Facile synthesis and photophysical properties of 1,2-phenylene-bridged porphyrin dimers

Article abstract of DOI:10.1016/j.tetlet.2009.02.081

Facile synthesis of 1,2-phenylene-bridged porphyrin dimers via Pd-catalyzed cross-coupling reaction and their photophysical properties only moderately perturbed by inter-porphyrin electronic interactions are reported.

Full text of DOI:10.1016/j.tetlet.2009.02.081

Tetrahedron Letters 50 (2009) 3333–3337
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Facile synthesis and photophysical properties of 1,2-phenylene-bridged
porphyrin dimers
*
*
Kenta Osawa, Naoki Aratani , Atsuhiro Osuka
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Facile synthesis of 1,2-phenylene-bridged porphyrin dimers via Pd-catalyzed cross-coupling reaction and
their photophysical properties only moderately perturbed by inter-porphyrin electronic interactions are
reported.
Received 14 January 2009
Revised 6 February 2009
Accepted 12 February 2009
Available online 15 February 2009
Ó 2009 Elsevier Ltd. All rights reserved.
Keywords:
Cross coupling
Exciton coupling
Porphyrinoid
Oligomers
The design and construction of new electronically interacting
porphyrin oligomers have been pursued because of their potential
applications for near-infrared dyes, nonlinear optical (NLO) mate-
rials, molecular devices, and so on.1 Among these, aromatic-
spacer-bridged porphyrin arrays exhibit large excitonic interac-
tions between neighboring porphyrins in spite of their relatively
simple structures.2 This feature is advantageous for large NLO
properties such as two-photon absorption (TPA) properties and
optical limiting.3 Recently, we prepared various aromatic-spacer-
bridged porphyrin dimers by Pd-catalyzed cross-coupling reac-
tions.4 When such porphyrin dimers have free-meso positions, they
can be used as building blocks for synthesis of higher oligomers.
Along this line, 1,4-phenylene- and 1,3-phenylene-bridged dimers
were iteratively coupled to form linear4a and zig-zag porphyrin ar-
rays,4b respectively. Intramolecular cyclization reactions of the lat-
ter arrays have been shown effective to construct medium and
large porphyrin rings.4b–d
Herein, we describe the synthesis, X-ray crystal structure, and
photophysical properties of 1,2-phenylene-bridged porphyrin di-
mers. Although many face-to-face porphyrin dimers have been
prepared so far, the transition metal-catalyzed cross-coupling
method has not been applied for the synthesis of 1,2-phenylene-
bridged porphyrin dimer.5 It is noteworthy that the X-ray crystal
structures of 1,2-phenylene-bridged porphyrin dimers are very
rare, and only a couple of crystal structures have been reported
before.5b,d
We envisioned a synthetic route toward the 1,2-phenylene-
bridged porphyrin as illustrated in Scheme 1. 5,15-Diaryl-10
-boronylporphyrin 1a was prepared from 5,15-bis(3,5-dioctyloxy-
phenyl)porphyrin by NBS bromination, zinc insertion, and Pd-cat-
alyzed borylation in a three-step yield of 74%.6 A coupling reaction
of 1a and 1,2-diiodobenzene was performed with Pd2(dba)3, trifu-
rylphosphine, CsF, and Cs2CO3 in a mixture of THF/DMF/H2O (v/v/
v = 2:1:0.1) at 90 °C for 3 h. Sequential separation by gel perme-
ation chromatography (GPC) and silica gel column chromatogra-
phy gave the desired 1,2-phenylene-bridged dimer 2a in 5%
yield.7 In this reaction, benzene-fused porphyrin 4a (54%) and
meso–meso-linked porphyrin dimer 3a (5%) were formed along
with deborylated porphyrin 5a. The formation of the ring fusion
product was previously reported in the similar systems, and the
spectroscopic data of 4a are fully consistent with its structure.8,9
In order to suppress the fusion reaction, we examined various
reaction conditions using 1b as a substrate and finally found that
the yield of 2b was much improved (40%) with suppression of for-
mation of 4b under strongly basic conditions (Pd(PPh3)4, Ba(OH)2,
toluene, and H2O).9–11 Electrospray ionization time-of-flight (ESI-
TOF) mass spectra of 1,2-phenylene-bridged porphyrin dimers
showed the parent ion peaks of m/z 2152.1800 for 2a (calcd for
(C134H170N8O8Zn2)+ = 2152.1805) and m/z 1574.7089 for 2b (calcd
for (C102H106N8Zn2)+ = 1574.7109), respectively.
