An electron-deficient porphyrin tape

Article abstract of DOI:10.1002/asia.201200247

Hexakis(pentafluorophenyl)-substituted meso-meso-linked Zn ^II-diporphyrin (9), which was prepared by the acid-catalyzed cross-condensation of 1,1,2,2-tetrapyrroethane (5) with dipyrromethane dicarbinol (6), was converted into meso-meso,β-β,β-β triply linked Zn^II-diporphyrin 3 by oxidation with 2,3-dichloro-5,6- dicyanobenzoquinone (DDQ) and Sc(OTf)₃. Beside the red-shifted absorption spectrum and split first oxidation potential that are common to the triply-linked Zn^II-diporphyrins, diporphyrin 3 exhibited considerably improved chemical stability owing to a lowered HOMO and good solubility in common organic solvents. The two-photon absorption (TPA) cross-section and S₁-state lifetime of compound 3 were 1700 GM and 3.3 ps, respectively.

Full text of DOI:10.1002/asia.201200247

DOI: 10.1002/asia.201200247
An Electron-Deficient Porphyrin Tape
Hirotaka Mori,[a] Takayuki Tanaka,[a] Naoki Aratani,[a, c] Byung Sun Lee,[b]
Pyosang Kim,[b] Dongho Kim,*[b] and Atsuhiro Osuka*[a]
Abstract: Hexakis(pentafluorophenyl)-
substituted meso–meso-linked ZnII–di-
porphyrin (9), which was prepared by
the acid-catalyzed cross-condensation
of 1,1,2,2-tetrapyrroethane (5) with di-
pyrromethane dicarbinol (6), was con-
verted into meso–meso,b-b,b-b triply
linked ZnII–diporphyrin 3 by oxidation
with 2,3-dichloro-5,6-dicyanobenzoqui-
none (DDQ) and Sc
G
porphyrins, diporphyrin 3 exhibited
red-shifted absorption spectrum and
split first oxidation potential that are
common to the triply-linked ZnII–di-
considerably improved chemical stabili-
ty owing to a lowered HOMO and
good solubility in common organic sol-
vents. The two-photon absorption
(TPA) cross-section and S1-state life-
time of compound 3 were 1700 GM
and 3.3 ps, respectively.
Keywords: conjugation
voltammetry · dimer · electron-defi-
cient compounds · porphyrinoids
Introduction
due to their high-lying HOMOs. Recently, by combining
electron-rich- and electron-poor porphyrins, we have devel-
oped hybrid porphyrin tapes with improved solubility and
chemical stability compared with their parent porphyrin
tapes.[10] As an extension of this strategy, herein we report
the synthesis and characterization of an electron-deficient
triply linked porphyrin tape (3) that consists of only penta-
fluorophenyl-substituted ZnII–porphyrin units (Scheme 1).
This structure was used to examine the influence of the elec-
tron-deficient substituents on the stability, solubility, and
electronic properties of porphyrin tapes.
Extensive efforts have been devoted to the exploration of p-
conjugated porphyrins owing to their potential use in vari-
ous applications, such as organic semiconductors, photody-
namic therapy (PDT), nonlinear optics (NLO), and photo-
voltaics.[1–3] Among these, we have developed meso–meso,b-
b,b-b triply linked porphyrin arrays (porphyrin tapes) that
exhibited exceptionally red-shifted absorption bands as
a consequence of extensive p-conjugation.[4] Several variants
of these porphyrin tapes have also been created with unique
attributes, such as 2D-extended L- and T-shaped tapes,[5]
self-organized amphiphilic columnar liquid crystals,[6] cova-
lently linked C60-conjugates,[7] C60-binding hosts,[8] and
a square-shaped porphyrin sheet.[9] Despite these develop-
ments, porphyrin tapes still face serious drawbacks, such as
poor solubility and facile oxidative degradation. The former
arises from their flat molecular shapes whilst the latter is
[a] H. Mori, Dr. T. Tanaka, Dr. N. Aratani, Prof. Dr. A. Osuka
Department of Chemistry
Graduate School of Science, Kyoto University
Sakyo-ku, Kyoto 606-8502 (Japan)
Fax : (+81)75-753-3970
Scheme 1. Structures of meso--meso,b-b,b-b triply linked diporphyrins 1–
3.
