Coordination Geometrical Effect on Ligand-to-Metal Charge Transfer-Dependent Energy Transfer Processes of Luminescent...

Photophysical properties of europium (Eu(III)) complexes are affected by ligand-to-metal charge transfer (LMCT) states. Two luminescent Eu(III) complexes with three tetramethylheptadionates (tmh) and pyridine (py), [Eu(tmh)₃(py)₁] (seven-coordinated monocapped-octahedral structure) and [Eu(tmh)₃(py)₂] (eight-coordinated square antiprismatic structure), were synthesized for geometrical-induced LMCT level control. Distances between Eu(III) and oxygen atoms of tmh ligands were estimated using single-crystal X-ray analyses. The contribution percentages of π-4f mixing in HOMO and LUMO at the optimized structure in the ground state were calculated using DFT (LC-BLYP). The Eu-O distances and their π-4f mixed orbitals affect the energy level of LMCT states in Eu(III) complexes. The LMCT energy level of an eight-coordinated Eu(III) complex was higher than that of a seven-coordinated Eu(III) complex. The energy transfer processes between LMCT and Eu(III) ion were investigated using temperature-dependent and time-resolved emission lifetime measurements of ⁵D₀ → ⁷F transitions of Eu(III) ions. In this study, the LMCT-dependent energy transfer processes of seven- and eight-coordinated Eu(III) complexes are demonstrated for the first time.