Multinuclear Ag Clusters Sandwiched by Pt Complex Units: Fluxional Behavior and Chiral-at-Cluster Photoluminescence

Multinuclear Ag clusters sandwiched by Pt complex units were synthesized and characterized by single crystal X-ray diffraction and NMR studies. The sandwich-shaped multinuclear Ag complexes showed two different types of fluxional behavior in solution: rapid slippage of Pt complex units on the Ag₃ core and a reversible demetalation-metalation reaction by the treatment with Cl anion and Ag ion, respectively. The Ag₂ complex obtained by demetalation reaction from the Ag₃ complex displayed U to Z isomerization. These multinuclear Ag complexes showed strong photoluminescence whose properties depended on the existence of Pt→Ag dative bonds. The Ag₃ complex, identified to be "chiral-at-cluster", was optically resolved by the formation of a diastereomeric salt with a chiral anion. The enantiomers show circular dichroism (CD) and circularly polarized luminescence (CPL) properties which is unprecedented for compounds based on a chiral sandwich structure. Theoretical calculations allow to understand their structural features and photophysical properties.