Discotic liquid crystals of transition metal complexes 49~?: establishment of helical structure of fullerene moieties in columnar mesophase of phthalocyanine-fullerene dyads

摘要

A homologous series of the phthalocyanine-fullerene dyads, C_n-PcM(OFbaC60) (n = 6, 8, 10, 12; M = Cu, Ni, Co: 3a-3f), have been synthesized to obtain homeotropic alignment at rt and investigate the effects of spacer chain length (n = 6, 8, 10, 12) and central metal (M = Cu, Ni, Co) on the mesomorphism. Interestingly, the shorter-spacer-substituted (n = 6, 8; M = Cu) dyads 3a and 3b showed a hexagonal columnar mesophase (Col_h), whereas the longer-spacer-substituted (n = 10, 12; M = Cu, Ni, Co) dyads 3c-3f showed a tetragonal columnar mesophase (Col_(tet)). Moreover, each of the homologs 3a-3e shows perfect homeotropic alignment in both the Col_h and Col_(tet) mesophases at rt. More interestingly, these columnar mesophases gave a very unique XRD reflection peak denoted as Peak H in a very small angle region of 0.8 < 2q < 2.0 degree. We have established at the first time from our developed two new XRD sample preparation techniques that the Peak H is due to the helical structure of fullerenes around columns formed by one-dimensionally stacked Pc cores. 1D nano array structure of donor and acceptor between two electrodes is recently proposed to obtain higher photoelectric conversion efficiency for organic thin film solar cells. This 1D nano array structure is almost compatible with the present homeotropically aligned Pc-C_(60) dyads 3a-3f between two glass plates. Hence, these novel Pc-C_(60) dyads 3a-3f may be very suitable to organic thin film solar cells.