Alkynyl corroles: Synthesis by Sonogashira coupling reaction and the physicochemical properties

Article abstract of DOI:10.1142/S1088424610001842

Alkynyl corroles were synthesized from iodidphenyl corrole precursor by using Sonogashira coupling reaction with or without the presence of copper(I) iodide co-catalyst. The alkynyl group on corrole macrocycle has a significant effect on the photophysical and electrochemical properties of free-base and metal corrole derivatives.

Full text of DOI:10.1142/S1088424610001842

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2010; 14: 150–157
DOI: 10.1142/S1088424610001842
Published at http://www.worldscinet.com/jpp/
Alkynyl corroles: synthesis by Sonogashira coupling reaction
and the physicochemical properties
Hai-Ying Zhana, Hai-Yang Liu*aš, Jun Lua, A-Zhong Wanga, Li-Li Youb, Hui Wang*b,
Liang-Nian Jib and Huan-Feng Jiang*a
a Department of Chemistry, South China University of Technology, Guangzhou 510641, China
b State Key Laboratory of Optoelectronics Materials and Technologies/MOE Laboratory of Bioinorganic and
Synthetic Chemistry, Sun Yat-Sen University, Guangzhou 510275, China
Received 25 January 2009
Accepted 22 April 2009
ABSTRACT: Alkynyl corroles were synthesized from iodidphenyl corrole precursor by using
Sonogashira coupling reaction with or without the presence of copper(I) iodide co-catalyst. The alkynyl
group on corrole macrocycle has a significant effect on the photophysical and electrochemical properties
of free-base and metal corrole derivatives.
KEYWORDS: corrole, Sonogashira coupling reaction, fluorescence, electrochemistry.
by Gryko and co-workers quite recently [13]. Herein, we
wish to report the synthesis of several new alkynyl cor-
roles by using Sonogashira reaction with iodided free-
INTRODUCTION
Corroles are one meso-carbon shorter analogs of por-
phyrin. The first synthesis of corroles may be traced back
base corrole and its metal (Cu and Mn) complexes as
to the 1960s and for more than 30 years, the elaborate and
precursors (Table 1). The fluorescence and electrochemi-
time-consuming preparation of corroles had presented a
cal properties of synthesized alkynyl corroles were also
formidable obstacle in the study of corroles. This situa-
examined.
tion was not changed until 1999 when the direct synthesis
of meso-triarylcorroles [1, 2] and the rational two-step
RESULTS AND DISCUSSION
synthesis of A2B-type meso-substituted corroles [3] were
discovered. Nowadays, a number of well-established
synthetic protocols are available for corroles, and an
increasing amount of effort is devoted to the study of
their properties and applications [4–7].
Sonogashira coupling reaction [8] of terminal acety-
lenes with aryl or vinyl halides provides a powerful tool
for C−C bond formation. Despite the wide reporting
of studies [9–12] on preparation of new porphyrins by
using this reaction, examples of corroles bearing alkynyl
groups prepared by Sonogashira coupling reaction are
rare. So far, the only example for the synthesis of alkynyl
corroles by Sonogashira coupling reaction was reported
Synthesis
Sonogashira coupling reaction is generally co-
catalyzed by CuI with an amine as base and a phosphine
as ligand for palladium catalyst [16, 17]. In this work,
we chose Pd2(dba)3 as initial catalyst as it is air-stable
and shows good results in alkynyl porphyrin prepara-
tion [11]. The dative ligand throughout the investigation
was consistently triphenylphospine, since it is relatively
cheap, easy to handle, non-toxic and air-stable. Firstly,
we use copper and manganese iodidphenylcorroles (1b
and 1c) as reactants. As shown in Table 1, when Sono-
gashira reaction is co-catalyzed by CuI, the reaction
of the copper corrole 1b and manganese corrole 1c with
2 equiv. of phenylacetylene resulted in formation of
2b and 2c with an isolated yield of 73.4% and 76.2%,
respectively (Table 1, entries 1, 2). The addition of copper
š
SPP full member in good standing
*Correspondence to: Hai-Yang Liu, email: chhyliu@scut.edu.
