Metal-involved C???d_z2-Pt^II tetrel bonding as a principal component of the stacking interaction between arenes and the platinum(II) square-plane

The half-lantern Pt-2(II) complexes [Pt((CN)-N-boolean AND)(mu-(SN)-N-boolean AND)](2) ((CN)-N-boolean AND = 2-naphtylbenzothiazolate 1; 2-phenylbenzothiazolate 2; (SN)-N-boolean AND = 2-thiopyridine) were crystallized with electron-deficient arenes such as hexafluorobenzene (C6F6) and octafluoroanthraquinone (OFA) to furnish cocrystals 1 center dot C6F6, 2 center dot C6F6, and 1 center dot(OFA)(2), all studied by X-ray crystallography. The obtained structural data revealed that structure-determining pi-pi stacking occurred between the arenes and metal square-planes. Density functional theory calculations, employing a set of computational tools, verified the contribution of the C center dot center dot center dot d(z)(2)-Pt-II noncovalent bond in the overall stacking forces. Orbital interaction analysis using the charge displacement function (CDF) combined with the extended transition state natural orbital for chemical valence theory (ETS-NOCV) method demonstrated the significance of the d(z2)(Pt) -> pi*(C) charge-transfer interaction, which allows the attribution of the C center dot center dot center dot Pt contact to a metal-involved tetrel bonding. Many-body interaction analysis demonstrates a positive cooperative effect between the fragments of the half-lantern complex and the perfluoroarenes favoring the occurrence of supramolecular chains.