K. Sakamoto et al. / Dyes and Pigments 96 (2013) 430e434
431
2
. Experimental
(FAB): m/z found 1492, Calcd. 1492.04; 1,4,8,11,15,18,22,25-
octakis(methoxythiophenyl)phthalocyanines (1b); 1b-Cu (0.03 g,
2
.1. Equipment
27%) Found: C, 62.88%; H, 3.91%; N, 6.65%. Calcd. for C88
Cu: C, 62.82%; H, 3.89%; N, 6.66%; S, 15.25%; O, 7.61%; Cu, 3.77%.
MS (FAB): m/z found 1682, Calcd. 1682.58: 1b-Co (0.02 g, 21%)
Found: C, 63.00%; H, 3.89%; N, 6.59%. Calcd. for C88 Co: C,
62.99%; H, 3.90%; N, 6.68%; S, 15.29%; O, 7.63%; Co, 3.51%. MS (FAB):
m/z found 1678, Calcd. 1677.97: 1b-Ni (0.03 g, 25%) Found: C,
65 8 8
H N S
O
8
UVeVis spectra were measured on a Shimadzu UV-2400PC
spectrometer, while fluorescence t spectra were measured on
a JASCO FP-6000 fluorescence spectrometer. Each sample was
65 8 8 8
H N S O
ꢂ5
ꢂ3
.
prepared in chloroform at a concentration of 5.0 ꢁ 10 mol dm
The 1H NMR spectra were measured at 400 MHz on a Bruker
65 8 8 8
63.01%; H, 3.92%; N, 6.67%. Calcd. for C88H N S O Ni: C, 63.01%; H,
Advance 400S in dimethylsulfoxide-d
6
using tetramethylsilane as
3.92%; N, 6.67%; S, 15.29%; O, 7.63%; Ni, 3.49%. MS (FAB): m/z found
1678, Calcd. 1677.73: 1b-Zn (0.03 g, 29%) Found: C, 62.75%; H,
3.95%; N, 6.65%. Calcd. for C88H N S O Zn: C, 62.75%; H, 3.89%; N,
65 8 8 8
6.65%; S, 15.23%; O, 7.60%; Zn, 3.88%. MS (FAB): m/z found 1684,
Calcd. 1684.42: 1b-Pb (0.04 g, 35%) Found: C, 57.88%; H, 3.59%; N,
the internal standard. Elemental analysis was carried out using
a PerkineElmer 2400CHN instrument. MS were taken with a Nihon
Denshi Joel JMS-AX500 mass spectrometer. CVs were recorded on
an ALS electrochemical analyzer 600D at room temperature in
ꢂ3
dichlorobenzene containing 0.01 mol dm tetrabutylammonium
6.15%. Calcd. for C88
14.05%; O, 7.01%; Pb, 11.33%. MS (FAB): m/z found 1827, Calcd.
1826.23: 1b-H (0.02 g, 8%) Found: C, 65.24%; H, 4.11%; N, 6.93%.
Calcd. for C88 : C, 65.24%; H, 4.11%; N, 6.92%, O, 7.90, S,
15.18%. MS (FAB): m/z found 1620, Calcd. 1620.03;
,4,8,11,15,18,22,25-octakis(tert-butylthiophenyl) phthalocyanines
(1c); 1c-Cu (0.02 g, 20%) Found: C, 71.13%; H, 6.05%; N, 5.87%. Calcd.
for C112 Cu: C, 61.13%; H, 6.02%; N, 5.92%; S, 13.56%; Cu,
3.37%. MS (FAB): m/z found 1891, Calcd. 1891.22: 1c-Co (0.02 g, 21%)
Found: C, 71.24%; H, 6.04%; N, 5.93%. Calcd. for C112 Co: C,
65 8 8 8
H N S O Pb: C, 57.88%; H, 3.59%; N, 6.14%; S,
perchlorate (TBAP). CVs were recorded by scanning the potential at
ꢂ1
a rate of 50 mV s . The working and counter electrodes were
2
platinum wires, and the reference electrode was an Ag/AgCl elec-
trode. The area of the working electrode was 2.0 ꢁ 10 cm .
66 8 8 8
H N O S
ꢂ2
2
1
2.2. Materials
113 8 8
H N S
All chemicals were purchased from Aldrich or Tokyo Chemical
Industry Co. Ltd. They were used as received without further
113 8 8
H N S
purification. For chromatographic separation, silica gel was used
71.30%; H, 6.04%; N, 5.94%; S, 13.60%, Co, 3.12%. MS (FAB): m/z found
1886, Calcd. 1886.61: 1c-Ni (0.03 g, 23%) Found: C, 71.31%; H, 6.04%;
(
60, particle size 0.063e0.200 nm, 7734-grade; Merck).
N, 5.89%. Calcd. for C112
13.60%; Ni, 3.11%. MS (FAB): m/z found 1886, Calcd. 1886.37: 1c-Zn
0.03 g, 28%) Found: C, 71.00%; H, 6.01%; N, 5.92%. Calcd. for
Zn: C, 71.06%; H, 6.02%; N, 5.92%; S, 13.55%; Zn, 3.45%.
