Alkali Metal–Substitution–Induced Confinement Effect for Designing High Phase–Transition–Temperature Molecular–Based Compounds Exhibiting Strong Photoluminescence.

Organic–inorganic hybrid phase–transition molecular materials have attracted increasing attention due to their excellent properties of combining inorganic and organic components. However, few research has been conducted on rare‐earth–based bimetallic organic–inorganic hybrids. Here, we successfully constructed a series of rare–earth–based organic–inorganic hybrid multifunctional materials, (C6H14N2)2EuX(NO3)6O2 (X=Na, K, Rb), with reversible phase transition, switchable dielectric, photoluminescence and semiconductor properties. Specifically, the phase‐transition temperature of three compounds are determined to be 364, 405 and 440 K, respectively. By the confinement effect caused by the variation of alkali metal elements in the two–dimensional structure, the phase transition temperature is successfully increased by 76 K. Meanwhile, the solid–state photoluminescence of three compounds displays bright red light at room temperature. Additionally, the bandgaps of three compounds are determined to be 3.21, 3.53 and 3.32 eV, respectively. It is expected that the strategy of alkali metal substitution proposed in this work will provide new thoughts for the design of multifunctional organic‐inorganic hybrid crystals. [ABSTRACT FROM AUTHOR]