The 1H NMR spectrum of 2b in CDCl3 at room temperature
shows broad peaks in the aromatic region (Fig. 1a), whereas the
sharp peaks for 2b are observed in THF-d8 (Fig. 1b). In the latter
spectrum, four doublet peaks observed at 9.56, 8.92, 8.60, and
* Corresponding authors. Tel.: +81 75 753 4007; fax: +81 75 753 3970 (N.A.); tel.:
+81 75 753 4008; fax: +81 75 753 3970 (A.O.).
E-mail addresses: aratani@kuchem.kyoto-u.ac.jp (N. Aratani), osuka@kuchem.
kyoto-u.ac.jp (A. Osuka).
0040-4039/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2009.02.081

3334
K. Osawa et al. / Tetrahedron Letters 50 (2009) 3333–3337
8.57 ppm have been assigned to the porphyrin b protons. A singlet
peak at 9.67 ppm and a set of mutually coupled multiplet peaks at
8.63 and 8.16 ppm have been assigned to the meso-protons and
1,2-phenylene protons, respectively. The signals for aryl groups
are observed as four peaks at 7.81, 7.65, 7.53, and 7.48 ppm, indi-
cating the discrimination of inside and outside of two porphyrin
planes and the rotational restriction of aryl groups at room temper-
ature. These spectral data suggest that the two porphyrin rings in
Ar
Ar
Ar
Ar
N
Zn
N
N
N
N
N
N
N
N
N
I
I
a or b
+
Ar
pinB
Zn
+
Zn
Zn
N
N
N
N
N
N
N
N
Zn
(0.5 eq.)
N
Ar
Ar
Ar
N
3a
Ar
Ar
Ar
1a: Ar = 3,5-dioctyloxyphenyl
1b: Ar = 4-octylphenyl
1c: Ar = 4-tert-butylphenyl
2a
2b
2c
N
N
N
N
Zn
+
+
Zn
N
N
N
N
O
O
Bpin =
B
Ar
4a
4b
Ar
5a
5b
Scheme 1. Suzuki–Miyaura cross-coupling reaction of 1. Reagents: (a) Pd2(dba)3, Cs2CO3, CsF, trifurylphosphine, THF, DMF, and H2O; (b) Pd(PPh3)4, Ba(OH)2, toluene, and
H2O.
*
*
*
β
β
β
β
meso
Ar
Ar Ar Ar
Ph
Ph
10
9.5
9
8.5
8
7.5
7
δ
/ ppm
Figure 1. 1H NMR spectra of 2b at room temperature (a) in CDCl3 and (b) in THF-d8.
Figure 2. X-ray crystal structure of 1,2-phenylene-bridged porphyrin dimer 2cÁ(thf)2. (a) Top view and (b) side view. The thermal ellipsoids are scaled to the 50% probability
level. tert-Butyl groups, a solvent molecule, and hydrogen atoms are omitted for clarity. Coordinating molecules at side view are also omitted for clarity.

K. Osawa et al. / Tetrahedron Letters 50 (2009) 3333–3337
3335
2b tend to be stacked seriously in non-coordinating solvents but be
dissociated in coordinating ones.