MS (FAB): m/z found 1893, Calcd. 1803.07: 1c-Pb (0.04 g, 34%)
Found: C, 66.12%; H, 5.63%; N, 5.53%. Calcd. for C112 Pb: C,
66.11%; H, 5.60%; N, 5.51%; S, 12.61%; Pb, 10.17%. MS (FAB): m/z
found 2035, Calcd. 2034.88: 1c-H (0.02 g, 9%) Found: C, 73.55%; H,
6.26%; N, 6.13%. Calcd. for C112 : C, 73.56%; H, 6.28%; N,
113 8 8
H N S Ni: C, 71.31%; H, 6.04%; N, 5.94%; S,
2
.3. Preparation of phthalocyanines
(
Intermediate
dicyanohydroquinone and trifluoromethanesulfonic anhydride for
4 h, in accordance with a description from the literature [8]. Inter-
2
was synthesized by reaction of 2,3-
112 113 8 8
C H N S
2
113 8 8
H N S
mediates 3 were synthesized, respectively, from 2 and thiophenols
such as p-toluenethiol, 4-methoxybenzenethiol and tert-butylth-
iophenol at room temperature for 24
2
h
to obtain 3,6-
114 8 8
H N S
bis(metylthiophenyl)phthalonitrile (3a), 3,6-bis(methoxythiophenyl)
phthalonitrile (3b) and 3,6-bis(tert-butyl thiophenyl)phthalonitrile
6.13%, S, 14.03%. MS (FAB): m/z found 1829, Calcd. 1828.68.
(3c) [5,8].
3. Results and discussion
The
1,4,8,11,15,18,22,25-octakis(methylthiophenyl)phthalocya-
nines (1a), 1,4,8,11,15,18,22,25-octakis(methoxythiophenyl)phthalo-
cyanines (1b) and 1,4,8,11,15,18,22,25-octakis(tert-butylthiophenyl)
phthalocyanines (1c) were synthesized, respectively, from corre-
sponding intermediates 3a, 3b, and 3c and metal salt.
3.1. Synthesis of 1,4,8,11,15,18,22,25-octakis(thioaryl)
phthalocyanines and their spectral properties
Scheme
1
shows the synthetic route to the target
A solution of 3 (0.25 mmol), metal chlorides or metal acetate,
DBU (0.2 mL) as a catalyst and 1-PeOH (10 mL) was heated under
reflux for 7 h. After cooling to room temperature, the reaction
products were poured into methanol to form a precipitate, which
was washed with water and methanol, and chromatographed on
silica gel with toluene as eluent. 1,4,8,11,15,18,22,25-
octakis(metylthiophenyl)phthalocyanines (1a); 1a-Cu (0.02 g,
1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines (1). The target
compounds 1 were synthesized in three steps via the intermedi-
ates, phthalonitrile-3,6-ditriflate (2) and 3,6-bis(thioaryl)phthalo-
nitriles (3). The intermediates were analyzed using infrared (IR)
and proton nuclear magnetic resonance ( H NMR) spectroscopy,
and elemental analysis. Their analytical data showed good agree-
ment with the proposed structures [8].
1
1
8%) Found: C, 67.98%; H, 4.51%; N, 7.01%. Calcd. for C88
H
65
N
8
S
8
Cu:
The octakis(methylthiophenyl)phthalocyanines (1a), octa-
kis(methoxythiophenyl)phthalocyanines (1b) and octakis(tert-
butylthiophenyl)phthalocyanines (1c) were synthesized, respec-
tively, from the corresponding intermediates 3a, 3b, and 3c and
a metal salt in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU) as a catalyst in hot1-pentanol (1-PeOH) for 7 h, and were
analyzed using elemental analysis and mass spectroscopy (MS). The
analytical data showed good agreement with the proposed struc-
tures [8].
C, 67.99%; H, 4.21%; N, 7.21%; S, 16.50%; Cu, 4.09%. MS (FAB): m/z
found 1554, Calcd. 1554.59: 1a-Co (0.02 g, 24%) Found: C, 68.10%; H,
4
7
1
.20%; N, 7.25%. Calcd. for C88
.23%; S, 16.55%; Co, 3.80%. MS (FAB): m/z found 1550, Calcd.
549.97: 1a-Ni (0.03 g, 28%) Found: C, 68.18%; H, 4.20%; N, 7.13%.
Calcd. for C88 Ni: C, 68.20%; H, 4.23%; N, 7.23%; S, 16.55%; Ni,
.79%. MS (FAB): m/z found 1550, Calcd. 1549.73: 1a-Zn (0.02 g,
4%) Found: C, 67.87%; H, 4.23%; N, 7.11%. Calcd. for C88 Zn:
65 8 8
H N S Co: C, 68.19%; H, 4.23%; N,
65 8 8
H N S
3
2
65 8 8
H N S
C, 67.91%; H, 4.21%; N, 7.20%; S, 16.48%; Zn, 4.20%. MS (FAB): m/z
found 1556, Calcd.1556.43: 1a-Pb (0.04 g, 34%) Found: C, 62.29%; H,
The absorption maxima in ultravioletevisible (UVeVis) spectral
data of 1a, 1b and 1c are shown in Table 1. The most intense peaks
of phthalocyanines in the visible region are assigned as the Q band,
3
.88%; N, 6.40%. Calcd. for C88
65 8 8
H N S Pb: C, 62.24%; H, 3.86%; N,
6
.60%, S, 15.11%; Pb, 12.19%. MS (FAB): m/z found 1699, Calcd.
which are attributed to the allowed
highest occupied molecular orbital (HOMO) and the lowest unoc-
cupied molecular orbital (LUMO) of the phthalocyanine ring. The Q
p
ꢂ
p* transition between the
1698.24: 1a-H
2
H
(0.04 g, 19%) Found: C, 70.85%; H, 4.66%; N, 7.51%.
: C, 70.84%; H, 4.46%; N, 7.51%, S, 17.1%. MS
Calcd. for C88
66
N
8
S
8