New PtIIdiimine–dithiolate complexes containing a 1,2-dithiolate-1,2-closo-dicarbadodecarborane: an experimental and theoretical investigation

Pintus, Anna, Aragoni, M. Carla, Coles, Simon J., Coles (née Huth), Susanne L., Isaia, Francesco, Lippolis, Vito, Musteti, Ana-Daniela, Teixidor, Francesc, Viñas, Clara and Arca, Massimiliano (2014) New PtIIdiimine–dithiolate complexes containing a 1,2-dithiolate-1,2-closo-dicarbadodecarborane: an experimental and theoretical investigation. Dalton Transactions, 43 (36), 13649-13660. (doi:10.1039/c4dt01929f). (PMID:25100300)

Abstract

Five new [Pt(N^N)(dtoc)] complexes (; N^N = diimine: 2,2'-bipyridine and its 4,4'-alkyl/aryl-substituted derivatives or 1,10-phenanthroline; dtoc^2- = 1,2-dithiolate-1,2-closo-dicarbadodecaborane) have been synthesized and characterized by spectroscopic and electrochemical methods, and by means of X-ray diffraction in the case of complexes and . Hybrid DFT and time-dependent (TD) DFT calculations were performed on complexes and the previously reported complex [Pt(Ph₂phen)(dtoc)] (; Ph₂phen = 4,7-diphenyl-1,10-phenanthroline) both in the gas phase and in the presence of several solvents (CH₂Cl₂, CHCl₃, CH₃CN, acetone, THF, DMF, DMSO, and toluene) to gain an insight into the electronic structure of the complexes and explain their experimental features. Theoretical calculations allowed for the determination of structure-property relationships within the series of the six complexes considered, and the prediction of their second order nonlinear optical (SONLO) properties by evaluating their first static hyperpolarizabilities (β_tot).

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Contributors

Author: Simon J. Coles

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