cn; Hui Wang, email: stswh@zsu.edu.cn and Huan-Feng Jiang,
email: jianghf@scut.edu.cn, fax: +86 20-87112906
Copyright © 2010 World Scientific Publishing Company

ALKYNYL CORROLES
151
Table 1. Synthesis of alkynyl corrole derivativesa
I
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
Pd2(dba)3/PPh3/CuI
Et3N/CH2Cl2
N
N
N
N
N
N
N
N
+
M
M
F
F
F
F
M=3H 2a
Cu 2b
M=3H 1a
Cu 1b
Mn 2c
Mn 1c
Substrate
1b
Catalyst
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
CuI, mol.%
Product
2b
2c
Yield, %b
73.4
76.2
70.5
71.0
54.8
58.0
5.0
1
2
3
4
5
6
10
10
—
—
—
10
1c
1b
1c
1a
1a
2b
2c
2a
2a
2b
2b
1b
—
7
1a
Pd2(dba)3
100
62.5
3.0
8
1b
1b
1a
1a
1a
1a
—
—
100
—
—
—
—
—
—
9
—
—
10c
11c
12c
13d
Pd2(dba)3
Pd(OAc)2
PdCl2
2a
96
2a
92
2a
94
PdCl2(PPh)3
2a
97
a
Conditions: catalyst (10 mol.%) and CuI (0–100 mol.%), PPh3 (1 equiv.), iodidphenylcorrole (0.2 mmol), phenylacetylene
(2 equiv.), Et3N (30 mL), DCM (60 mL), rt, nitrogen, 16 h. b Isolated yield. c The reaction was carried out at 60 °C for 4 h. d The
reaction was carried out at reflux for 4 h in the absence of PPh3.
salts as co-catalysts in typical Sonogashira reactions may
cause difficulty in recovering reagent (alkyne), making
the reaction less environmental friendly [8]. Sonogashira
reactions without CuI have been developed [18, 19]. In
our experiments, when the reaction were performed in
the absence of CuI, the alkynylation could also go on
smoothly to give an isolated yield of 2b in 70.5% and 2c
in 71% (Table 1, entries 3, 4).
The functionalization of free-base corroles is more
challenging due to their intriguing and erratic reactivity,
such as the observations in bromination [20], hydroform-
ylation of corrole [21] and the reaction of corrole with
CI4 [22]. The Sonogashira reaction of metal-free cor-
roles offers another way of preparing free-base corrole
derivatives. In the absence of CuI, free-base corrole 1a
reacted with phenylacetylene to give 2a in a lower yield
(54.8%) than that of corresponding metal corrole homol-
ogous reactants (Table 1, entry 5). When the reaction was
carried out in the presence of co-catalyst CuI, the isolated
yield of free-base 2a increased slightly to 58.0% (Table
1, entry 6). Interestingly, copper corrole 2b could also
be isolated with a yield of 5% under these conditions.
This result indicated that some of the copper ions may
have inserted into the N4 coordination core of corrole in
the reaction. To address this issue, the reaction was per-
formed with an increased amount of CuI up to 100 mol.%.
It turned out the yield of copper corrole 2b increased to
62.5% (Table 1, entry 7), and no free-base corrole 2a
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152
H.-Y. ZHAN ET AL.
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
CuI
N
N
N
N
N
HN
HN
Cu
F
F
F
F
Et3N/CH2Cl2
NH
F
Scheme 1. Reaction of H3TPFC and copper(I) iodide
could be isolated. In this case, copper corrole 1b could
be isolated with a yield of 3%. Since copper can be effi-
ciently removed from corroles by reductive demetalation
[23–26], the insertion of copper into corrole is not a sig-
nificant problem when using typical Sonogashira reac-
tion for the preparation of alkynyl corroles. To test the
reactivity between free-base corrole and CuI, 5,10,15-
tris(pentafluorophenyl)corrole (H3TPFC) was reacted
with 2 equiv. of CuI in CH2Cl2/Et3N (V/V, 2/1) at room
temperature for 1 h, and CuTPFC was obtained with
a yield of 97%. This represents a new method for the
preparation of copper corrole (Scheme 1). Since copper
corrole is generally prepared by reaction of Cu(II) salt
(such as copper(II) acetate and copper(II) dichloride)
and corrole in DMF or pyridine [27–29]. It is noteworthy
that the reaction of H3TPFC and CuI did not occur with-
out Et3N after 24 h. Furthermore, Sonogashira reaction of
corroles cannot go on without Pd2(dba)3 catalyst (Table
1, entries 8–9). When the reaction was performed at the
elevated temperature (60 °C) for 4 h, the yield of 2a
increased sharply (Table 1, entry 10). Excellent yields
could also be obtained with different palladium salts as
catalyst (Table 1, entries 11–13).