E-mail: osuka@kuchem.kyoto-u.ac.jp
[b] B. S. Lee, P. Kim, Prof. Dr. D. Kim
Spectroscopy Laboratory for Functional
p-Electronic Systems and Department of Chemistry
Yonsei University
Results and Discussion
Typically, meso–meso-linked porphyrin precursors have
been prepared by AgI-promoted oxidative-coupling reac-
tions.[11] Because this oxidative coupling should be unfavora-
ble for electron-deficient pentafluorophenyl-substituted por-
phyrin substrates, we adopted a different approach to meso–
meso-linked diporphyrin 8, that is, the cross-condensation of
1,1,2,2-tetrapyrroethane (5) with dipyrromethane dicarbinol
(6, Scheme 2). The formation of compound 5 was originally
Seoul 120-749 (Korea)
Fax : (+82)2-364-7050
E-mail: dongho@yonsei.ac.kr
[c] Dr. N. Aratani
PRESTO
Japan Science and Technology Agency (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201200247.
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75.5 and 77.98, respectively. With porphyrin 7 in hand, we
examined the oxidative coupling of its ZnII complex (7-Zn)
under various conditions. As expected, the inertness of com-
plex 7-Zn toward oxidative coupling was confirmed by the
recovery of the monomer, even after oxidations with AgPF6
or DDQ and Sc
Diporphyrin 8 was metalated with Zn
quantitatively afford ZnII–diporphyrin 9, which was then
oxidized with DDQ and Sc(OTf)3 to furnish triply linked di-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
1
porphyrin 3 in 66% yield (Scheme 3). The H NMR spec-
Scheme 2. Synthesis of diporphyrin 8.
reported by Dolphin and co-workers as a byproduct in the
reductive synthesis of meso-unsubstituted dipyrromethane[12]
but has not been used for the synthesis of porphyrin macro-
cycles.[13] After an extensive investigation, we found that the
trifluoroacetic acid (TFA)-catalyzed condensation of 1,4-di-
oxane-2,3-diol (4) with pyrrole afforded compound 5 in
13% yield. This reaction was carried out at low temperature
because compound 5 underwent facile scrambling into tri-
pyrromethane at ambient temperature. Then, the synthesis
of diporphyrin 8 was attempted by the acid-catalyzed cross-
condensation of compound 5 with dipyrromethane dicarbi-
nol (6).[14] The use of TFA or methanesulfonic acid led to
complete scrambling of compound 5, thereby giving porphy-
rin monomer 7 as the major product with trace amounts of
compound 8. The scrambling was suppressed by the use of
p-toluenesulfonic acid monohydrate. Under these condi-
tions, the condensation of compounds 5 and 6 gave com-
pound 8 (3.7% yield), along with compound 7 (8.1% yield).
The structure of compound 8 was determined by X-ray dif-
fraction (Figure 1). The asymmetric unit contained two
Scheme 3. Synthesis of porphyrin tape 3.
trum of compound 3 showed two doublets at d=7.71 and
7.67 ppm owing to the outer peripheral b-protons and a sin-
glet at d=7.09 ppm that was due to the bay-area b-protons.
To our delight, compound 3 was quite soluble in common
organic solvents and highly stable as a solution in air. Crys-
tals of compound 3 that were suitable for XRD were ob-
tained from the slow diffusion of MeOH into a solution in
chlorobenzene. Figure 2 shows the solid-state structure of
compound 3 in which the porphyrin core was almost copla-
nar with a relatively small mean plane deviation (0.036 ꢁ).
À
dimers in which two porphyrins were held with a Cmeso Cmeso
bond distance of 1.494 and 1.514 ꢁ, and a dihedral angle of
À
À
The Cmeso Cmeso and two Cb Cb bond lengths were 1.49 and
À
1.44 ꢁ, respectively, and the Zn -Zn distance was 8.44 ꢁ.
These structural features were similar to those of previously
reported compounds 1[15] and 2,[10] but the crystal-packing
structure was unique, in that diporphyrins 3 were stacked
with an interporphyrin separation of about 6.83 ꢁ without
meaningful offset (see the Supporting Information).
Figure 3 shows the UV/Vis/NIR absorption spectra of
compounds 9, 1, and 3, along with hexakis(3,5-di-tert-butyl-
phenyl) meso–meso-linked Zn–diporphyrin 10 in CHCl3.
