Bis(diphenyl)phosphinomethane Platinum(II) complex of 1-(benzo[d]thiazol-2-yl)-3-phenylthiourea: Crystal structure and DFT study

Abstract

This study extensively describes synthesizing and characterizing a novel Pt(II) thiourea complex and its mixed ligand bisdiphenylphosphinomethane complex. The first complex [Pt(BtztH)2] is obtained by reacting K2PtCl4 and 1-(benzo[d]thiazol-2-yl)-3-phenylthiourea in 1:2 molar ratio. The second complex [Pt(Btzt)(dppm)] was synthesized by reacting dichlorobis(diphenyl)phosphinomethane platinum(II) complex with 1-(benzo[d]thiazol-2-yl)-3-phenylthioure in equimolar ratio with the presence of Et3N. Both complexes adopt square planar geometry, which were determined by FT-IR, 1H-nmr and X-ray crystallography. In comparison with the first complex, the second complex has doubly deprotonated, resulting in a dianion Pt(II) complex, which was determined by X-ray single crystal measurement. The asymmetric unit contained two unique molecules with distorted square planar geometry. A couple of non-covalent or intermolecular interactions stabilized the solid-state supramolecular assembly. Hirshfeld surface analysis was conducted in order to have a deeper understanding of the supramolecular assembly. Enrichment ratio calculations determined the pair of chemical species with the highest propensity for making interatomic contact. The [Pt(Btzt)(dppm)] compound was also investigated theoretically. The DFT study was performed by using B3LYP/Def2-TZVP method. Theoretical findings indicate that the HOMO-LUMO gaps range from 2.2 to 3.22 eV, indicating that the compounds possess favorable semiconductor properties. Within these complexes, the coordinated atoms exhibit strong electron donations to the Pt cation, while the Pt cation demonstrates significant back-donation to the ligand.