Second order non-linear optical activity of arsenic and antimony dithiolene complexes

Abstract

Synthesis and characterization of dithiolene complexes of arsenic and antimony in trivalent state have been reported. A four coordinated structural motif results in a ladder like arrangement in the arsenic complex due to the inter-anionic As–S interaction which is replaced by Sb–π interaction with the counter cation in the solid state structure of the similar antimony complex. Electronic structure calculations on ground state geometries and the time-dependent density functional theoretical calculations were performed in order to characterize the absorption spectra incorporating solvent effects. Notably, both the complexes display intense second order optical non-linearity as has been determined using hyper-Rayleigh scattering technique in dichloromethane solution and the results are corroborated by DFT calculations.