PhotoluminescentLiquid Crystalline Nickel(II) Complexes
diaminocyclohexane (0.05 g, 0.5 mmol). The mixture was heated to
reflux for 3 h with a few drops of acetic acid to yield the yellow
Schiff base, N,NЈ-bis[4-(4Ј-n-alkoxy)salicylidene]-trans-1,2-diami-
nocyclohexane. The compound was collected by filtration and
recrystallized from absolute ethanol.
7.13 (dd, J = 1.4, J = 8.1 Hz, 1 H, H1), 6.30 (d, J = 6.1 Hz, 1 H,
H2), 6.28 (s, 1 H, H3), 3.88 (q, J = 4 Hz, 8 H, CH2CH3), 3.21 (t, J
= 5.4 Hz, 2 H, OCH2), 1.81–1.89 (m, 4 H, cyclohexyl), 1.61 (m, 2
H, cyclohexyl), 1.41 (m, 2 H, cyclohexyl), 0.85 (t, J = 6.7 Hz, 6 H,
CH3), 0.84 (m, CH2 in side chain) ppm.
N,NЈ–Bis[4-(4Ј-octadecyloxy)salicylidene]-trans-1,2-diaminocyclo-
hexane (18dch): Yield 0.33 g (75%); m.p. 115 °C. FAB-MS: m/z =
859 [M + H]+. C56H94N2O4 (858.7): calcd. C 78.2, H 10.0, N 3.2;
found C 78.1, H 10.2, N 3.1. 1H NMR (400 MHz, CDCl3): δ =
13.40 (s, 1 H, ph-OH), 8.04 (s, 1 H, N=CH), 7.04 (dd, J = 1.5, J
= 8.2 Hz, 1 H, H1), 6.37 (d, J = 6.1 Hz, 1 H, H2), 6.30 (s, 1 H, H3),
3.94 (q, J = 4 Hz, 8 H, CH2CH3), 3.20 (t, J = 5.6 Hz, 2 H, OCH2),
1.80–1.95 (m, 4 H, cyclohexyl), 1.63 (m, 2 H, cyclohexyl), 1.40 (m,
2 H, cyclohexyl), 0.87 (t, J = 6.8 Hz, 6 H, CH3), 0.84 (m, CH2 in
side chain) ppm. 13C NMR (75.45 MHz, CDCl3, 25 °C): δ = 130.06
(C1), 106.31 (C2), 102.11 (C3), 160.30 (C6), 70.97 (C7), 28.81 (C8),
23.01 (C9), 161.62 (C10), 115.64 (C11), 159.73 (C12) ppm. IR
Ni-14dch: Yield 0.57 g (80%). C48H76N2NiO4 (803.85): calcd. C
71.7, H 9.5, N 3.4; found C 71.5, H 9.4, N 3.5. FAB-MS: m/z =
803 [M + H]+. IR (KBr): ν = 1615 [ν(C=N)], 1145 [ν(C–O), phen-
˜
olic] cm–1. 1H NMR (400 MHz, CDCl3): 8.01 (s, 1 H, N=CH), 6.91
(dd, J = 1.4, J = 8.1 Hz, 1 H, H1), 6.34 (d, J = 6.0 Hz, 1 H, H2),
6.25 (s, 1 H, H3), 3.85 (q, J = 4 Hz, 8 H, CH2CH3), 3.22 (t, J =
5.3 Hz, 2 H, OCH2), 1.78–1.91 (m, 4 H, cyclohexyl), 1.64 (m, 2 H,
cyclohexyl), 1.37 (m, 2 H, cyclohexyl), 0.91 (t, J = 6.5 Hz, 6 H,
CH3), 0.85 (m, CH2 in side chain) ppm.
Acknowledgments
(KBr): ν = 3445 [br, ν(OH)] 1622 [s, ν(C=N)], 1143 [s, ν(C–O)]
˜
cm–1.
The authors thank the Department of Science and Technology
(DST), New Delhi and the University Grants Commission, New
Delhi, for financial support. Prof. R. C. Deka (Tezpur University,
India) is thanked for assistance with the theoretical calculations.
Sophisticated Analytical Instrumentation Facility, North East Hill
University, Shillong is acknowledged for spectral results.
