Supramolecular Assembly of Metal Complexes by (Aryl)I...dz2 [PtII] Halogen Bonds

The theoretical data for the half-lantern complexes [{Pt(CN<^>)(mu-SN<^>)}(2)] [1-3; CN<^> is cyclometalated 2-Ph-enzothiazole; SN<^> 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 dz2 orbitals to provide assembly with electrophilic species. Complexes 1-3 were co-crystallized with bifunctional halogen bonding (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 through (Aryl)I...dz2[Pt-II] XBs between iodine sigma-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 iodine atoms of the perfluoroarene linkers and (Pt-II)(2) moieties. The Pt-195 NMR, UV/Vis, and CV studies indicate that XB is preserved in CH(D)(2)Cl-2 solutions.