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

The theoretical data for the half-lantern complexes [{Pt( )(μ- )} ] [1-3; is cyclometalated 2-Ph-benzothiazole; is 2-SH-pyridine (1), 2-SH-benzoxazole (2), 2-SH-tetrafluorobenzothiazole (3)] indicate that the Pt⋅⋅⋅Pt orbital interaction increases the nucleophilicity of the outer d orbitals to provide assembly with electrophilic species. Complexes 1-3 were co-crystallized with bifunctional halogen bonding (XB) donors to give adducts (1-3) ⋅(1,4-diiodotetrafluorobenzene) and infinite polymeric [1⋅1,1'-diiodoperfluorodiphenyl] . X-ray crystallography revealed that the supramolecular assembly is achieved through (Aryl)I⋅⋅⋅d [Pt ] XBs between iodine σ-holes and lone pairs of the positively charged (Pt ) centers acting as nucleophilic sites. The polymer includes a curved linear chain ⋅⋅⋅Pt ⋅⋅⋅I(arene )I⋅⋅⋅Pt ⋅⋅⋅ involving XB between iodine atoms of the perfluoroarene linkers and (Pt ) moieties. The Pt NMR, UV/Vis, and CV studies indicate that XB is preserved in CH(D) Cl solutions.