The absorption spectrum of compound 9 was similar to that
of compound 10, thereby exhibiting split Soret bands at 418
and 456 nm. The absorption features of compound 3 were
also similar to those of compounds 1 or 2, with three main
bands: a Soret-like band at 414 nm, a red-shifted Soret band
Figure 1. X-ray crystal structure of diporphyrin 8; only one of the two
dimer molecules is shown. Thermal ellipsoids are set at 30% probability.
Solvent molecules are omitted for clarity.
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An Electron-Deficient Porphyrin Tape
linked diporphyrins 1–3, which could be regarded as D-D,
D-A, and A-A (D: a 3,5-di-tert-butylphenyl-substituted
donor-type porphyrin, and A: a pentafluorophenyl-substitut-
ed acceptor-type porphyrin), respectively, were used to ex-
amine the effects of charge-transfer interactions on TPA
property.[10] A wavelength-scanning open-aperture Z-scan
method was used to determine TPA, with the NIR pulses
generated from an NIR optical parametric amplifier that
was pumped by a femtosecond Ti:sapphire regenerative am-
plifier system with a 130 fs pulse-width. We measured the
TPA values by photoexcitation in the wavelength range of
850–1150 nm (9) and 1400–2100 nm (3), at which the one-
photon absorption contribution was negligible (Figure 4).
Figure 2. X-ray crystal structure of 3. Thermal ellipsoids are set at 30%
probability. Solvent molecules are omitted for clarity.
Figure 4. One- (OPA) and two-photon absorption (TPA) spectra of com-
pounds 9 (top) and 3 (bottom) in CH2Cl2. TPA spectra are plotted at lex/
2.
The highest TPA values and excited-state lifetimes are listed
in Table 1. In compounds 9 and 3, the maximum TPA cross-
sections were 240 and 1700 GM, respectively; the TPA value
per porphyrin units (s2/N) of compound 3 was about seven
Table 1. TPA cross-section (s2) values and excited-state lifetimes of com-
pounds 1, 2, 3, and 9.
s2[GM]
s2/N[GM][a]
lex[nm]
ts[ps]
1
2
3
9
1900
2200
1700
240
950
1100
850
1700
1650
1700
1050
4.5
3.7
3.3
120
1.6ꢂ103
[a] TPA cross-section per porphyrin unit.
times larger than that of compound 9, thus showing that the
TPA values were strongly associated with effective p-conju-
gation. Compared with dimer 1 (D-D) and dimer 2 (D-A),
the TPA values of dimer 3 were relatively small. Seemingly,
the D-D and D-A structures were more effective at enhanc-
ing TPA than the A-A system and charge-transfer interac-
tion played some role in TPA enhancement.[17]
To explore the excited-state dynamics of triply linked por-
phyrin dimers 1–3, femtosecond transient absorption (TA)
measurements were carried out (for compound 3, see
Figure 5; for compounds 1 and 2, see the Supporting Infor-
mation). In the TA spectrum of compound 3, sharp and in-
Figure 3. UV/Vis/NIR absorption (solid) and fluorescence spectra
(dashed) of a) compounds 9 and 10, and b) compounds 1 and 3 in CHCl3.
at 559 nm, and extensively red-shifted Q-band-like bands at
945 and 1077 nm.
Extensive studies were carried out to elucidate the molec-
ular-structure–TPA-property relationship.[4b] The most im-
portant factor for the enhancement of TPA was presumably
the extension of p-electron conjugation. Another effective
factor that was proposed to enhance TPA was charge-trans-
fer interactions.[16] In this context, meso--meso,b-b,b-b triply
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Figure 6. CVs of a) compound 1 and b) compound 3 in CH2Cl2 with 0.1m
Bu4NPF6 as an electrolyte (V versus ferrocene/ferrocenium ion pair; ref-
erence electrode: Ag/AgClO4; working electrode: Pt electrode; counter
electrode: Pt wire electrode; scan rate: 0.05 VsÀ1).