N,NЈ–Bis[4-(4Ј-hexadecyloxy)salicylidene]-trans-1,2-diaminocyclo-
hexane (16dch): Yield 0.31 g (76%); m.p. 118 °C. FAB-MS: m/z =
803 [M + H]+. C52H86N2O4 (802.6): calcd. C 77.7, H 10.7, N 3.4;
found C 77.9, H 10.6, N 3.1. 1H NMR (400 MHz, CDCl3): δ =
13.41 (s, 1 H, ph-OH), 8.14 (s, 1 H, N=CH), 7.02 (dd, J = 1.5, J
= 8.2 Hz, 1 H, H1), 6.33 (d, J = 6.0 Hz, 1 H, H2), 6.31 (s, 1 H, H3),
3.90 (q, J = 4 Hz, 8 H, CH2CH3), 3.22 (t, J = 5.4 Hz, 2 H, OCH2),
1.82–1.91 (m, 4 H, cyclohexyl), 1.61 (m, 2 H, cyclohexyl), 1.41 (m,
2 H, cyclohexyl), 0.89 (t, J = 6.7 Hz, 6H, CH3), 0.84 (m, CH2 in
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˜
1141 [s, ν(C–O)] cm–1.
N,NЈ–Bis[4-(4Ј-tetradecyloxy)salicylidene]-trans-1,2-diaminocyclo-
hexane (14dch): Yield 0.26 g (77%); m.p. 121 °C. FAB-MS: m/z =
747 [M + H]+. C48H78N2O4 (746.6): calcd. C 77.1, H 10.5, N 3.7;
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13.41 (s, 1 H, ph-OH), 8.02 (s, 1 H, N=CH), 7.01 (dd, J = 1.5, J
= 8.2 Hz, 1 H, H1), 6.35 (d, J = 6.0 Hz, 1 H, H2), 6.28 (s, 1 H, H3),
3.88 (q, J = 4 Hz, 8 H, CH2CH3), 3.23 (t, J = 5.4 Hz, 2 H, OCH2),
1.79–1.93 (m, 4 H, cyclohexyl), 1.66 (m, 2 H, cyclohexyl), 1.39 (m,
2 H, cyclohexyl), 0.91 (t, J = 6.7 Hz, 6H, CH3), 0.88 (m, CH2 in
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side chain) ppm. IR (KBr): ν = 3434 [br, ν(OH)], 1625 [s, ν(C=N)],
˜
1143 [s, ν(C–O)] cm–1.
Synthesis of Nickel(II) Complexes (Ni-ndch): General procedure: Li-
gand 18dch (0.85 g, 1 mmol), 16dch (0.80 g, 1 mmol) or 14dch
(0.74 g, 1 mmol) was dissolved in the minimum volume of absolute
ethanol. Ni(OAc)2·4H2O (0.02 g, 0.1 mmol) in methanol was then
added slowly, and the mixture was stirred for 2 h at room tempera-
ture. The brown solid was collected by filtration, washed with di-
ethyl ether and recrystallized from chloroform/ethanol (1:1).
Ni-18dch: Yield 0.67 g (78%). C56H92N2NiO4 (916.06): calcd. C
73.4, H 10.1, N 3.0; found C 73.3, H 10.2, N, 3.1. FAB-MS): m/z
= 915 [M + H]+. IR (KBr): ν = 1612 [ν(C=N)], 1141 [ν(C–O),
˜
phenolic] cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.91 (s, 1 H,
N=CH), 6.04 (dd, J = 1.2, J = 8.1 Hz, 1 H, H1), 6.31 (d, J = 6.1 Hz,
1 H, H2), 6.21 (s, 1 H, H3), 3.72 (q, J = 3.9 Hz, 8 H, CH2CH3),
3.10 (t, J = 5.4 Hz, 2 H, OCH2), 1.40–1.85 (m, 4 H, cyclohexyl),
1.63 (m, 2 H, cyclohexyl), 1.40 (m, 2 H, cyclohexyl), 0.81 (t, J =
6.7 Hz, 6 H, CH3), 0.82 (m, CH2 in side chain) ppm.
Ni-16dch: Yield 0.61 g (75%). C52H78N2NiO4 (853.91): calcd. C
72.6, H 9.8, N 3.2; found C 72.4, H 9.7, N 3.1. FAB-MS: m/z =
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olic] cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.11 (s, 1 H, N=CH),
Eur. J. Inorg. Chem. 2011, 5390–5396
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