Decisive influence of the metal in multifunctional gold, silver, and copper metallacycles: High quantum yield phosphorescence, color switching, and liquid crystalline behavior

Three cyclic trinuclear pyrazolate complexes with Au(I), Ag(I), or Cu(I) have been studied. These complexes have interesting and distinct optical and thermal properties depending on the metal, namely, liquid crystalline behavior, red or deep-red phosphorescence at room temperature, thermoluminochromism, and response to silver ions. The selected ligand, 4-hexyl-3,5-dimethylpyrazolate, maximizes the effect that the nature of the metals has on the properties of the complexes, thus allowing the intermolecular metallophilic interactions to be responsible for the optical properties. Moreover, the gold and silver complexes show columnar liquid crystal phases at high temperature. All of the complexes have good solubility properties for processing as poly(methyl methacrylate) (PMMA) doped films. Films of the gold, silver, and copper complexes show interesting optical behavior such as wide-range color switching or phosphorescence turn-on upon cooling. In addition, films of the gold complex show a bright color switching (red to blue) in the presence of silver ions. The gold and copper complexes are bright phosphors with phosphorescent quantum yields of 90% in PMMA films, the highest values reported for this class of compounds at room temperature.This work was supported by MINECO-FEDER, UE (projects MAT2015-66208-C3-1-P, CTQ2015-70174-P, CTQ2014-53033-P, CTQ2016-75816C2-1-P), Gobierno de Aragón FSE, UE, and Catedra IQE (Industrias Quimicas del Ebro) for a postgraduate grant (J.C.).Peer reviewe