Figure 5. Transient absorption spectra of triply linked porphyrin dimer 3;
inset shows the decay profiles. lpump =1050 nm; lprobe =560 and 680 nm.
tense ground-state bleach (GSB) signals were observed in
the range of 500–650 nm, which were accompanied by an ex-
cited-state absorption (ESA) band in the region of 650–
750 nm. These dynamic spectroscopic features of compound
3 were similar to those of compounds 1 and 2. The temporal
profile of compound 3 was governed by a fast recovery pro-
cess (ts =3.3 ps), which was much faster than that of singly
linked dimer 9 (ts =1.6 ns, see the Supporting Information).
It was possible to explain the ultrafast internal conversion in
terms of the energy-gap law, which meant that there was
a strong correlation between the ordering of the S1-state en-
ergies and lifetimes.[4,17]
with DDQ and ScACHTNUTRGNEUNG(OTf)3. Dimer 3 exhibited red-shifted ab-
sorption bands and a split first oxidation potential, which
are common for electron-rich porphyrin tapes. The TPA
value of compound 3 was 1700 GM, much larger than that
of the singly linked dimer 9 but slightly smaller than those
of D-D- and D-A-type tapes 1 and 2. The S1-state lifetime
of compound 3 was 3.3 ps. Dimer 3 displayed better solubili-
ty and improved chemical stability owing to its positively
shifted HOMO, which encouraged its incorporation into
more-elaborate molecular systems; work on the develop-
ment of such systems is underway in our laboratory.
The electrochemical potentials of these electron-deficient
diporphyrins were measured by cyclic voltammetry in
CH2Cl2. The CV of meso–meso-linked diporphyrin 9 showed
reversible oxidation and reduction waves (0.72, À1.48, and
À1.60 V) that were positively shifted from those of the
parent diporphyrin (0.43, 0.32, and À1.89 V; see the Sup-
porting Information) by about 0.40 V. The CVs of com-
pounds 1 and 3 are shown in Figure 6. As in compound 1,
the first oxidation potential of compound 3 was split (DE=
0.28 V), owing to the electronic communication between the
two porphyrins, which was comparable to that of compound
1 (0.31 V). More importantly, the first oxidation potential of
compound 3 (0.41 V) was positively shifted from that of
compound 1 by 0.44 V, and the first and second reduction
potentials were reversible waves at À0.79 and À1.01 V. The
higher first oxidation potential of compound 3 was consis-
tent with its chemical stability towards oxidative degrada-
tion. On the basis of these electrochemical data, the electro-
chemical HOMO–LUMO gaps were 1.10 and 1.20 eV for
compounds 1 and 3, respectively.
Experimental Section
General
1H NMR and 19F NMR spectra were recorded on a JEOL ECA-600 spec-
trometer (600 MHz for 1H and 565 MHz for 19F nuclei). Chemical shifts
(d) are reported in ppm relative to the residual solvent as the internal
reference for the 1H NMR spectra (d=7.260 ppm) and hexafluoroben-
zene as an external reference for the 19F NMR spectra (d=À162.9 ppm).
UV/Vis/NIR spectra were recorded on a Shimadzu UV-3100PC spec-
trometer. HRMS (ESI-TOF) of samples in MeCN were recorded on
a BRUKER microTOF instrument in positive- or negative-ion modes. X-
ray data were recorded on a Rigaku-Raxis imaging plate system. Unless
otherwise noted, materials that were obtained from commercial suppliers
were used without further purification. Column chromatography on silica
gel was performed on Wakogel C-300 and C-400. Thin-layer chromatog-
raphy (TLC) was carried out on Al sheets coated with silica gel 60 F254
(Merck 5554).
1,1,2,2-Tetrapyrroethane (5)
TFA (160 mL, 2.1 mmol, 5 mol%) was added to a solution of 1,4-dioxane-
2,3-diol (4, 5.0 g, 42 mmol) in pyrrole (58 mL, 840 mmol, 20 equiv) and
the resulting solution was stirred under a N2 atmosphere at 08C. After
2 h, the reaction was quenched by the addition of triethylamine and un-
reacted pyrrole was removed by distillation under reduced pressure. The
residue was purified by column chromatography on silica gel (n-hexane/
CH2Cl2, 1:1). Recrystallization from CH2Cl2/n-hexane gave the product
as a white powder (1.6 g, 5.5 mmol, 13% yield). The spectroscopic data
were the same as those reported previously.[12]
Conclusions
Triply linked electron-deficient diporphyrin 3 was prepared
by the cross-condensation of 1,1,2,2-tetrapyrroethane (5)
with dipyrromethane dicarbinol (6), followed by oxidation
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An Electron-Deficient Porphyrin Tape
meso–meso-Linked Diporphyrin (8)
1.652 gcmÀ3; T=93(2) K; R1 =0.0753 [I>2s(I)]; Rw =0.2214 (all data);
GOF=1.012; crystals were grown from PhCl/MeOH.
