Discotic liquid crystals of transition metal complexes 51: Synthesis and mesomorphism of flat-pumpkin-shaped phthalocyanine-fullerene dyads

Abstract

We have synthesized a novel type of donor–acceptor liquid crystalline material, phthalocyanine-fullerene ( Pc - C 60) dyad, [m,p,m′-( C 14 O )3 PhO ]6 PcCu - C 60 (7), and the Pc precursors, [m,p,m′-( C 14 O )3 PhO ]6 PcCu - OFBA (6) and [m,p,m′-( C 14 O )3 PhO ]6 PcCu - OH (5), and established their mesomorphism by using a polarizing optical microscope, a differential scanning calorimeter and a small angle X-ray diffractometer. Very interestingly, their corresponding previous parent Pc derivative, [m,p,m′-( C 14 O )3 PhO ]8 PcCu (4), shows a very wide temperature region ca. 90°C of a bicontinuous Cub(Pn3m) mesophase, whereas the present children Pc precursors (5 and 6) and Pc- C 60 dyad 7 show not the Cub mesophase but a Colho mesophase. It is also noteworthy that the staking distance in the Colho mesophase of the Pc- C 60 dyad 7was a very big value of ca. 9.1 Å, which is the biggest in discotic liquid crystals to our best knowledge. It may be originated from the biggest excluded volume caused by thermal fluctuation of peripheral long alkoxy chains at m, m′-positions. The excluded volume caused by thermal fluctuation of the peripheral long chains is so big that the molecular shape of the Pc derivative 4 and the Pc- C 60 dyad 7 very resembles a flat pumpkin.