–3.80 (trans; m, 4H ꢃ 4/5, ester ꢃ), 3.78–3.65 (trans;
m, 4H ꢃ 4/5, ester ꢃ), 2.10 (trans & cis; br, 2H, Im H4), 1.68
(trans & cis; s, 6H, NCH3); 13C NMR (150 MHz, CDCl3) ꢂ
ꢀ
two olefin moieties were observed in a ca. 1:2 ratio. Asterisk ( )
and prime (0) indicate signals of major and minor isomers, respec-
tively. No mark indicates that peaks of both isomers are overlap-
172.90 (C=O; cis), 172.4 (C=O; trans), 150.6 (Porꢃ), 149.6
ꢀ
(Porꢃ), 149.5 (Porꢃ), 148.0 (Porꢃ), 143.8 (Im N=C–N), 134.7
1
ped. H NMR (600 MHz, CDCl3) ꢂ 9.72 (trans & cis; d, J ¼ 4:2
(Ph), 134.6 (Ph), 132.8 (Porꢀ1), 129.8 (Porꢀ3), 128.80 (CH=CH;
ꢀ
127.4 (Ph), 126.6 (Ph), 126.2 (Ph), 121.5 (Im CH), 118.0 (Im
Hz, 4H, Porꢀ2), 9.60 (trans & cis; d, J ¼ 4 Hz, 4H, Porꢀ1),
cis), 128.7 (CH=CH; trans), 128.0 (Porꢀ2), 127.5 (Porꢀ4),
ꢀ
8.860 (cis; d, J ¼ 4 Hz, 4H ꢃ 1/3, Porꢀ3), 8.82 (trans; d, J ¼ 4
ꢀ
ꢀ
Hz, 4H ꢃ 2/3, Porꢀ3), 6.06–6.04 (trans; m, J ¼ 1:2 Hz, 4H ꢃ
CH), 117.3 (meso), 63.4 (–OCH2; trans), 58.90 (–OCH2; cis),
2/3, CH=CH), 5.930 (cis; t, J ¼ 6:0 Hz, 4H ꢃ 1/3, CH=CH),
43.2 (ester ꢃ), 32.7 (NCH3), 31.4 (ester ꢀ); UV–vis (CHCl3):
413 (Abs.; 0.0722), 436 (0.0739), 565 (0.0124), 617 (0.079) nm;
Fluorescence (Ex = 413 nm, CHCl3): 620, 676 nm; MALDI-
TOF Mass of C80H64N12O8Zn2 Calcd: 1448.36; Found: 1449.47
(M + H)þ.
ꢀ
5.46 (trans & cis; s, 2H, Im CH), 5.35 (trans; d, J ¼ 4 Hz, 4H
ꢃ 2/3, Porꢀ4), 5.300 (cis; d, J ¼ 4 Hz, 4H ꢃ 1/3, Porꢀ4), 5.29–
5.22 (trans & cis; m, 4H, heptyl-C1), 5.15–4.95 (trans & cis; m,
8H, ester ꢂ), 4.92–4.870 (cis; m, 8H ꢃ 1/3, –OCH2), 4.79–4.770

374 Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
Covalent Linking of Porphyrin Dimers
Covalently Linked Dimer 7e: In a similar manner as for the
preparation of 7a, the covalent linking of D-5e (40 mg, 52 mmol)
was carried out to give 7e (36 mg, 93%). Split signals due to iso-
mers with respect to two olefin moieties were observed in a ca. 1:4
CH=CH–), 4.19 (m, 4H, –CH2–O–), 3.17–3.08 (m, 2H, –CH2–),
3.06–2.95 (m, 2H, –CH2–), 2.13 (d, J ¼ 1:1 Hz, 1H ꢃ 1/4, Im
H4), 2.11 (d, J ¼ 1:1 Hz, 1H ꢃ 3/4, Im-H4), 1.70 (s, 3H ꢃ 3/4,
NMe), 1.68 (s, 3H ꢃ 1/4, NMe); UV–vis (CHCl3): 414 (Abs.;
0.69), 438 (0.74), 529 (0.012), 567 (0.059), 619 (0.034) nm;
MALDI-TOF Mass of C80H72N12O4Zn2 Calcd (max. peak):
1396.3; Found: 1398.5 (M + H)þ.
