2 O (3), where L [12][13][14][15][16] are N 3 -Schiff bases appended with linear C 12-16 carbon chains at the nitrogen atoms, were obtained in good yields by facile one-pot reactions. The single crystal X-ray structure of complex 1 shows a tetragonally compressed CoN 6 coordination geometry. The melting temperatures of 1 -3 were lower than 373 K, while their decomposition temperatures were above 473 K. All complexes have high-spin Co(II) centres at 300 K and exhibit a columnar mesophase above 383 K. Complexes 1 and 3 showed a normal thermal spin-crossover behaviour with weak hysteresis loops at about 320 K. Hence, these complexes showed uncoupled phase transitions (class iiia). 1 The values for the Seebeck coefficient (S e ) of the cobalt redox couples formed from 1 and 2 were 1.89±0.02 mV K -1 and 1.92±0.08 mV K -1 , respectively, identifying them as potential thermoelectrochemical materials.
A dimeric iron(II) complex, trans-[Fe2(CH3COO)4(L1)2] (1), and a trinuclear iron(II) complex, [Fe3(CH3COO)4(H2O)4(L2)] (2), were studied as potential dye-sensitised solar cell materials. The structures of both complexes were deduced by a combination of instrumental analyses and molecular modelling. Variable-temperature magnetic susceptibility data suggested that 1 was made up of 56.8% high-spin (HS) and 43.2% low-spin (LS) Fe(II) atoms at 294 K and has a moderate antiferromagnetic interaction (J = −81.2 cm−1) between the two Fe(II) centres, while 2 was made up of 27.7% HS and 72.3% LS Fe(II) atoms at 300 K. The optical band gaps (E
o) for 1 were 1.9 eV (from absorption spectrum) and 2.2 eV (from fluorescence spectrum), electrochemical bandgap (E
e) was 0.83 eV, excited state lifetime (τ) was 0.67 ns, and formal redox potential (E′(FeIII/FeII)) was +0.63 V. The corresponding values for 2 were 3.5 eV (from absorption spectrum), 1.8 eV (from fluorescence spectrum), 0.69 eV, 2.8 ns, and +0.41 V.
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