Push–pull thiophene chromophores for electro-optic applications: from 1D linear to β-branched structures

Abstract

We report the synthesis and characterization of a novel series of push–pull chromophores bearing 1D linear and β-branched thiophenes as π-conjugated spacers between a 2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline electron donor unit and dicyano- and tricyanovinylene electron acceptor groups. The effect of the introduction of β-thiophenes on the linear and nonlinear (NLO) optical properties as well as electrochemical and thermal data is studied in detail by performing a comparative study between the branched and 1D linear systems. In addition, a parallel DFT computational study is used to evaluate structure–property relationships. The non-linear optical behavior of the molecules both in solution and in solid state as electro-optic (EO) films using a guest–host approach shows very promising performance for electro-optic applications with high molecular first hyperpolarizabilities (μβ) of 4840 × 10⁻⁴⁸ esu and electro-optic coefficients r₃₃ reaching 650 pm V⁻¹. One highlight is that the electro-optic films of the β-branched chromophores are superior in terms of thermal stability in device operation as measured by a transmissive modified reflective Teng-Man method. This work provides guidelines for the design of improved electro-optic materials including β-branched chromophores which could be useful for practical EO applications, where both enhanced β and r₃₃ values together with chemical and thermal stability are necessary.