Three new cobalt(ii) complexes, [Co(L12)2](BF4)2 (1), [Co(L14)2](BF4)2?H2O (2) and [Co(L16)2](BF4)2?H2O (3), where L12-16 are N3-Schiff bases appended with linear C12-16 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 CoN6 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 normal thermal spin-crossover behaviour with weak hysteresis loops at about 320 K. Hence, these complexes showed uncoupled phase transitions (class iiia). The values for the Seebeck coefficient (Se) 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.