The important role of the isolation group (TBDPS) in designing efficient organic nonlinear optical FTC type chromophores

Abstract

Highly efficient and thermally stable nonlinear optical chromophores based on the same thiophene π-conjugation and tricyanofuran acceptor (TCF) possessing different isolation groups attached to electron-donating moiety have been synthesized and systematically investigated in this paper. Density functional theory (DFT) was used to calculate the HOMO–LUMO energy gaps and first-order hyperpolarizability (β) of these chromophores. These new chromophores showed excellent thermal stability with their decomposition temperatures all above 250 °C. Most importantly, the molecular hyperpolarizability of these chromophores can be effectively translated into large electro-optic (EO) coefficients (r33) in poled polymers. The doped films-B containing 25 wt % chromophore F1 displayed an r33 value of 52 pm/V at 1310 nm, and the doped films-C containing F2 showed a value of 91 pm/V at the concentration of 35 wt %. These values are all much higher than the traditional FTC chromophore (39 pm/V). These results revealed that the introduced isolation group can reduce intermolecular electrostatic interactions thus enhance the macroscopic EO activity. Besides, the position of the isolation group plays an equally important role in achieving the ultra large EO coefficients of materials. These properties, together with the good solubility, suggest the potential use of these new chromophores as advanced materials devices.