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RESEARCH PRODUCT

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

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The theoretical data for the half-lantern complexes [{Pt( CN^ )(μ- SN^ )}2 ] [1-3; CN^ is cyclometalated 2-Ph-benzothiazole; 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 d z2 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⋅⋅⋅d z2 [PtII ] XBs between iodine σ-holes and lone pairs of the positively charged (PtII )2 centers acting as nucleophilic sites. The polymer includes a curved linear chain ⋅⋅⋅Pt2 ⋅⋅⋅I(areneF )I⋅⋅⋅Pt2 ⋅⋅⋅ involving XB between iodine atoms of the perfluoroarene linkers and (PtII )2 moieties. The 195 Pt NMR, UV/Vis, and CV studies indicate that XB is preserved in CH(D)2 Cl2 solutions.