Reversible Humidity-Driven Transformation of a Bimetallic {EuCo} Molecular Material: Structural, Sorption, and Photoluminescence Studies.

Functional molecule-based solids built of metal complexes can reveal a great impact of external stimuli upon their optical, magnetic, electric, and mechanical properties. We report a novel molecular material, {[Eu(HO)(pyrone)][Co(CN)]}·HO (, = 2; , = 1), which was obtained by the self-assembly of Eu and [Co(CN)] ions in the presence of a small 2-pyrrolidinone (pyrone) ligand in an aqueous medium. The as-synthesized material, , consists of dinuclear cyanido-bridged {EuCo} molecules accompanied by two H-bonded water molecules. By lowering the relative humidity (RH) below 30% at room temperature, undergoes a single-crystal-to-single-crystal transformation related to the partial removal of crystallization water molecules which results in the new crystalline phase, . Both and solvates exhibit pronounced Eu-centered visible photoluminescence. However, they differ in the energy splitting of the main emission band of a D → F origin, and the emission lifetime, which is longer in the partially dehydrated . As the ↔ structural transformation can be repeatedly reversed by changing the RH value, the reported material shows a room-temperature switching of detailed luminescent features including the ratio between emission components and the emission lifetime values.