Supramolecular Assembly of Metal Complexes by (Aryl)I⋯dz2[PtII] Halogen Bond

Abstract

The theoretical data for the half‐lantern complexes [Pt(C^N)(μ‐S^N)] 2 ( 1 – 3 ; С^N is cyclometalated 2‐Ph‐benzothiazole; S^N is 2‐SH‐pyridine 1 , 2‐SH‐benzoxazole 2 , 2‐SH‐tetrafluorobenzothiazole 3 ) indicate that the Pt···Pt orbital interaction leads to an increment of the nucleophilicity of the outer d z 2 ‐orbitals to provide assembly with electrophilic species. 1 – 3 were co‐crystallized with bifunctional halogen bond (XB) donors to give adducts ( 1 – 3 ) 2 ∙(1,4‐diiodotetrafluorobenzene) and infinite polymeric [ 1 ·1,1’‐diiodoperfluorodiphenyl] n . X‐ray crystallography revealed that the supramolecular assembly is achieved via (Aryl)I∙∙∙ d z 2 [Pt II ] XB between iodine σ‐holes and lone pairs of the positively charged (Pt II ) 2 centers, acting as nucleophilic sites. The polymer includes a curved linear chain ···Pt 2 ···I(arene F )I···Pt 2 ··· involving XB between iodines of the perfluoroarene linkers and (Pt II ) 2 moieties. The 195 Pt NMR, UV‐vis, and CV studies indicate that XB is preserved in CH(D) 2 Cl 2 solutions.