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

• A series of platinum(II) cyclometalated isocyanide complexes were prepared. • The X-ray diffraction data suggest the presence of (isocyano group)•••PtII interactions. • The isocyano nitrogen atom acts as a π-hole donor toward a d z 2-orbital of PtII atom. • Non-covalent interactions were studied by DFT calculations (NCI and QTAIM methods). • The CSD analysis verified more examples of (isocyano group)•••[ d9 -/ d8 -M] interactions. A series of platinum(II) isocyanide complexes [Pt(ppy)Cl(CNR)] (ppy = 2-phenylpyridinato-C2, N; R = Mes 1 , C 6 H 2 –2,6-Me 2 –4-Br 2 , C 6 H 2 –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)···PtII interactions where the nitrogen atom of the isocyano group acts as a π-hole donor toward a d z 2-orbital of PtII. 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 d9 and d8 - metal-centers (AuI, AuIII, AgI, PtII, PdII, NiII, RhI) to be performed. [Display omitted] [ABSTRACT FROM AUTHOR]