Fig. 1. UV-vis spectra of corrole in toluene
From the above observations, metal corrole is a better
precursor than free-base corrole in Sonogashira coupling
reaction at room temperature, with the former giving a
significantly higher isolated yield of target alkynyl cor-
role ; the different metal corroles (Cu and Mn) give simi-
lar yields. When the reaction was carried out at 60 °C,
free-base corrole 2a was obtained with the best yield. This
temperature is suitable for Sonogashira coupling reaction
of iodidphenylcorrole and phenylacetylene. There is no
big difference in the catalytic activity of different palla-
dium salts. Also, free-base corrole can react with CuI to
give copper corrole in the presence of triethylamine in
dichloromethane.
Fig. 2. Fluorescence spectra of corroles in toluene at room
temperature (λex = 560 nm, 1.0 × 10-5 M)
The Soret bands of the Cu and Mn-complexes 1b, 2b,
1c and 2c are located around 411 nm (± 1 nm). Soret
bands of these metal corroles blue-shifted significantly
compared to free-base 1a and 2a.
Fluorescence spectra. The steady-state fluorescence
spectra of corroles 1a, 2a and 3a in toluene at room tem-
peratureareshowninFig.2.Transientfluorescencespectra
were recorded by the method described in the Experi-
mental section, and the transient fluorescence spectra of
these free-base corroles are shown in Fig. 3. Fluorescence
quantum yields were determined using TPP as a standard
(Φfl = 0.11) [30]. The fluorescence emission maxima
Photophysical properties
UV-vis spectra. Figure 1 shows the UV-vis spectra of
the free-base corrole 1a and 2a, and metal corrole 1b,
1c, 2b and 2c in toluene. All investigated corroles exhib-
ited typical UV-vis spectra of free-base, copper(III) or
manganese(III) corrole. The Soret bands of 1a and 2a are
located at 420 and 425 nm, respectively. A red shift of
about 5 nm was observed in the alkynation of 1a to 2a.
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 152–157

ALKYNYL CORROLES
153
(λmax), quantum yield (Φfl) and lifetime (τ) are summa-
rized in Table 2. No emission was observed for metal
corroles 1b, 1c, 2b and 2c due to the suppression by the
central metal ions. For the purpose of discussion, the emis-
sion spectra of 10-phenyl-5,15-dis(pentafluorophenyl)
corrole (3a) and tetraphenylporphyrin (TPP) were also
measured. When excited by 560 nm wavelength light,
fluorescence intensity of 2a and 3a is several times stron-
ger than that of 1a, and the maximum emission shifts to
lower energy by 7 and 6 nm, respectively (Fig. 2). 1a is
a weak emitter, with Φfl = 0.005 and lifetime of 1.27 ns
because of the heavy-atom effect caused by iodide [31].
Therefore, a close analog corrole 3a was used as a refer-
ence to evaluate the alkynation effect on the fluorescence
property of synthesized 2a here. It could be seen that the
fluorescence quantum yield of 2a (0.132) is obviously
larger than that of 3a (0.106). Fluorescence lifetime of
2a (4.55 ns) is also longer than that of 3a (3.94 ns). The
Φfl and τ values for 2a and 4a [32] in toluene are similar.
5,10,15-tris(pentafluorophenyl)corrole (4a) exhibited a
lower fluorescence lifetime (3.7 ns, [33]) in CH2Cl2 than
in toluene with the similar fluorescence quantum yield.
Electrochemical properties
Cyclic voltammograms of free-base corrole (1a and
2a), copper corroles (1b and 2b) and manganese corroles
(1c and 2c) are shown in Fig. 4, and their redox potentials
are shown in Table 3. The first comprehensive study on
the electrochemistry of meso-substituted free-base cor-
roles was carried out in PhCN [34]. In this paper, cyclic
voltammetry (CV) of free-base corrole 1a and 2a were
performed in CH3CN because of their electrochemical
lability in dichloromethane. The CV of 1a in CH3CN
consists of one irreversible reduction (at Epc = -0.24 V)
and four oxidations processes between -0.5 and +1.7 V
(vs. SCE). The first and fourth oxidations located at peak
potentials of 0.03 and 1.39 V are irreversible (scan rate:
0.1 V/s). Two additional reversible oxidations
Fig. 3. Fluorescence decay curve of corroles in toluene
located at E1/2 = 0.50 and 0.86 V are observed
for this compound. The CV of 2a in CH3CN
only displays one reversible reduction (at E1/2
= -0.88V) and one reversible oxidation (at E1/2
Table 2. Fluorescence data of corroles 1a, 2a, 3a and 4a at 295 K
R2
R1
R1
R1
R1
1a: R1=H; R2=I
2a: R1=H; R2=
3a: R1=R2=H
= 0.31 V) between -1.4 and +0.6 V (vs. SCE).
