Composing NLO Chromophore as a Puzzle: Electrochemistry-based Approach to Design and Effectiveness

A series of D-pi-A, D-pi-D '-pi-A, D-pi-A '-pi-A nonlinear optical chromophores with vinylene pi-electron bridges or bridges with pi-deficient/pi-excessive heterocyclic moieties along with the corresponding precursors D-vinylene, D-pi-D ', D '-pi-A, D-pi-A ' and A '-pi-A are synthesized and studied both experimentally and computationally. The effect of the heterocycle in the pi-electron bridge on the oxidation/reduction potentials and the energy gap (Delta E-el) is investigated in detail. The properties of the D-pi-A '(D ')-pi-A chromophores are shown to correlate with those of building blocks: the oxidation potential is determined by the D-vinylene, and the reduction potential is determined by A '(D ')-pi-A truncated compounds. The contribution of the acceptor to the oxidation potential of chromophores in comparison with those of the precursors was estimated and analyzed in terms of electronic communication between the end groups. A good correlation between the Delta E-el and the chromophores' first hyperpolarizability is revealed.