ꢀ
ratio. Asterisk ( ) and prime (0) indicate signals of major and minor
isomers, respectively. 1H NMR (600 MHz, CDCl3) ꢂ 9.9330 (cis; d,
ꢀ
J ¼ 4:2 Hz, 4H ꢃ 1/5, Porꢀ2), 9.928 (trans; d, J ¼ 4:2 Hz, 4H ꢃ
ꢀ
4/5, Porꢀ2), 9.650 (cis; d, J ¼ 4:2 Hz, 4H ꢃ 1/5, Porꢀ1), 9.62
(trans; d, J ¼ 4:2 Hz, 4H ꢃ 4/5, Porꢀ1), 8.900 (cis; d, J ¼ 4:2
ꢀ
References
Hz, 4H ꢃ 1/5, Porꢀ3), 8.89 (trans; d, J ¼ 4:2 Hz, 4H ꢃ 4/5,
ꢀ
Porꢀ3), 6.47–6.45 (trans; dd, J ¼ 2:0 Hz, 4H ꢃ 4/5, CH=CH),
1
a) D. Holten, D. F. Bocian, and J. S. Lindsey, Acc. Chem.
6.400 (cis; br.t, J ¼ 6:0 Hz, 4H ꢃ 1/5, CH=CH), 5.41–5.40 (trans
Res., 35, 57 (2002). b) H. L. Anderson, Chem. Commun., 1999,
2323. c) N. Aratani and A. Osuka, Bull. Chem. Soc. Jpn., 74,
1361 (2001). d) P. D. Harvey, ‘‘The Porphyrin Handbook,’’ ed
by K. M. Kadish, K. M. Smith, and R. Guilard, Elsevier Science
(2003), Vol. 18, pp. 63–250. e) K. Ogawa and Y. Kobuke, ‘‘Self-
Assembled Porphyrin Arrays,’’ in ‘‘Encyclopedia of Nanoscience
and Nanotechnology,’’ ed by H. S. Nalwa, to be published in
2003, American Scientific Pub.
ꢀ
& cis; m, 8H, ester ꢀ), 5.44 (trans; d, J ¼ 4:2 Hz, 4H ꢃ 4/5,
Porꢀ4), 5.42 (trans & cis; s, 2H, Im H5), 5.370 (cis; d, J ¼ 4:2
Hz, 4H ꢃ 1/5, Porꢀ4), 5.200 (cis; dd, J ¼ 6:0, 12 Hz, 4H ꢃ 1/5,
–OCH2), 5.100 (cis; dd, J ¼ 6:0, 12 Hz, 4H ꢃ 1/5, –OCH2),
ꢀ
ꢀ
5.07 (trans; d, J ¼ 10:2 Hz, 4H ꢃ 4/5, –OCH2), 5.00 (trans;
d, J ¼ 10:2 Hz, 4H ꢃ 4/5, –OCH2), 4.10–4.020 (cis; m, 4H ꢃ
1/5, ester ꢃ), 3.82–3.750 (cis; m, 4H ꢃ 1/5, ester ꢃ), 3.89–3.80
ꢀ
ꢀ
(trans; m, 4H ꢃ 4/5, ester ꢃ), 3.73–3.60 (trans; m, 4H ꢃ 4/5, es-
ter ꢃ), 2.00 (trans & cis; br, 2H, Im H4), 1.68 (trans & cis; s, 6H,
NCH3), 0.74 (trans & cis; s, 18H, TMS); 13C NMR (150 MHz,
2
a) Y. Kobuke and H. Miyaji, J. Am. Chem. Soc., 116, 4111
(1994). b) K. Ogawa and Y. Kobuke, Angew. Chem., Int. Ed., 39,
4070 (2000). c) Y. Kobuke and K. Ogawa, Bull. Chem. Soc. Jpn.,
76, 689 (2003).
CDCl3) ꢂ 172.80 (C=O; cis), 172.3 (C=O; trans), 152.30 (Porꢃ;
ꢀ
cis), 152.1 (Porꢃ; trans), 150.4 (Porꢃ; trans), 150.30 (Porꢃ;
3
a) K. Ogawa, T. Zhang, K. Yoshihara, and Y. Kobuke, J.
ꢀ
ꢀ
cis), 149.90 (Porꢃ; cis), 149.8 (Porꢃ; trans), 147.6 (Porꢃ; trans),
Am. Chem. Soc., 124, 22 (2002). Other systems based on porphyrin
wires are also reported: b) S. M. Kuebler, R. G. Denning, and H. L.
Anderson, J. Am. Chem. Soc., 122, 339 (2000). c) T. E. O. Screen,
J. R. G. Thorne, R. G. Denning, D. G. Bucknall, and H. L.
Anderson, J. Am. Chem. Soc., 124, 9712 (2002).