Complex1bdisplaysthreeredoxprocesses
at E1/2 = -1.02, 0.03 and 1.04 V vs. SCE. The
F
F
F
F
F
F
F
F
N
HN
HN
F
F
NH
4a: R1=R2=R3=F
reversible one-electron reduction at E1/2
=
-1.02 V is metal-centered (Cu(II)/Cu(III))
and the first reversible oxidation can be con-
fidently assigned to be corrole-centered [35].
Except for two reversible redox processes at
E1/2 = 0.06 and 0.97 V (Table 2), 2b under-
goes an irreversible reduction at Epc = -1.11
V and an irreversible oxidation at Epa = 1.53
V. No evidence of dimerization is observed
upon the electrochemical oxidation. This is
different from the case of (OEC)Cu [36]. Due
Corroles Solvent λex, nm
λ
max, nm
Φfl a
τ, ns
1.27b
4.55b
3.94b
4.8, 4.3c
Reference
1
2
3
4
1a toluene
2a toluene
3a toluene
4a toluene
CH2Cl2
560
560
560
550
407
647
654
653
0.005
0.132
0.106
this work
this work
this work
32
645, 707 0.13
643, 700 0.14
3.7, 1.1
33
a
b
Tetraphenylporphyrin was used as a standard (Φfl = 0.11). Excitation at
420 nm. c Excitation at 373 nm.
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154
H.-Y. ZHAN ET AL.
Fig. 4. Cyclic voltammograms (CVs) of corroles 1a, 2a, 1b, 2b, 1c and 2c (0.1 M TBAPF6, SCE as reference electrode, glass carbon
disc electrode as working electrode; scan rate 0.1 V/s)
to the formation of [(OEC)Cu]2 dimer, the first oxidation
of (OEC)Cu involved two stepwise abstractions of one
electron from each macrocycle, or CE mechanism for the
electrochemistry of (OEC)Cu.
Manganese corrole complex 1c undergoes a reversible
reduction at E1/2 = -1.47 V, irreversible reduction at Epc =
-1.14 V and two reversible oxidations at E1/2 = 0.02 and
0.33 V. While complex 2c undergoes a reversible reduc-
tion at E1/2 = -1.72 V, one quasi-reversible reduction at
E1/2 = -0.91 V and a single reversible oxidation at E1/2
=
0.36 V. Based on the previous electrochemical study of
manganese corroles [37, 38], the reversible oxidation at
E1/2 = 0.02 for 1c and E1/2 = 0.36 V for 2c may be assigned
to Mn(III)/Mn(IV) redox couple. Thus, a 340 mV
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ALKYNYL CORROLES
155
Table 3. Redox potential data of corrole complexes
E1/2a/V vs. SCE
caliber. After passing through a monochro-
mator, it was recorded by a streak camera
(Hamamatsu C1587) and a CCD (Hama-
matsu C4742-95). The fluorescence lifetime
can be determined with a 30 ps resolution by
the deconvolution procedure. All measure-
ments were carried out at room temperature.
Cyclic voltammetry was carried out with
Auto LAB PGSTAT 30. A three-electrode
system was used and consisted of a glassy
carbon working electrode, a platinum wire
counter electrode and a saturated calomel
reference electrode (SCE). The SCE elec-
trode was separated from the bulk of the
solution by a fritted-glass bridge of low
porosity that contained the solvent/support-
ing electrolyte mixture. Half-wave poten-
tials were calculated as E1/2 = (Epa + Epc)/2
and are referenced to SCE.
