Highly emissive polymorphs of anhydrous cadmium tetracyanoplatinate and their solvated coordination networks

Abstract

Two anhydrous polymorphs of cadmium cyanoplatinate Cd[Pt(CN)₄] coordination polymers have been synthesized and thermally, spectroscopically, and structurally characterized. α-Cd[Pt(CN)₄] and β-Cd[Pt(CN)₄] are densely packed, highly emissive 3-D solids, with quantum yields of 0.85 (λ_em = 520 nm) and 0.79 (λ_em = 448 nm) respectively. Their mutual hydrate, Cd(H₂O)[Pt(CN)₄]·2H₂O, forms a complex 3-D coordination polymer with Cd–O–Cd bridges and Pt–Pt interactions. Additionally, exposure of solid α-Cd[Pt(CN)₄] and β-Cd[Pt(CN)₄] to several solvent vapours results in the formation of 2-D cyanometallate sheets of the adduct compounds CdL₂[Pt(CN)₄] (L = DMSO, DMF, and pyridine). Cd(pyridine)₂[Pt(CN)₄] shows a significantly lower quantum yield (0.32) in comparison to the parent Cd[Pt(CN)₄] coordination polymers. Upon heating CdL₂[Pt(CN)₄] preferentially forms the kinetic product α-Cd[Pt(CN)₄].