Supramolecular Assembly of Metal Complexes by (Aryl)I⋅⋅⋅d z 2 [Pt II ] Halogen Bonds

The theoretical data for the half‐lantern complexes [{Pt( C N ^ )(μ‐ S N ^ )} 2 ] [ 1 – 3 ;C 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 increases the nucleophilicity of the outer dz2orbitals 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 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 iodine atoms 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.