To a solution of tetrapyrroethane (5, 500 mg, 1.72 mmol) and dicarbinol
6[14b] (2.65 g, 3.79 mmol, 2.2 equiv) in dry CH2Cl2 (100 mL) was added p-
toluenesulfonic acid monohydrate (372 mg, 1.89 mmol, 1.1 equiv), and
the resulting solution was stirred under a N2 atmosphere at ambient tem-
perature for 1 h. After the addition of DDQ (2.35 g, 10.3 mmol,
6.0 equiv), the solution was stirred for a further 1 h and then passed
through a short alumina column to remove any tar. The reaction mixture
was purified by GPC and column chromatography on silica gel to afford
porphyrin 7 (225 mg, 278 mmol, 8.1% yield) and diporphyrin 8 (104 mg,
64 mmol, 3.7% yield). The spectroscopic data of compound 7 were the
same as those reported previously.[18]
Crystallographyic Data
CCDC 871954 (3) and CCDC 871954 (8) contain the supplementary crys-
tallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Two-photon-Absorption Experiments
The TPA spectrum was measured in the NIR region by using the open-
aperture Z-scan method with 130 fs pulses from an optical parametric
amplifier (Light Conversion, TOPAS) operating at a repetition rate of
3 kHz that was generated from a Ti:sapphire regenerative amplifier
system (Spectra-Physics, Hurricane). After passing through a 10 cm focal
length lens, the laser beam was focused and passed through a 1 mm
quartz cell. Because the position of the sample cell could be controlled
along the laser beam direction (z axis) by using the motorcontrolled
delay stage, the local power density within the sample cell could be
simply controlled under constant laser intensity. The transmitted laser
beam from the sample cell was then detected by using the same photo-
diode as that used for reference monitoring. The on-axis peak intensity
of the incident pulses at the focal point (I0) was in the range of 40–
60 GWcmÀ2. For a Gaussian beam profile, the nonlinear absorption coef-
ficient can be obtained by curve fitting of the observed open-aperture
traces T(z) to Equation (1), where a0 is the linear absorption coefficient,
l is the sample length, and z0 is the diffraction length of the incident
beam.
1
8: H NMR (600 MHz, CDCl3, 298 K): d=9.00 (m, 8H; b-H), 8.61 (d, J=
4.6 Hz, 4H; b-H), 8.15 (d, J=4.6 Hz, 4H; b-H), À2.31 ppm (brs, 4H;
inner NH); 19F NMR (565 MHz, CDCl3, 298 K): d=À126.44 (m, 12F; o-
F), À151.15 (t, J=22.0 Hz, 2F; p-F), À151.27 (t, J=22.0 Hz, 4F; p-F),
À161.19 (dt, 1J=6.1 Hz, 2J=23.0 Hz, 4F; m-F), À161.39 ppm (dt, 1J=
6.1 Hz, 2J=23.0 Hz, 8F; m-F); UV/Vis (CHCl3): lmax (e)=410 (209000),
447 (215000), 518 (61000), 591 (18000), 647 (3500), 664 nm
(4000 molÀ1 dm3 cmÀ1); HRMS (ESI-TOF, positive-ion mode): m/z calcd
for C76H21N8F30: 1615.1405; found: 1615.1384 [M+H]+.
Crystal data: C76H20F30N8·2.5C2H4Cl2; Mw =1862.38; triclinic; space
group: P-1 (No. 2); a=18.5492(3), b=21.5458(4), c=22.1560(4) ꢁ; a=
68.6717(9), b=89.6696(9), g=64.5465(8)8; V=7327.5(2) ꢁ3; Z=4;
1calcd =1.688 gcmÀ3; T=93(2) K; R1 =0.1051 [I>2s(I)]; Rw =0.3173 (all
data); GOF=1.069. Crystals were grown from 1,2-dichloroethane/
MeOH.
meso–meso-Linked ZnII–Diporphyrin (9)
To a solution of compound 8 (83.5 mg, 51.7 mmol) in MeOH (100 mL)
was added ZnACHTUNGTRENNUNG(OAc)2·2H2O (190 mg, 1.1 mmol, 20 equiv) and the result-
ing solution was stirred under a N2 atmosphere at ambient temperature.
