Coordination Geometrical Effect on Ligand-to-Metal Charge Transfer-Dependent Energy Transfer Processes of Luminescent Eu(III) Complexes

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) (py) ] (seven-coordinated monocapped-octahedral structure) and [Eu(tmh) (py)...

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Veröffentlicht in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2021-01, Vol.125 (1), p.209-217
Hauptverfasser: Ferreira da Rosa, Pedro Paulo, Miyazaki, Shiori, Sakamoto, Haruna, Kitagawa, Yuichi, Miyata, Kiyoshi, Akama, Tomoko, Kobayashi, Masato, Fushimi, Koji, Onda, Ken, Taketsugu, Tetsuya, Hasegawa, Yasuchika
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Sprache:eng
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Zusammenfassung: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) (py) ] (seven-coordinated monocapped-octahedral structure) and [Eu(tmh) (py) ] (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-4 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-4 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 D → F 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.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.0c09337