Luminescence Tunable Europium and Samarium Complexes: Reversible On/Off Switching and White-Light Emission

Single-molecule functional materials with luminescence tunable by external stimuli are of increasing interest due to their application in sensors, display devices, biomarkers, and switches. Herein, new europium and samarium complexes with ligands having triphenylamine (TPA) groups as the redox center and 2,2'-bipyridine (bpy) as the coordinating groups and diketonate (tta) as the second ligand have been constructed. The complexes show white-light emission in selected solvents for proper mixtures of the emission from Ln³⁺ ions and the ligands. Meanwhile, they exhibit reversible luminescence switching on/off properties by controlling the external potential owing to intramolecular energy transfer from the Ln³⁺ ions to the electrochemically generated radical cation of TPA. Time-dependent density functional theory (TD-DFT) calculations have been performed to study the electronic spectra. The proposed intramolecular energy transfer processes have been verified by density functional theory (DFT) studies.