Systematic studies on side-chain structures of phthalocyaninato-polysiloxanes: Polymerization and self-assembling behaviors

A series of dihydroxysilicon phthalocyanines having soluble side chains were synthesized and their bulk-state polymerization capability was investigated. Detailed spectroscopic study of the obtained phthalocyaninato-polysiloxanes revealed that strong electron donating ability and small steric hindrance of the peripheral substituents are the dominant factors to afford high-molecular weight polymers. The polymers show the behaviors of columnar liquid crystal (LC), which is clarified by the presence of clear X-ray diffraction patterns with a hexagonal lattice and birefringent textures in polarized optical microscopy. Because of the siloxane covalent bonds through central silicon atoms, phthalocyaninato-polysiloxanes accommodate one-dimensional phthalocyanine arrays with strong π-electronic couplings, thus exhibiting colmnar LC property even for the derivatives carrying short peripheral chains and leading to the relatively higher density of π-electron systems in the materials. This tendency is different from typical discotic small molecules that require optimum side chain structures for LC formation.