6.0
5.0
4.0
3.0
2.0
1.0
0.0
To obtain the structural information, 5,15-bis(4-tert-butyl-
phenyl)porphyrin dimer 2c was prepared from 1c in the same
manner.11 The single crystals of 2c suitable for X-ray diffraction
analysis were grown by vapor slow diffusion of acetonitrile into
THF solution.12 The X-ray structure shows that the two porphyrin
rings are connected by a 1,2-phenylene-bridge to form a pac-man
conformation with a dihedral angle between two porphyrin planes
of 66.9° (Fig. 2). This is largely different from the b-octaalkyl por-
phyrin 6 that shows a parallel face-to-face structure (dihedral an-
gle is only 6.6°).5b The center-to-center distance between zinc
atoms of 2c is 7.0 Å and still this close proximity is quite favorable
for the efficient EEH, and actually the rapid state-to-state energy
transfer rates have been observed for such systems.2a The porphy-
rin rings exhibit planar structures with some mean plane devia-
tions (0.08–0.13 Å) for each of the 25 core atoms. Two THF
molecules are coordinated with the central zinc(II) ions at the inte-
rior side, which contributes to increments in both the mean plane
deviation of porphyrin rings and dihedral angle between porphyrin
planes. The X-ray crystal structure of 1c suggests the potential use
of 1,2-phenylene-bridged diporphyrins as a host for preferential
guest binding at the interior side.
2b in THF
2b in CH Cl
2
2
5b in THF
6 in THF
ε
300 350 400 450 500 550 600 650 700
Wavelength / nm
in THF
in CH Cl
2
2
N
Zn
N
N
N
N
Zn
N
N
N
6
This synthetic method allows the stepwise preparation of a
mono-metallated hybrid 1,2-phenylene porphyrin dimer in a pre-
dictable manner.2 meso-Bromoporphyrin 7 was reacted with an ex-
cess amount of 1,2-diboronylbenzene that was prepared from 1,2-
diiodobenzene by Ni-catalyzed borylation reaction.13 From this
reaction mixture, a borylated product was separated and metallat-
ed with Zn(OAc)2 to give 8, which was again coupled with 7 under
the same conditions, to furnish hybrid porphyrin dimer 9 (12% in
three steps) (Scheme 2).14
500
550
600
650
700
750
800
Wavelength / nm
Figure 3. (a) UV–vis absorption and (b) fluorescence spectra (excited at Soret band)
of 2b in CH2Cl2 and in THF. Red and blue lines in Figure 3a show UV–vis absorption
spectrum of 5b and 6 in THF, respectively.
in CH2Cl2 as compared with that in THF (Fig. 3b). These observa-
tions again indicate more stacking interactions of the two porphy-
rin rings in non-coordinating solvents.
Figure 4a shows the UV–vis absorption spectrum of 9, along
with that of its bis-zinc complex. The steady-state fluorescence
spectra are shown in Figure 4b. Upon photoexcitation at around
410 nm, 9 exhibits the fluorescence predominantly from the free
base porphyrin moiety, indicating the effective excitation energy
transfer.
The UV–vis absorption spectrum of 2b in THF shows a broader
and slightly but distinctly blue-shifted Soret band (409 nm;
FWHM = 1052 cmÀ1
)
relative to that of 5b (413 nm;
FWHM = 675 cmÀ1), while it is narrower than that of 6 (402 nm;
FWHM = 1392 cmÀ1), indicating that the strength of exciton cou-
pling of 2b is distinctly weaker than that of 6 (Fig. 3a). The fluores-
cence spectrum of 2b shows a considerable decrease in its intensity
Ar
Ar
Ar
N
Bpin
NH
HN
NH
N
N
N
Bpin
N
a
b
7
Br
+
Zn
+
Ar
Bpin
HN
N
N
N
N
N
(5 eq.)
(1 eq.)
Zn
N
Ar
Ar
N
Ar
7
8
9
Ar = 4-dodecyloxyphenyl
Scheme 2. Stepwise cross-coupling reaction. Reagents: (a) (i) Pd2(dba)3, Cs2CO3, CsF, trifurylphosphine, toluene, and DMF, then (ii) Zn(OAc)2Á2H2O; (b) Pd2(dba)3, Cs2CO3, CsF,
trifurylphosphine, THF, DMF, and H2O.

