Supramolecular Assembly of Metal Complexes by (Aryl)I⋅⋅⋅d[PtII] Halogen Bonds

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.