Intermolecular (Isocyano group)•••PtII interactions involving coordinated isocyanides in cyclometalated PtII complexes

A series of platinum(II) isocyanide complexes [Pt(ppy)Cl(CNR)] (ppy = 2-phenylpyridinato-C-2, N; R = Mes 1, C6H2-2,6-Me-2-4-Br 2, C6H2-2-F-3-Cl-4-Br 3, naphthalen-2-yl 4) were prepared and characterized by high resolution ESI-MS, 1D and 2D NMR, IR, UV-Vis absorption, and photoluminescence spectroscopies, as well as single-crystal X-ray diffraction. Analysis of X-ray diffraction data allowed us to identify (isocyano group)center dot center dot center dot Pt-II interactions where the nitrogen atom of the isocyano group acts as a pi-hole donor toward a d(z)(2)-orbital of Pt-II. The presence of these noncovalent interactions was confirmed by DFT calculations followed by NCI analysis and topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method). Processing of CSD data allowed verification of the contacts between coordinated isocyano moieties and various d(9) and d(8)- metal-centers (Au-I, Au-III, Ag-I, Pt-II, Pd-II, Ni-II, Rh-I) to be performed. (c) 2021 Elsevier B.V. All rights reserved.

Automated summary

A series of platinum(II) isocyanide complexes were synthesized and characterized in this study. Noncovalent interactions between the isocyanide group and platinum atom were identified using X-ray diffraction analysis and confirmed by DFT calculations and analysis of the electron density distribution. The contacts between the isocyanide moiety and various metal centers were also verified.