After 12 h, the reaction mixture was washed with water, dried over
Na2SO4, and the solvent was removed under reduced pressure to afford
the product as a red solid (86.2 mg, 49.5 mmol, 96% yield). 1H NMR
(600 MHz, CDCl3, 298 K): d=9.08 (m, 8H; b-H), 8.67 (d, J=4.6 Hz, 4H;
b-H), 8.18 ppm (d, J=4.6 Hz, 4H; b-H); 19F NMR (565 MHz, CDCl3,
298 K): d=À136.70 (m, 12F; o-F), À151.86 (t, J=22.0 Hz, 2F; p-F),
À151.98 (t, J=22.0 Hz, 4F; p-F), À161.74 (dt, 1J=5.9 Hz, 2J=23.5 Hz,
4F; m-F), and À161.78 ppm (dt, 1J=5.9 Hz, 2J=23.5 Hz, 8F; m-F); UV/
Vis (CHCl3): lmax (e)=320 (37000), 418 (203000), 456 (210000), 563
After the nonlinear absorption coefficient has been obtained, the TPA
cross-section s(2) of one solute molecule (in GM, where 1 GM=
10À50 cm4 sphotonÀ1 moleculeÀ1) can be determined by using Equation (2),
where NA is the Avogadro constant, d is the concentration of the com-
pound in solution, h is the Planck constant, and n is the frequency of the
incident laser beam.
(51000), 602 nm (14000 molÀ1 dm3 cmÀ1); fluorescence (CHCl3, lex
=
418 nm): lmax =597, 652 nm; HRMS (ESI-TOF, negative-ion mode): m/z
calcd for C76H16N8F30Zn2Cl: 1776.9244; found: 1776.9220 [M+Cl]À.
Transient Absorption Experiments
meso–meso,b-b,b-b Triply Linked ZnII–Diporphyrin (3)
The femtosecond time-resolved transient absorption (TA) spectrometer
used for this study consisted of a femtosecond optical parametric amplifi-
er (Quantronix, Palitra-FS) pumped by a Ti:sapphire regenerative ampli-
fier system (Quantronix, Integra-C) operating at 1 kHz repetition rate
and an accompanying optical-detection system. The generated OPA
pulses had a pulse width of about 100 fs and an average power of 1 mW
in the range of 450–800 nm, which were used as pump pulses. White light
continuum (WLC) probe pulses were generated with a sapphire window
(2 mm thick) by focusing a small portion of the fundamental 800 nm
pulses, which were picked off by a quartz plate before entering into the
OPA. The time delay between the pump and probe beam was carefully
controlled by making the pump beam travel along a variable optical
delay (Newport, ILS250). The intensities of the spectroscopically dis-
persed WLC probe pulses were monitored by a miniature spectrograph
(OceanOptics, USB2000+). To obtain the time-resolved transient absorp-
tion difference signal (DA) at a specific time, the pump pulses were chop-
ped at 25 Hz and absorption-spectra intensities were saved alternately
with or without pump pulses. Typically, 6000 pulses were used to excite
the samples and to obtain the TA spectra at a particular delay time. The
polarization angle between the pump and the probe beam was set at the
magic angle (54.78) by using a Glan-laser polarizer with a half-wave re-
tarder to prevent polarization-dependent signals. The cross-correlation
To a solution of compound 9 (55.0 mg, 31.6 mmol) in dry toluene (80 mL)
was added ScACHTUNGTRENNUNG(OTf)3 (77.9 mg, 158 mmol, 5.0 equiv) and DDQ (35.9 mg,
158 mmol, 5.0 equiv) and the resulting solution was stirred under a N2 at-
mosphere at 1108C for 6 h. After cooling to RT, THF was added to the
reaction mixture and the resulting solution was passed through an alumi-
na column with THF as an eluent. The solution was evaporated and re-
crystallization from CH2Cl2/MeOH gave the product as violet crystals
(36.4 mg, 20.9 mmol, 66% yield). 1H NMR (600 MHz, CDCl3, 298 K): d=
7.71 (d, J=4.6 Hz, 4H; b-H), 7.67 (d, J=4.6 Hz, 4H; b-H), 7.09 ppm (s,
1
4H; bay-area); 19F NMR (565 MHz, CDCl3, 298 K): d=À137.17 (dd, J=
7.3 Hz, 2J=25.7 Hz, 8F; o-F), À137.43 (dd, 1J=7.3 Hz, 2J=25.7 Hz, 4F;
o-F), À151.88 (m, 6F; p-F), À161.14 ppm (m, 12F; m-F); UV/Vis
(CH2Cl2): lmax(e)=414 (137000), 523 (54600), 559 (128000), 601 (91400),
661 (35000), 945 (13300), 1077 nm (13600 molÀ1 dm3 cmÀ1); fluorescence
(CHCl3, lex =414 nm): lmax =1101, 1272 nm; HRMS (ESI-TOF, negative-
ion mode): m/z calcd for C76H12N8F30Zn2Cl: 1772.8931; found: 1772.8920
[M+Cl]À.