3336
K. Osawa et al. / Tetrahedron Letters 50 (2009) 3333–3337
In summary, we have demonstrated the facile synthetic proto-
col of 1,2-phenylene-bridged porphyrin dimers via Suzuki–Miya-
ura reaction. These stacked -conjugated structures lead to
strong intramolecular electronic interactions that depend on sol-
vent. Further fabrications of these arrays are subjects of further
investigation.
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
p
mono-Zn complex 9
bis-Zn complex
Acknowledgments
This work was partially supported by Grants-in-Aid for Scien-
tific Research (No. 19205006, and 20108001 ‘pi-Space’) from the
Ministry of Education, Culture, Sports, Science and Technology, Ja-
pan. N.A. thanks a Grant-in-Aid for Young Scientists (B) and GCOE
program ‘Integrated Materials Science’ for financial support.
ε
x 5
References and notes
300 350 400 450 500 550 600 650 700
Wavelength / nm
1. (a) Wasielewski, M. R. Chem. Rev. 1992, 92, 435–461; (b) Gust, D.; Moore, T. A.;
Moore, A. L. Acc. Chem. Res. 2001, 34, 40–48; (c) Holten, D.; Bocian, D. F.;
Lindsey, J. S. Acc. Chem. Res. 2002, 35, 57–69; (d) Aratani, N.; Osuka, A. Bull.
Chem. Soc. Jpn. 2001, 74, 1361–1379; (e) Yeow, E. K. L.; Ghiggino, K. P.; Reek, J.
N. H.; Crossley, M. J.; Bosman, A. W.; Schenning, A. P. H. J.; Meijer, E. W. J. Phys.
Chem. B 2000, 104, 2596–2606; (f) Choi, M.-S.; Aida, T.; Yamazaki, T.; Yamazaki,
I. Chem. Eur. J. 2002, 8, 2668–2678.
2. (a) Cho, H. S.; Jeong, D. H.; Yoon, M.-C.; Kim, Y. H.; Kim, Y.-R.; Kim, D.; Jeoung, S.
C.; Kim, S. K.; Aratani, N.; Shinmori, H.; Osuka, A. J. Phys. Chem. A 2001, 105,
4200–4210; (b) Cho, S.; Yoon, M.-C.; Kim, C. H.; Aratani, N.; Mori, G.; Joo, T.;
Osuka, A.; Kim, D. J. Phys. Chem. C 2007, 111, 14881–14888.
mono-Zn complex 9
bis-Zn complex
3. (a) Senge, M. O.; Fazekas, M.; Notaras, E. G. A.; Blau, W. J.; Zawadzka, M.; Locos,
O. B.; Ni Mhuircheartaigh, E. M. Adv. Mater. 2007, 19, 2737–2774; (b) Song, J.;
Jang, S. Y.; Yamaguchi, S.; Sankar, J.; Hiroto, S.; Aratani, N.; Shin, J.-Y.;
Easwaramoorthi, S.; Kim, K. S.; Kim, D.; Shinokubo, H.; Osuka, A. Angew. Chem.,
Int. Ed. 2008, 47, 6004–6007.
4. (a) Peng, X.; Nakamura, Y.; Aratani, N.; Kim, D.; Osuka, A. Tetrahedron Lett. 2004,
45, 4981–4984; (b) Peng, X.; Aratani, N.; Takagi, A.; Matsumoto, T.; Kawai, T.;
Hwang, I.-W.; Ahn, T. K.; Kim, D.; Osuka, A. J. Am. Chem. Soc. 2004, 126, 4468–
4469; (c) Hori, T.; Aratani, N.; Takagi, A.; Matsumoto, T.; Kawai, T.; Yoon, M.-C.;
Yoon, Z. S.; Cho, S.; Kim, D.; Osuka, A. Chem. Eur. J. 2006, 12, 1319–1327; (d) Hori,
T.; Peng, X.; Aratani, N.; Takagi, A.; Matsumoto, T.; Kawai, T.; Yoon, Z. S.; Yoon,
M.-C.; Yang, J.; Kim, D.; Osuka, A. Chem. Eur. J. 2008, 14, 582–595.
