510
M. Canlıca et al. / Polyhedron 30 (2011) 508–514
transparent thin-layer electrochemical (OTTLE) cell connected to a
Bio analytical system (BAS) CV 27 voltammogram and using Cary
1E UV–Vis spectrophotometer.
H) 7.26 (2H, d, J = 8.4 Hz, Ar-H). Anal. Calc. for C36H18N4O2: C,
80.29; H, 3.37; N, 10.40. Found: C, 79.37; H, 3.68; N, 8.96%. MS
(m/z): Calc. 538.55. Found [M]+: 538.1.
2.3.4. 4,40-(1,10-Binaphthyl-8,80-diylbis(oxy))diphthalonitrile (7)
The synthesis of complex 7 was as outlined for complex 6 ex-
cept 2 instead of 1 was employed. The amounts of all the reagents
were the same. A light yellow solid was obtained. Yield: 2.1 g. M.p.
2.3. Syntheses
The CoPc derivatives were prepared using standard phthalocya-
nine synthetic procedures. The target precursor was prepared by a
nucleophilic aromatic substitution reaction of 3-nitrophthalonitri-
le (1) or 4-nitrophthalonitrile (2) with 1,10-binaphthyl-8,80-diol 3,
Schemes 1 and 2.
150 °C. IR(KBr) (m
max/cmꢀ1): 3072 (Ar-CH), 2232 (C„N), 1586
(C@C), 1278 (C–O–C). 1H NMR (DMSO-d6): d, ppm 8.20 (2H, d,
J = 8.8 Hz, Ar-H), 8.08 (2H, d, J = 8.4 Hz, Ar-H), 7.85 (2H, d,
J = 8.8 Hz, Ar-H), 7.55 (2H, t, J = 7.8 Hz, Ar-H), 7.49 (2H, s, Ar-H),
7.39 (2H, t, J = 7.2 Hz, Ar-H), 7.30 (2H, d, J = 8.4 Hz, Ar-H), 7.16
(2H, d, 8.0 Hz, Ar-H), 6.93 (2H, d, J = 8.4 Hz, Ar-H). Anal. Calc. for
2.3.1. 3-(80-Hydroxy-1,10-binaphthyl-8-yloxy)phthalonitrile (4)
Compound 3 (3.31 g, 11.55 mmol) was dissolved in dry DMSO
(15 mL) and 1 (2 g, 11.55 mmol) was added under inert atmo-
sphere. To this reaction mixture finely ground anhydrous potas-
sium carbonate (1.60 g, 11.55 mmol) was added. After 4 h of
stirring at room temperature further potassium carbonate
(0.40 g, 2.88 mmol) was added and this same amount was added
again after 24 h of stirring. After a total of 48 h of stirring, the reac-
tion mixture was poured into water (50 mL) resulting in the forma-
C36H18N4O2: C, 80.29; H, 3.37; N,10.40. Found: C, 79.43; H, 4.05;
N, 9.83%. MS (m/z): Calc. 538.55. Found 538.0.
2.3.5. (3)-Tetra(1,10-binaphthoxy)phthalocyaninato cobalt(II) (8)
Compound 4 (0.100 g) was refluxed in the presence of excess
cobalt (II) chloride and DBU (0.2 mL) in n-pentanol (20 mL) for
18 h. The mixture was cooled to room temperature, followed by
addition of methanol (30 mL) to precipitate out the dark green
crude product. The precipitate was washed repeatedly with meth-
anol followed by chromatography on silica gel using chloroform as
the eluting solvent. Yield: 0.025 g. M.p. >350 °C. UV–Vis (DMSO)
tion of
a light yellow precipitate. The crude product was
centrifuged and further purified by chromatography over a silica
gel column using a CHCl3 as eluent. The product was recrystallized
from ethanol and then the pure product was dried using P2O5.
White solid. Yield: 1.9 g. M.p. 60 °C IR(KBr) (m
max/cmꢀ1): 3487
kmax/nm (log
e
/dmꢀ3 molꢀ1 cmꢀ1): 690 (4.34), 370 (4.38).
(Ar-OH), 3059 (Ar-CH), 2233 (C„N), 1575 (C@C), 1268 (C–O–C).
1H NMR (DMSO-d6): d, ppm 8.18 (2H, d, J = 9.0 Hz, Ar-H), 8.08
(2H, d, J = 8.1 Hz, Ar-H), 7.85 (1H, t, J = 7.3 Hz, Ar-H), 7.55 (2H, t,
J = 7.4 Hz, Ar-H), 7.50–7.45 (4H, m, Ar-H), 7.35 (2H, t, J = 7.2 Hz,
Ar-H), 7.2 (1H, s, OH), 7.12 (2H, d, J = 8.0 Hz, Ar-H). Anal. Calc. for
IR[(KBr)
m
max/cmꢀ1]: 3465 (Ar-OH), 1589 (C@C), 1254 (C–O–C).
Anal. Calc. for C112H64N8O8Co: C, 78.73; H, 3.78; N, 6.56. Found:
C, 77.91; H, 3.85; N, 6.490%. MS (m/z): Calc. 1708.69. Found
[M+3H]+: 1711.4.
C
28H16N2O2: C, 81.54; H, 3.91; N, 8.79. Found: C, 81.29; H, 3.68;
2.3.6. (4)-Tetra(1,10-binaphthoxy)phthalocyaninato cobalt(II) (9)
The synthesis of complex 9 was as outlined for complex 8 ex-
cept 5 instead of 4 was employed. The amounts of all the reagents
were the same except for 5 (0.095 g). Yield: 0.035 g. M.p. >350 °C.
N, 8.96%. MS (m/z): Calc. 412.12. Found [M]+: 411.67.