ꢀ
ꢀ
147.50 (Porꢃ; cis), 145.4 (Im N=C–N), 132.0 (Porꢀ1), 130.8
(CH=CH; trans), 129.80 (CH=CH; cis), 129.0 (Porꢀ2), 128.6
ꢀ
ꢀ
(Porꢀ3; trans), 128.50 (Porꢀ3; cis), 127.8 (Porꢀ4), 121.9 (Im
ꢀ
CH), 118.2 (Im CH), 109.0 (meso), 100.6 (meso), 99.9 (meso;
trans), 99.80 (meso; cis), 98.8 (meso), 63.4 (–OCH2; trans),
ꢀ
4
(2003).
5
R. Takahashi and Y. Kobuke, J. Am. Chem. Soc., 125, 2372
59.00 (–OCH2; cis), 43.2 (ester ꢃ), 32.8 (NCH3), 31.4 (ester ꢀ),
29.8 (TMS–CꢅC–), 0.7 (TMS); UV–vis (CHCl3): 425 (Abs.;
0.0930), 445 (01505), 579 (0.0153), 637 (0.0253) nm; Fluores-
cence (Ex = 425 nm, CHCl3): 640, 698 nm; MALDI-TOF Mass
of C78H72N12O8Si2Zn2 Calcd: 1488.4; Found: 1489.1 (M + H)þ.
Covalently Linked Dimer 7f: In a similar manner as for the
preparation of 7a, the covalent linking of D-5f (20 mg, 28 mmol)
was carried out to give 7f (20 mg, quant). 1H NMR (600 MHz,
CDCl3) ꢂ 9.58–9.52 (m, J ¼ 4:3, others Hz, 2H, Porꢀ1), 9.09 (d,
J ¼ 4:3 Hz, 2H ꢃ 1/8, Porꢀ2), 9.06 (d, J ¼ 4:3 Hz, 2H ꢃ 6/8,
Porꢀ2), 9.03–8.99 (m, 2H, Porꢀ3 + 2H ꢃ 1/8, Porꢀ2), 8.73–
8.67 (m, 1H, o-Ph), 8.12 (d, J ¼ 7:2 Hz, 1H ꢃ 1/4, o-Ph), 8.09
(d, J ¼ 6:6 Hz, 1H ꢃ 3/4, o-Ph), 7.94 (t, J ¼ 7:2 Hz, 1H, m-
Ph), 7.85 (t, J ¼ 7:2 Hz, 1H, m-Ph), 7.78–7.72 (m, 1H, p-Ph),
6.44 (m, 2H ꢃ 7/8, CH=CH), 6.10 (m, 2H ꢃ 1/8, CH=CH),
5.51 (d, J ¼ 1:1 Hz, 1H ꢃ 1/4, Im H4), 5.50 (d, J ¼ 1:1 Hz, 1H
ꢃ 3/4, Im H5), 5.47 (d, J ¼ 4:3 Hz, 2H ꢃ 1/4, Porꢀ4), 5.44 (d, J ¼
4:3 Hz, 2H ꢃ 3/4, Porꢀ4), 5.43–5.36 (m, 2H ꢃ 3/4, ꢃCH2), 5.25–
5.17 (m, 2H ꢃ 1/4, ꢃCH2), 5.16–5.07 (m, 2H, ꢃCH2), 4.67 (m, 4H
ꢃ 1/8, –CH2–CH=CH–), 4.46–4.38 (m, 4H ꢃ 7/8, –CH2–
a) A. Nomoto and Y. Kobuke, Chem. Commun., 2002,
1104. b) A. Nomoto, H. Mitsuoka, H. Ozeki, and Y. Kobuke,
Chem. Commun., 2003, 1074.
6 Review: T. M. Trnka and R. H. Grubbs, Acc. Chem. Res.,
34, 18 (2001).
7 Supplied from Molecular Simulation Inc. Version 4.6 and
‘‘Universal’’ parameters were used.
8
(1991).
9
J. Otera, N. Danoh, and H. Nozaki, J. Org. Chem., 56, 5307
a) C. W. Lee and R. H. Grubbs, Org. Lett., 2, 2145 (2000).
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10 A. J. Phillips and A. D. Abell, Aldrichimica Acta, 32, 75
(1999).
11 P. M. Gannett, D. L. Nagel, P. J. Reilly, T. Lawson, J.
Sharpe, and B. Toth, J. Org. Chem., 53, 1064 (1988).
12 R. W. Hoffmann and I. Muenster, Liebigs Ann. Recl., 1997,
1143.