Metal ion Compound Solvent
Reduction
-0.24b
Oxidation
0.03b, 0.50, 0.86, 1.39c
0.31
none
none
Cu
1a
2a
1b
2b
1c
2c
CH3CN
CH3CN
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
-0.88
-1.02
0.03, 1.04
-1.11b
0.06, 0.97, 1.53c
0.02, 0.33
Mn
-1.47, -1.14b
-1.72, -0.91d
0.36
a E1/2 = (Epa + Epc)/2, SCE as reference, scan rate = 0.1 V/s. b Epc. c Epa for a scan
rate of 0.1 V/s. d E1/2 for one quasi-reversible reduction.
positive shift of Mn(III)/Mn(IV) couple from 1c to 2c was
observed. This indicates the alkynyl group on the meso-
phenyl of corrole may exert an electron-withdrawing
effect on the corrole macrocycle.
General Sonogashira coupling procedure
Corrole (0.2 mmol), CuI (0–100 mol.%), Pd2(dba)3
(10 mol.%), 1 equiv. of PPh3 and Et3N (30 mL) were
mixed in DCM (60 mL). The reaction mixture was satu-
rated with nitrogen and 2 equiv. of phenylacetylene were
added. After stirring 16 h at room temperature, solvent
was removed under reduced pressure and the reaction
mixture was purified by preparative TLC on silica gel
eluted with n-hexane/CH2Cl2 (3/1 to 1/1) to yield the
products.
5-(pentafluorophenyl)dipyrromethane was prepared
according to previously published methods, spectral
properties were consistent with literature data [14]. The
free-base corroles (1a and 3a) were synthesized accord-
ing to the published general procedures [15].
EXPERIMENTAL
General
Reagents (Sigma-Aldrich and Alfa Aesar) were of
synthetic grade and used without further purification. Tri-
ethylamine (Et3N) and dichloromethane (CH2Cl2) were
distilled from CaH2 under argon. Pyrrole was freshly
distilled before use. Tetra-n-butylammonium hexafluoro-
phosphate (TBAPF6) was purchased from Sigma Chemi-
cal Co. And dried under vacuum at 40 °C for at least one
week prior to use.
Preparation of 10-(4-iodophenyl)-5,15-bis(penta-
fluorophenyl)corrole (1a). (isolated yield: 12%). H
1
Preparative thin-layer chromatography was carried out
on silica gel plates loaded with Merck silica gel 60 GF254.
Column chromatography was performed on Merck 60
NMR (400 MHz; CDCl3): δH, ppm 7.89–7.91 (2H, m,
Ph), 8.08–8.10 (2H, m, Ph), 8.55–8.56 (2H, m, pyr-
role-H), 8.66–8.71 (4H, m, pyrrole-H), 9.10–9.11 (2H,
m, pyrrole-H). 19F NMR (376.498 MHz; CDCl3): δF, ppm
-137.84 (4F, m, Ph), -152.63 (2F, m, Ph), -161.63–161.81
(4F, m, Ph). UV-vis (toluene): λmax, nm (ε × 103 M-1.cm-1)
420 (0.944), 564.0 (0.149), 615 (0.089), 639 (0.06). MS
(FAB): m/z 832 (calcd. for [M + H]+ 832.43).
Preparation of copper complex of 10-(4-iodo-
phenyl)-5,15-bis(pentafluorophenyl)corrole (1b). An
approximate three-fold excess of copper(II) acetate
hydrate (145 mg, 0.73 mmol) was added to a solution
of 1a (200 mg, 0.24 mmol) in 10 mL methanol in one
portion. TLC examinations (silica gel; n-hexane/CH2Cl2,
2:1) revealed that the starting material was fully con-
sumed at room temperature within 2 h. The solvents
were evaporated and the product was purified by chro-
matography on silica gel with n-hexane/CH2Cl2 (3:1) as
eluent. 161 mg 1b was obtained (isolated yield: 75%).
1
silica gel (300–400 mesh). H NMR and 19F NMR spec-
tra were recorded on Bruker Avance DRX (400 MHz or
300 MHz) spectrometers. UV-vis spectra were measured
on a Hitachi U-3010 spectrophotometer. Mass spectra
(FAB mode) were recorded on a VG Analytical spectrom-
eter in the positive-ion mode using m-nitrobenzyl alcohol
(Aldrich) as a matrix. Absorption spectra of all of the sam-
ples were measured by a PerkinElmer Lambda 850 UV-
vis spectrometer. Fluorescence spectra were recorded by a
Combined Fluorescence Lifetime and Steady State Spec-
trometer (FLS920). The fluorescence decay curves were
measured by a time-resolved fluorescence spectroscopic
experimental setup. A Nd:YAG laser (EKSPLA PL2143)
and an OPG system (EKSPLA PG401SH/DFG2-10) gen-
erated the laser pulse (420 nm, 10 Hz) with a full width at
half maximum (FWHM) of 22 ps as a light source. The
fluorescence was collected with a pair of lenses with big
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 155–157

156
H.-Y. ZHAN ET AL.