2.3.2. 4-(80-Hydroxy-1,10-binaphthyl-8-yloxy)phthalonitrile (5)
The synthesis of complex 5 was as outlined for complex 4 ex-
cept 2 instead of 1 was employed. The amounts of all the reagents
were the same. A white solid was obtained. Yield: 2.0 g. M.p. 113 °C
UV–Vis (DMSO) kmax/nm (log
e
/dmꢀ3 molꢀ1 cmꢀ1): 680 (4.35), 373
(4.79). IR[(KBr)
m
max/cmꢀ1]: 3465 (Ar-OH), 1579 (C@C), 1255 (C–O–
C). Anal. Calc. for C112H64N8O8Co: C, 78.73; H, 3.78; N, 6.56. Found:
C, 78.97; H, 3.94; N, 6.44%. MS (m/z): Calc. 1708.69. Found
[M+3H]+: 1711.3.
IR(KBr) (m
max/cmꢀ1): 3465 (Ar-OH), 3054 (Ar-CH), 2232 (C„N),
1586 (C@C), 1246 (C–O–C). 1H NMR (DMSO-d6): d, ppm 8.20 (2H,
d, J = 9.2 Hz, Ar-H), 8.08 (1H, d, J = 8.0 Hz, Ar-H), 7.85 (2H, d,
J = 8.4 Hz, Ar-H), 7.7 (1H, b, OH), 7.55 (2H, t, J = 7.4 Hz, Ar-H),
7.48 (2H, d, J = 7.2 Hz Ar-H), 7.46 (1H, s, Ar-H), 7.38 (2H, t,
J = 7.4 Hz, Ar-H), 7.16 (1H, d, J = 8.0 Hz, Ar-H), 6.93 (2H, d,
J = 7.6 Hz, Ar-H). Anal. Calc. for C28H16N2O2: C, 81.54; H, 3.91; N,
6.79. Found: C, 81.09; H, 3.62; N, 10.22%. MS (m/z): Calc. 412.12.
Found [M]+: 412.37.
2.3.7. 10,110,150,250-[Tetrakis(4,40-(1,10-binaphthyl-8,80-
diyl(oxy))diphenyl)]bis-phthalocyaninato dicobalt(II) (10)
A mixture of complex 6 (0.100 g) and cobalt (II) chloride
(0.100 g) was ground to a fine powder and heated in sealed glass
tube for 15 min under argon atmosphere at 550 °C. After cooling
to room temperature, the blue-green reaction product was washed
with hot methanol and hot water. The product was separated by
column chromatography on silica gel with a solvent mixture chlo-
roform–methanol (2:1). Yield: 0.038 g. M.p. >350 °C. UV–Vis
2.3.3. 3,40-(1,10-Binaphthyl-8,80-diylbis(oxy))diphthalonitrile (6)
Compound 3 (3.31 g, 11.55 mmol) was dissolved in dry DMSO
(15 mL) and 1 (4 g, 23.10 mmol) was added under inert atmo-
sphere. To this reaction mixture finely ground anhydrous potas-
sium carbonate (3.19, 23.1 mmol) was added. After 4 h of stirring
at room temperature, further potassium carbonate (0.79 g,
5.77 mmol) was added and this same amount was added again
after 24 h of stirring. After a total of 96 h of stirring, the reaction
mixture was poured into water (50 mL) resulting in the formation
of light yellow precipitate. The crude product was centrifuged and
further purified by chromatography over a silica gel column using a
CHCl3 as eluent. The product was recrystallized from ethanol and
then the pure product was dried using P2O5. Yellow solid. Yield:
(DMSO) kmax/nm (log
e
/dmꢀ3 molꢀ1 cmꢀ1): 674 (4.69), 326 (4.69).
IR[(KBr)
m
max/cmꢀ1]: 3054 (Ar-CH), 1579 (C@C), 1245 (C–O–C).
Anal. Calc. for C144H72N16O8Co2: C, 76.12; H, 3.19; N, 9.86. Found:
C, 75.77; H, 3.19; N, 9.86%. MS (m/z): Calc. 2272.08. Found
[Mꢀ4H]+: 2268.48.
2.3.8. 20,100,160,240-[Tetrakis(4,40-(1,10-binaphthyl-8,80-
diyl(oxy))diphenyl)]bis-phthalocyaninato dicobalt(II) (11)
The synthesis of complex 11 was as outlined for complex 10 ex-
cept 7 instead of 6 was employed. The amounts of all the reagents
2.5 g. M.p. 142 °C IR(KBr)
(
m
max/cmꢀ1): 3080 (Ar-CH), 2230
were the same. Yield: 0.032 g. M.p. >350 °C. UV–Vis (DMSO) kmax
/
/
(C„N), 1570 (C@C), 1259 (C–O–C). 1H NMR (DMSO-d6): d, ppm
8.21 (2H, d, J = 8.8 Hz, Ar-H), 8.08 (2H, d, J = 8.4 Hz, Ar-H), 7.63
(2H, t, J = 7.2 Hz, Ar-H), 7.59 (2H, t, J = 7.6, Ar-H), 7.51–7.57 (4H,
m, Ar-H), 7.37 (2H, d, J = 8.4 Hz, Ar-H), 7.34 (2H, t, J = 8.0 Hz, Ar-
nm (log
e
/dmꢀ3 molꢀ1 cmꢀ1): 669 (4.70), 331 (4.81). IR[(KBr)mmax
cmꢀ1]: 3054 (Ar-CH), 1588 (C@C), 1231 (C–O–C). Anal. Calc. for
C
144H72N16O8Co2: C, 78.73; H, 3.78; N, 6.56. Found: C, 77.97; H,
3.94; N, 6.44%. MS (m/z): 2272.08. Found [Mꢀ3H]+: 2269.48.