5. 1,2-Phenylene-bridged porphyrin dimers have been mainly synthesized by
stepwise acid-catalyzed cyclization reactions; (a) Meier, H.; Kobuke, Y.;
Kugimiya, S. J. Chem. Soc. Chem. Commun. 1989, 923–924; (b) Osuka, A.;
Nakajima, S.; Nagata, T.; Maruyama, K.; Toriumi, K. Angew. Chem., Int. Ed. Engl.
1991, 30, 582–584; (c) Naruta, Y.; Sasayama, M.-a.; Sasaki, T. Angew. Chem., Int.
Ed. Engl. 1994, 33, 1839–1841. Therien et al. have prepared it by the cobalt-
mediated alkyne trimerization reaction; (d) Fletcher, J. T.; Therien, M. J. J. Am.
Chem. Soc. 2000, 122, 12393–12394.
500
550
600
650
700
750
800
Wavelength / nm
Figure 4. (a) UV–vis absorption and (b) fluorescence spectra (excited at Soret band)
of 9 and its bis-zinc complex in CHCl3.
6. Hyslop, A. G.; Kellett, M. A.; Iovine, P. M.; Therien, M. J. J. Am. Chem. Soc. 1998,
120, 12676–12677.
7. Compound 2a: 1H NMR (600 MHz, CDCl3) d 9.70 (br, 2H, meso), 9.39 (d,
J = 5.0 Hz, 4H, b), 8.92 (br, 4H, b), 8.86 (m, 2H, Ph), 8.70 (d, J = 5.0 Hz, 4H, b), 8.54
(d, J = 5.0 Hz, 4H, b), 8.29 (m, 2H, Ph), 6.96 (br, 4H, Ar), 6.77 (br, 4H, Ar), 6.61 (br,
4H, Ar), 3.97 (t, J = 6.6 Hz, 8H, C8H17), 3.81 (m, 8H, C8H17), 1.78 (m, 16H, C8H17),
1.45–1.13 (m, 80H, C8H17), 0.96 (t, J = 6.6 Hz, 12H, C8H17), and 0.83 (t, J = 6.6 Hz,
N
Zn
N
Ar
N
Ar
Ar
N
N
Zn
Ar
N
N
12H, C8H17
) ppm; ESI-TOF MS: m/z 2152.1800, calcd for C134H170
N
N
N
N
N
N
N
N
N
N8O8Zn2 = 2152.1805; UV–vis (CH2Cl2): kmax = 407, and 550 nm, (THF): 412,
and 556 nm; Fluorescence (CH2Cl2, kex = 407 nm) kem = 598 and 649 nm, (THF,
kex = 412 nm) kem = 601 and 652 nm. Compound 4a: 1H NMR (600 MHz, CDCl3)
d 9.64 (s, 1H, meso), 9.11 (d, J = 5.0 Hz, 1H, b), 8.98 (d, J = 5.0 Hz, 1H, b), 8.89 (d,
J = 5.0 Hz, 1H, b), 8.83 (d, J = 5.0 Hz, 1H, b), 8.76 (d, J = 5.0 Hz, 1H, b), 8.75 (d,
J = 5.0 Hz, 1H, b), 8.05 (s, 1H, b), 7.93 (d, J = 7.2 Hz, 1H, Ph), 7.40 (d, J = 2.2 Hz,
1H, Ar), 7.40 (d, J = 2.2 Hz, 1H, Ar), 7.25 (d, J = 7.2 Hz, 1H, Ph), 6.89 (d, J = 7.2 Hz,
1H, Ph), 6.85 (d, J = 2.2 Hz, 2H, Ar), 6.84 (d, J = 2.2 Hz, 2H, Ar), 6.81 (d, J = 7.2 Hz,
1H, Ph), 4.13 (m, 8H, C8H17), 1.83 (m, 8H, C8H17), 1.49–1.27 (m, 40H, C8H17),
and 0.87 (m, 12H, C8H17) ppm.
a
Zn
Zn
Ar
Ar
N
N
Zn
N
Zn
N
Ar
N
N
N
Ar
N
Ar
10a
2a
Scheme 3. Ag(I)-promoted oxidative coupling reaction of 2a. Reagents: (a) AgPF6,
8. (a) Fox, S.; Boyle, R. W. Chem. Commun. 2004, 1322–1323; (b) Shen, D.-M.; Liu,
C.; Chen, Q.-Y. Chem. Commun. 2005, 4982–4984.
