Multiply biphenyl substituted zinc(II) porphyrin and phthalocyanine as components for molecular materials

Abstract

The preparation and physico-chemical characteristics of zinc(II) porphyrin and phthalocyanine derivatives with biphenyl units are reported. These compounds have been prepared as components for molecular electronics systems and rotor-based molecular machines, where the biphenyl units can act as paddles because they are oriented quasi-perpendicularly to the plane of the aromatic macrocycles which would be coordianted through the transition metal ion by an axial ligand. The minimalist design along with the absence of solubilizing groups leads to a low solubility of the compounds in organic solvents; the phthalocyanines is only sparingly soluble while the porphyrin is more easily manipulated, but in any case the concentration of both compounds is sufficient for surface deposition. The luminescence of the compounds is characteristic of the central unit, although it is clear in the absorption spectra that the phthalocyanine derivative has a particularly strong tendency to aggregate non-specifically. The porphyrin forms microcrystals while the phthalocyanines which bears eight biphenyl units forms amorphous aggregates from 1,2-dichlorobenzene reminiscent of glasses of other biphenyl derivatives, which is interesting for the preparation of amorphous materials for optics applications.