Organometallics
Article
14H), 1.43−1.50 (m, 10H), 2.12 (br, 4H), 2.45 (t, J = 7.5 Hz, 10H),
7.04 (d, J = 8.0 Hz, 10H), 8.00 (d, J = 8.0 Hz, 10H); 13C NMR (125
MHz, C6D6) δ 14.2, 22.5, 22.8, 33.9, 35.6, 36.1, 58.6, 100.2, 128.5,
130.1, 137.7, 142.5, 144.2, 144.8, 147.9, 148.9, 149.1, 152.4, 172.2;
UV−vis (solution in CH2Cl2) λmax (ε) 640 (1.1 × 104). Anal. Calcd for
C116H73S2Co: C, 87.63; H, 4.63. Found: C, 87.37; H, 4.81.
20 nm; Al, 80 nm) was deposited onto the film by thermal evaporation
through a shadow mask, resulting in a device with an active area of
0.04 cm2. The current density−voltage characteristics under AM 1.5G
solar illumination (100 mW cm−2) was recorded using a Keithley 2400
source measurement unit.
4.2.8. Synthesis of Pentakis(4-n-butylphenyl)[60]fullerenyl
Cobalt(III) Benzene-1-aminate-2-thiolate (8). A mixture of cobalt
trisulfide complex 1a (154 mg, 100 μmol) and bis(2-nitrophenyl)
disulfide (1.5 g, 5.0 mmol) in chlorobenzene (7 mL) was heated to
140 °C. The reaction was complete within 12 h to give a dark green
solution, which could be monitored with HPLC (Buckyprep,
toluene/iPrOH 6/4). The resulting reaction mixture was filtered
through a pad of silica gel, and the filtrate was reprecipitated with
MeOH. The crude mixture was purified with preparative HPLC
(Nacalai Tesque, Buckyprep, toluene/iPrOH 5.5/4.5) and reprecipi-
tated with MeOH to give the dark blue solid 5 (31 mg, 19 μmol,
19%): 1H NMR (500 MHz, C6D6) δ 0.82 (t, J = 7.5 Hz, 15H), 1.14−
1.21 (m, 10H), 1.38−1.46 (m, 10H), 2.40 (t, J = 7.5 Hz, 10H), 6.80 (t,
J = 7.5 Hz, 1H), 6.87 (d, J = 8.5 Hz, 1H), 6.98 (d, J = 8.5 Hz, 10H),
7.37 (t, J = 8.0 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 8.07 (d, J = 8.0 Hz,
10H), 10.53 (s, 1H); 13C NMR (125 MHz, C6D6) δ 14.1, 22.5, 33.7,
35.4, 58.4, 98.2, 119.2, 119.9, 125.6, 128.8, 129.6, 131.9, 137.0, 142.8,
144.1, 144.8, 147.8, 148.7, 149.1, 152.5, 154.2, 165.0; UV−vis
(solution in CH2Cl2) λmax (ε) 628 (1.1 × 104). Anal. Calcd for
C116H70NSCo: C, 88.81; H, 4.50; N, 0.89. Found: C, 87.96; H, 4.79;
N, 0.88.
ASSOCIATED CONTENT
* Supporting Information
■
S
Figures giving UV−vis spectra for 4, 5, and 7, J−V
1
characteristics for 9, and H and 13C NMR spectra for 3−9.
This material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Author
5841-1476.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Institutes of Natural Science. This work
was supported by the Funding Program for Next-Generation
World-Leading Researchers (No. GR030, Y.M.).
4.2.9. Synthesis of Pentakis(4-n-butylphenyl)[60]fullerenyl
Cobalt(III) Naphthalene-1,2-dithiolate (9). A mixture of cobalt
trisulfide complex 1a (57.0 mg, 37 μmol) and dinaphthyl disulfide
(589 mg, 1.85 mmol) in chlorobenzene (2.5 mL) was heated to 140
°C. The reaction was complete within 12 h to give a dark green
solution, which could be monitored with HPLC (Buckyprep,
toluene/iPrOH 6/4). The resulting reaction mixture was filtered
through a pad of silica gel, and the filtrate was reprecipitated with
MeOH. The crude mixture was purified with preparative HPLC
(Nacalai Tesque, Buckyprep, toluene/iPrOH 5.5/4.5) and reprecipi-
tated with MeOH to give a dark green solid of the title compound (30
mg, 19 μmol, 50%): 1H NMR (500 MHz, C6D6) δ 0.80 (t, J = 7.5 Hz,
15H), 1.14−1.18 (m, 10H), 1.37−1.43 (m, 10H), 2.38 (t, J = 7.5 Hz,
10H), 6.97 (d, J = 8.5 Hz, 10H), 7.39−7.48 (m, 4H), 7.75 (d, J = 9.0
Hz, 1H), 8.00 (d, J = 8.5 Hz, 10H), 8.79 (d, J = 7.5 Hz, 1H); 13C
NMR (125 MHz, C6D6) δ 14.1, 22.5, 33.7, 35.4, 58.6, 101.1, 124.0,
125.3, 126.9, 127.3, 128.3, 128.6, 129.9, 130.1, 130.2, 135.2, 137.0,
142.9, 144.2, 144.6, 147.9, 148.8, 149.1, 152.0, 164.1, 165.2; UV−vis
(solution in CH2Cl2) λmax (ε) 705 (1.1 × 104). Anal. Calcd for
C120H71S2Co: C, 88.10; H, 4.39. Found: C, 87.65; H, 4.45.
4.3. Electrochemical Measurements. Electrochemical measure-
ments were performed using a BAS CV-50W voltammetric analyzer. A
glassy-carbon electrode was used as the working electrode. The
counter electrode was a platinum coil, and the reference electrode was
a Ag/Ag+ electrode. Cyclic voltammetry (CV) was performed at a scan
rate of 100 mV/s. All half-wave potentials E1/2 = (Epc + Epa)/2, where
Epc and Epa are the cathodic and anodic peak potentials, respectively.
The potential was corrected against Fc/Fc+.
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[60]fullerene cobalt ditholene complex in toluene was spin-coated
(1000 rpm) as an n layer. The thickness of the n layer using 8 was ∼30
nm. After thermal annealing of the p−n film, a Ca/Al electrode (Ca,
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dx.doi.org/10.1021/om400796p | Organometallics XXXX, XXX, XXX−XXX