CHCl3.
9. Bringmann, G.; Götz, D. C. G.; Gulder, T. A. M.; Gehrke, T. H.; Bruhn, T.; Kupfer,
T.; Radacki, K.; Braunschweig, H.; Heckmann, A.; Lambert, C. J. Am. Chem. Soc.
2008, 130, 17812–17825.
One of the key advantages of this synthetic strategy is that the
coupling products still bear two free meso-positions that are avail-
able for next reaction. Then we have tested the Ag(I)-promoted
oxidative coupling reaction of 2a. To a solution of 2a (0.5 mM) in
CHCl3 was added AgPF6 (1.0 equiv), and the resulting mixture
was stirred for 1.5 h at room temperature. Progress of the reaction
was monitored by MALDI-TOF mass spectroscopy. After the usual
workup, the products were separated over GPC-HPLC to give por-
phyrin tetramer 10a (13%) (Scheme 3).15
10. This is presumably due to an activation of the boron agent by intermediate
formation of a quaternary boronate anion. Miyaura, N.; Suzuki, A. Chem. Rev.
1995, 95, 2457–2483.
11. Compound 2b: 1H NMR (600 MHz, THF-d8) d 9.67 (br, 2H, meso), 9.56 (d,
J = 5.0 Hz, 4H, b), 8.92 (d, J = 5.0 Hz, 4H, b), 8.63 (m, 2H, Ph), 8.60 (d, J = 5.0 Hz,
4H, b), 8.57 (d, J = 5.0 Hz, 4H, b), 8.16 (m, 2H, Ph), 7.81 (dd, J = 7.3 Hz, 1.5 Hz,
4H, Ar), 7.65 (dd, J = 7.3 Hz, 1.5 Hz, 4H, Ar), 7.53 (dd, J = 7.3 Hz, 1.5 Hz, 4H, Ar),
7.48 (dd, J = 7.3 Hz, 1.5 Hz, 4H, Ar), 2.97 (t, J = 8.2 Hz, 8H, C8H17), 1.97 (tt,
J = 8.2 Hz, 8.2 Hz, 8H, C8H17), 1.64–1.41 (m, 40H, C8H17), and 0.97 (t, J = 8.3 Hz,
12H, C8H17
)
ppm; ESI-TOF MS m/z 1574.7089, calcd for C102H106

K. Osawa et al. / Tetrahedron Letters 50 (2009) 3333–3337
3337
N8Zn2 = 1574.7109; UV–Vis (CH2Cl2): kmax = 404, and 552 nm, (THF): 409, and
555 nm; Fluorescence (CH2Cl2, kex = 404 nm) kem = 608 and 653 nm, (THF,
kex = 409 nm) kem = 605 and 657 nm.
monitored by analytical GPC–HPLC. After stirring for 1.5 h at room
temperature, the mixture was diluted with water, and the porphyrin
products were extracted with CHCl3. The organic extract was washed with
water and dried over Na2SO4. After evaporation, the residue was dissolved with
CHCl3 and metallated with Zn(OAc)2Á2H2O. The desired compound was
separated over a recycling preparative GPC–HPLC to give 10a (4.0 mg, 13%).
