Inorganic Chemistry
Article
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S, 29.43. Found: C, 53.35, H, 5.87, S, 29.38%. H NMR (400 MHz,
CDCl3, δ): 7.36 (4H, d, J = 6.58 Hz, aromatic H), 7.28 (6H, m,
aromatic H), 3.72 (2H, dd, J = 11.97 Hz, 6.19 Hz, CH2OH), 3.42 (4H,
m, CH2S), 1.97 (4H, m, CH2CH2S), 1.70−1.30 (14H, m, CH2), 1.26
(1H, t, J = 5.29 Hz, OH), 0.93 (3H, t, J = 6.71 Hz, CH3). 13C NMR
(100 MHz, CDCl3, δ): 168.75, 140.80, 129.45, 128.21, 128.15, 62.85,
37.44, 37.21, 32.57, 31.67, 29.06, 28.84, 28.82, 27.69, 27.66, 25.33,
22.62, 14.11. HRMS (CI−CH4) (m/z): [M + H+] calcd for 655.0633;
found, 655.0635. UV−vis−NIR: λmax = 911 nm (35 157). IR: 699 (s),
747 (s), 883 (s, νR−C(=S)2), 1028 (s), 1157 (s, br, νCS), 1236 (s,
br), 1417 (s), 1448 (s), 2849, 2924, 3349 (br, νCH2−OH) cm−1.
Complex LE1−8. This was prepared from a mixture of HC1 (0.26
mmol) and HC8 (0.78 mmol) in 30 mL of CHCl3, giving a dark green
powder (23% yield). Anal. Calcd for C30H40NiO2S6: C, 52.70; H, 5.90;
AUTHOR INFORMATION
Corresponding Author
31 52.
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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Financial support from the French National Research Agency
(ANR-06-PSPV-004 and ANR-08-HABI-0014) is gratefully
acknowledged. Authors also thank Dr. B. Garreau-de Bonneval
and Prof. I. Malfant for fruitful discussions.
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S, 28.14. Found: C, 52.78, H, 5.86, S, 28.12%. H NMR (300 MHz,
REFERENCES
CDCl3, δ): 7.33 (7H, m, aromatic H), 6.80 (2H, d, J = 8.30 Hz,
aromatic H), 3.82 (3H, s, br, CH3OPh), 3.69 (2H, t, J = 6.07 Hz,
CH2OH), 3.41 (4H, m, CH2S), 1.96 (4H, m, CH2CH2S), 1.71−1.25
(15H, m, CH2 and OH), 0.92 (3H, t, J = 5.73 Hz, CH3). HRMS (CI−
CH4) (m/z): [M+] calcd for 682.0706; found, 682.0709. UV−vis−
NIR: λmax = 928 nm (34 590). IR: 689 (s), 1145 (s, br, νCS), 1171
(s), 1235 (s, br, νC−O), 1592 (s), 2848 (s), 2918 (s), 3323 (br,
νCH2−OH) cm−1.
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Complex LE1−9. This was prepared from a mixture of HC1 (0.26
mmol) and HC9 (0.78 mmol) in 30 mL of CHCl3, giving a dark green
powder (20% yield). Anal. Calcd for C49H78NiO3S6: C, 60.91; H, 8.14;
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S, 19.91. Found: C, 60.85, H, 8.07, S, 19.85%. H NMR (300 MHz,
CDCl3, δ): 7.30 (4H, d, J = 8.71 Hz, aromatic H), 6.80 (4H, d, J = 8.71
Hz, aromatic H), 3.96 (4H, t, J = 6.50 Hz, CH2OPh), 3.69 (2H, t, J =
6.40 Hz, CH2OH), 3.41 (4H, m, CH2S), 1.95 (4H, m, CH2CH2S),
1.80 (5H, m, CH2 and OH), 1.68−1.20 (48H, m, CH2), 0.91 (3H, t, J
= 5.73 Hz, CH3). 13C NMR (75 MHz, CDCl3, δ): 186.27, 186.06,
169.91, 159.56, 133.57, 130.61, 114.08, 68.14, 62.65, 37.34, 37.19,
31.93, 31.70, 29.60, 29.58, 29.41, 29.34, 29.25, 29.03, 28.83, 27.84,
27.82, 26.03, 25.36, 22.71, 22.63, 13.90. HRMS (CI−CH4) (m/z):
[M+] calcd for 964.3629; found, 964.3631. UV−vis−NIR: λmax = 951
nm (36 800). IR: 1161 (d, br, νCS), 1238 (s, br, νC−O), 1599 (s),
2852 (s), 2923 (s), 3345 (br, νCH2−OH).
Complex LE2−7. This was prepared from a mixture of HC2 (0.175
mmol) and HC7 (0.525 mmol) in 40 mL of CHCl3, giving a dark
green powder (13% yield). Anal. Calcd for C28H20NiOS4: C, 60.12; H,
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3.60; S, 22.92. Found: C, 60.18, H, 3.55, S, 22.86%. H NMR (300
MHz, CD2Cl2, δ): 7.46−7.28 (17H, m, aromatic H), 6.79 (2H, d, J =
8.70 Hz, aromatic H), 5.07 (1H, s, br, PhOH). 13C NMR (75 MHz,
CDCl3, δ): 182.74, 182.15, 156.92, 141.55, 141.23, 134.93, 130.65,
128.99, 128.88, 128.80, 128.46, 128.34, 115.35. HRMS (CI−CH4)
(m/z): [M+] calcd for 557.9750; found, 557.9766. UV−vis−NIR: λmax
= 871 nm (25 830).
Complex LE2−8. This was prepared from a mixture of HC2 (0.19
mmol) and HC8 (0.57 mmol) in 40 mL of CHCl3, giving a dark green
powder (22% yield). Anal. Calcd for C29H22NiO2S4: C, 59.09; H, 3.76;
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S, 21.76. Found: C, 59.13, H, 3.71, S, 21.69%. H NMR (300 MHz,
CDCl3, δ): 7.47−7.26 (14H, m, aromatic H), 6.79 (4H, m, aromatic
H), 5.14 (1H, s, br, PhOH), 3.84 (3H, s, CH3). 13C NMR (75 MHz,
CDCl3, δ): 168.75, 140.80, 129.45, 128.21, 128.15, 62.85, 37.44, 37.21,
32.57, 31.67, 29.06, 28.84, 28.82, 27.69, 27.66, 25.33, 22.62, 14.11.
HRMS (CI−CH4) (m/z): [M+] calcd for 587.9856; found, 587.9854.
UV−vis−NIR: λmax = 890 nm (23 480).
ASSOCIATED CONTENT
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S
* Supporting Information
Table showing the effect of ligands on the NIR absorption band
of molecule 2; cyclic voltammogram of complex LE1−5;
synthetic procedures of ligands and complexes and their
characterizations. This material is available free of charge via the
(10) (a) Ohta, K.; Takagi, A.; Muroki, H.; Yamamoto, I.; Matsuzaki,
K.; Inabe, T.; Maruyama, Y. J. Chem. Soc., Chem. Commun. 1986, 883−
2846
dx.doi.org/10.1021/ic402528j | Inorg. Chem. 2014, 53, 2841−2847