[Au(S–C ₆ F ₅ )] and [Au(S–C ₆ F ₄ –CF ₃ )]: Reactivity, Structure, DSC, and Calculation Studies

Reactions of HS-Ar^f (S-Ar^f = S-C₆F₅, S-C₆F₄-CF₃) with Au^I utilizing a new atom-economy method result in corresponding [Au(S-Ar^f)]_<i>n</i> metal-organic coordination polymers, which were studied by DSC, SEM-EDX, TGA, IR, and PL. Treatment of these complexes with pyridine under mild conditions results in the transformation of the starting polymers into new [{Au(py)₂}{Au(S-Ar^f)₂}]_<i>n</i> complexes of the polymeric structure, which were isolated and characterized by single-crystal X-ray diffraction (SCXRD). The linear [Au(py)₂]⁺ cations combine with linear [Au(S-Ar^f)₂]^- anions via Au···Au interactions into infinite chains. Such interactions were studied by quantum-chemical calculations. Treatment of [Au(S-C₆F₄-CF₃)]_<i>n</i> with DMSO gives crystals of [Au₄(S-C₆F₄-CF₃)₄]_<i>n</i>·<i>n</i>DMSO that have a unique polymeric structure.