1H NMR (CDCl3) d 9.74 (s, 2H, meso), 9.49 (d, J = 5.0 Hz, 2H, b), 9.43 (d,
J = 5.0 Hz, 2H, b), 9.39 (d, J = 5.0 Hz, 2H, b), 9.31 (d, J = 5.0 Hz, 2H, b), 8.97 (d,
J = 5.0 Hz, 2H, b), 8.93 (d, J = 5.0 Hz, 2H, b), 8.85 (m, 2H, Ph), 8.81 (d, J = 5.0 Hz,
2H, b), 8.80 (m, 2H, Ph), 8.72 (d, J = 5.0 Hz, 2H, b), 8.69 (d, J = 5.0 Hz, 2H, b), 8.58
(d, J = 5.0 Hz, 2H, b), 8.48 (d, J = 5.0 Hz, 2H, b), 8.33 (d, J = 5.0 Hz, 2H, b), 8.26 (m,
4H, Ph), 8.14 (d, J = 5.0 Hz, 2H, b), 7.83 (d, J = 5.0 Hz, 2H, b), 7.29 (d, J = 5.0 Hz,
2H, b), 7.00 (br, 2H, Ar), 6.93 (d, J = 5.0 Hz, 2H, b), 6.92 (br, 2H, Ar), 6.91 (br, 2H,
Ar), 6.87 (br, 2H, Ar), 6.78 (br, 2H, Ar), 6.77 (br, 2H, Ar), 6.68 (br, 2H, Ar), 6.60
(br, 2H, Ar), 6.59 (br, 2H, Ar), 6.58 (br, 2H, Ar), 6.53 (br, 2H, Ar), 6.29 (br, 2H, Ar),
4.00 (t, J = 6.6 Hz, 4H, C8H17), 3.97 (t, J = 6.6 Hz, 4H, C8H17), 3.81 (m, 8H, C8H17),
3.75–3.50 (m, 16H, C8H17), 1.70–0.65 (m, 216H, C8H17), 0.55 (m, 12H, C8H17),
12. Crystallographic data for 2c: C98H98N8O3Zn2, Mw = 1566.58, triclinic, space
group P-1 (No. 2), a = 14.651(3), b = 16.764(3), c = 18.008(5) Å,
b = 82.440(8),
= 65.107(7)°, V = 3976.4(15) Å3, Dc = 1.308 g/cm3, Z = 2,
R1 = 0.0657 (I > 2 (I)), Rw (all data) = 0.1722, GOF = 1.038. CCDC 714770.
a = 85.704(8),
c
r
13. Morgan, A. B.; Jurs, J. L.; Tour, J. M. J. Appl. Polym. Sci. 2000, 76, 1257–1268.
14. Compound 9: 1H NMR (600 MHz, THF-d8) d 9.67 (s, 1H, meso), 9.56 (s, 1H,
meso), 9.53 (d, J = 5.0 Hz, 2H, b), 9.41 (d, J = 5.0 Hz, 2H, b), 8.89 (d, J = 5.0 Hz, 2H,
b), 8.84 (d, J = 5.0 Hz, 2H, b), 8.76 (m, 1H, Ph), 8.71 (m, 1H, Ph), 8.57–8.54 (m,
8H, b), 8.25 (m, 2H, Ph), 7.80 (m, 4H, Ar), 7.60 (d, J = 8.0 Hz, 2H, Ar), 7.50 (d,
J = 8.0 Hz, 2H, Ar), 7.33 (d, J = 8.0 Hz, 2H, Ar), 7.25–7.21 (m, 6H, Ar), 4.30 (m, 8H,
C12H25), 2.02 (m, 8H, C12H25), 1.60–1.25 (m, 72H, C12H25), 0.92 (m, 12H,
C12H25), and À4.03 (s, 2H, NH) ppm; ESI-TOF MS: m/z 1799.0310, calcd for
C118H1141N8O4Zn = 1799.0394; UV–vis (CHCl3): kmax = 408, 521, 555, and
594 nm; Fluorescence (CHCl3, kex = 407 nm) kem = 656 and 718 nm.
15. Compound 2a (32 mg, 0.015 mmol) was dissolved in CHCl3 (30 mL), and the
reaction vessel was covered with foil. To the solution was added a solution of
0.12 M AgPF6 in CH3CN (0.015 mmol) all at once, and progress of reaction was
and 0.45 (m, 12H, C8H17) ppm; MALDI-TOF MS m/z 4300.1, calcd for
C268H338N16O16Zn4 = 4301.3; UV–vis (THF): kmax = 415, 481, and 572 nm;
Fluorescence (THF, kex = 415 nm) kem = 640 nm.