Discotic liquid crystals of transition metal complexes 38†: peripheral chain substituent position effect on columnar mesophase and stacking structures of novel phthalocyanine-based liquid crystals

In order to clarify the peripheral chain substitution position effect on columnar mesophase and stacking structures, we have synthesized three novel series of discotic liquid crystals (1-3) having octakis(phenoxy)phthalocyaninato copper(II) as a central core and one peripheral chain at the para position (1), meta position (2) or ortho position (3) of each phenoxy group, and three more novel series of discotic liquid crystals (4-6) having the same central core and two peripheral chains at para and meta positions (4), meta and meta positions (5) or ortho and meta positions (6) of each phenoxy group. Their columnar mesophase and stacking structures were investigated with a polarizing optical microscope, a differential scanning calorimeter and a temperature-dependent X-ray diffractometer. According to the results, their columnar mesophase and stacking structures strongly depended on the peripheral chain substitution positions and the number of peripheral chains. Derivatives 3 and 5 are viscous isotropic liquid at room temperature. Derivatives 1, 2, 4 and 6 exhibit various kinds of columnar mesophases: 1 Colhd; 2 Colhd and Colho; 4 Colhd, Colrd(P21/a), Coltet.d and Cub ( Pn [ three bar ] m ); 6 Colhd, Colrd(P21/a) and Colrd(X). Moreover, derivatives 1, 4 and 6 exhibit disordered columnar mesophases. However, derivative 2 only exhibits an ordered columnar mesophase and its X-ray diffraction pattern shows a sharp reflection corresponding to a very short intracolumnar stacking distance of 3.33 Å. Thus, we can drastically change the mesophase and stacking structures by the peripheral chain substitution positions and the number of peripheral chains at each phenoxy group. This is a new way of controlling mesomorphic structure.