Mitra Joyee, Pal Kuntal, Sarkar Sabyasachi
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, UP, India.
Dalton Trans. 2013 Oct 14;42(38):13905-11. doi: 10.1039/c3dt51585k. Epub 2013 Aug 7.
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.
三价砷和锑的二硫烯配合物的合成与表征已有报道。由于阴离子间的As-S相互作用，四配位结构单元在砷配合物中形成类似梯子的排列，而在类似锑配合物的固态结构中，这种相互作用被与抗衡阳离子的Sb-π相互作用所取代。为了表征包含溶剂效应的吸收光谱，进行了基态几何结构的电子结构计算和含时密度泛函理论计算。值得注意的是，使用超瑞利散射技术在二氯甲烷溶液中测定，这两种配合物均显示出强烈的二阶光学非线性，密度泛函理论计算也证实了该结果。