Crystal data: C76H18F30N8Zn2·5MeOH·2PhCl; Mw =2088.93; monoclinic;
space group: P21/c (No. 14); a=21.6317(7), b=6.9196(2), c=
28.9465(6) ꢁ; b=104.2737(14)8; V=4199.0(2) ꢁ3; Z=2; 1calcd
=
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Dongho Kim, Atsuhiro Osuka et al.
FULL PAPERS
full-width at half-maximum (fwhm) in the pump-probe experiments was
less than 200 fs and the chirp of WLC probe pulses was 800 fs in the
range of 400–800 nm. To minimize chirp, all of the reflection optics were
used in the path of the probe beam and a quartz cell of 2 mm path length
was used. After completing each set of fluorescence and TA experiments,
the absorption spectra of all of the compounds were carefully checked to
rule out the presence of artifacts or spurious signals arising from, for ex-
ample, degradation or photo-oxidation of the samples in question.
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Time-resolved fluorescence-lifetime experiments were performed by
using the time-correlated single-photon-counting (TCSPC) technique. As
an excitation light source, we used a home-made cavity-dumped Ti:sap-
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ultrashort pulses (100 fs at fwhm) pumped by a continuous wave (cw)
Nd-YVO4 laser (Coherent, Verdi). The output pulse of the oscillator was
frequency-doubled by a 1 mm thickness of a second harmonic crystal
(barium borate, BBO, CASIX). The fluorescence was collected by using
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51) with a thermoelectric cooler (Hamamatsu, C4878) that was connected
to a TCSPC board (Becker&Hickel SPC-130). The overall instrumental
response function was about 25 ps (fwhm). A vertically polarized pump
pulse by a Glan-laser polarizer irradiated the samples and a sheet polar-
izer, which was set at complementary angle to the magic angle (54.78),
was placed in the fluorescence-collection path to obtain polarization-in-
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Acknowledgements
This work was supported by Grants-in-Aid (Nos. 22245006 (A) and
20108006 “pi-Space”) from MEXT. T.T. acknowledges a JSPS Fellowship
for Young Scientists. The work at Yonsei University was supported by
the Midcareer Researcher Program (2010-0029668), an AFSOR/APARD
Grant (No. FA2386-09-1-4092), and by the World Class University (R32-
2010-000-10217) Programs of the Ministry of Education, Science, and
Technology (MEST) of Korea.
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Received: March 21, 2012
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ÝÝ These are not the final page numbers!

FULL PAPERS
Porphyrinoids
Hirotaka Mori, Takayuki Tanaka,
Naoki Aratani, Byung Sun Lee,
Pyosang Kim, Dongho Kim,*
Atsuhiro Osuka*
&&&& — &&&&
An Electron-Deficient Porphyrin Tape
Mix tape: A hexakis(pentafluoro-
phenyl)-substituted meso–meso,b-b,b-
b triply linked ZnII–diporphyrin exhib-
ited considerably improved chemical
stability, owing to a lowered HOMO,
and good solubility in common organic
solvents.
Chem. Asian J. 2012, 00, 0 – 0
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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