1H NMR (400 MHz; CDCl3): δH, ppm 7.16–7.20 (4H, m,
Ph), 7.29–7.31 (2H, m, pyrrole-H), 7.39–7.40 (2H, m,
pyrrole-H), 7.80–7.82 (2H, m, pyrrole-H), 7.93–7.94
(2H, m, pyrrole-H). 19F NMR (376.498 MHz; CDCl3):
δF, ppm -136.96–137.01 (4F, m, Ph), -152.15–152.26 (2F,
m, Ph), -160.69–160.79 (4F, m, Ph). UV-vis (toluene):
-138.3 (4F, m, Ph), -153.2 (2F, m, Ph), -162.1 (4F, m, Ph).
UV-vis (toluene): λmax, nm (ε × 103 M-1.cm-1) 418 (0.86),
568 (0.18) , 644 (0.12). MS (FAB): m/z 706 (calcd. for
[M + H]+ 706.58).
λ
max, nm (ε × 103 M-1.cm-1) 410 (0.525), 553 (0.06). MS
CONCLUSION
(FAB): m/z 892 (calcd. for [M + H]+ 892.95).
In summary, we have reported a general method for
the alkynylation of corroles via Sonogashira reaction.
The reaction proceeds smoothly with an isolated yield
from moderate to excellent. When using free-base cor-
role as precursor, the reaction product was always the
corresponding alkynyl copper(III) corrole in the pres-
ence of excess of CuI co-catalyst. It was also found that
copper corrole may be prepared by the reaction of free-
base corrole and CuI in CH2Cl2 at room temperature with
the addition of Et3N. This reveals a new method for the
preparation of copper corrole complex. Our preliminary
results also show the alkynyl group on corrole macro-
cycle has a significant effect on the photophysical and
electrochemical properties of free-base and metal corrole
derivatives.
Preparation of manganese complex of 10-(4-
iodophenyl)-5,15-bis(pentafluorophenyl)corrole (1c).
An approximate three-fold excess of manganese(II) ace-
tate tetrahydrate (175 mg, 0.72 mmol) was added to a
solution of 1a (200 mg, 0.24 mmol) in 10 mL methanol
in one portion. TLC examinations (silica gel; n-hexane/
CH2Cl2, 2:1) revealed that the starting material was fully
consumed at room temperature within 1 h. The solvents
were evaporated and the product was purified by chroma-
tography on silica gel with CH2Cl2 as eluent. 149 mg 1b
was obtained (isolated yield: 70.2%). 19F NMR (376.498
MHz; CDCl3): δF, ppm -172.03 (4F, m, Ph), -178.19–
179.17 (6F, m, Ph). UV-vis (toluene): λmax, nm (ε × 103
M-1.cm-1) 411 (0.13), 482 (0.041), 584 633 (0.023). MS
(FAB): m/z 884 (calcd. for [M + H]+ 884.34).
10-(4-(2-phenylethynyl)phenyl)-5,15-bis(penta-
fluorophenyl)corrole (2a). 1H NMR (400 MHz; CDCl3):
δH, ppm 7.39–7.42 (3H, m, Ph), 7.44–7.45 (2H, m, Ph),
7.65–7.68 (2H, m, Ph), 7.95 (2H, m, Ph), 8.16 (2H, m,
pyrrole-H), 8.56 (2H, m, pyrrole-H), 8.73 (2H, m,
pyrole-H), 9.11 (2H, m, pyrrole-H). 19F NMR (376.498
MHz; CDCl3): δF, ppm -138.02–138.43 (4F, m, Ph),
-150.38–150.91 (2F, m, Ph), -160.51–161.48 (4F, m, Ph).
UV-vis (toluene): λmax, nm (ε × 103 M-1.cm-1) 425 (1.064),
565.5 (0.155), 619 (0.108), 641 (0.069). MS (FAB): m/z
807 (calcd. for [M + H]+ 806.65).
Acknowledgements
This work was supported by the National Natural Sci-
ence Foundation of China (Grants 20771039, 20625205,
20971046 and 20871122) and National Key Founda-
tion Research Development Project (973) Item of China
(Grant 2007CB815306).
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