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

The theoretical data for the half‐lantern complexes [{Pt( )(μ‐ )}₂] [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)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 [Pt^II] XBs 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 ⋅⋅⋅Pt₂⋅⋅⋅I(arene^F)I⋅⋅⋅Pt₂⋅⋅⋅ involving XB between iodine atoms of the perfluoroarene linkers and (Pt^II)₂ moieties. The ¹⁹⁵Pt NMR, UV/Vis, and CV studies indicate that XB is preserved in CH(D)₂Cl₂ solutions.