Second hyperpolarizability of ethynyl-linked azobenzene molecular wires.

A series of oligomers consisting of ethynyl-linked azobenzene units was prepared using Pd-catalyzed cross coupling. The linear and nonlinear optical properties of the oligomers were investigated. The molecular second hyperpolarizability, gamma, followed the power law gamma proportional, variant n(2.12+/-0.05) (n is the number of repeat units) for unusually large molecular lengths exceeding 360 conjugated bonds (>49 nm). The exceptional exciton delocalization length is attributed to the rigidity of the conjugated backbone.