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Coordination Geometrical Effect on Ligand-to-Metal Charge Transfer-Dependent Energy Transfer Processes of Luminescent Eu(III) Complexes
| Title: | Coordination Geometrical Effect on Ligand-to-Metal Charge Transfer-Dependent Energy Transfer Processes of Luminescent Eu(III) Complexes |
| Authors: | da Rosa, Pedro Paulo Ferreira Browse this author | | Miyazaki, Shiori Browse this author | | Sakamoto, Haruna Browse this author | | Kitagawa, Yuichi Browse this author →KAKEN DB | | Miyata, Kiyoshi Browse this author | | Akama, Tomoko Browse this author | | Kobayashi, Masato Browse this author | | Fushimi, Koji Browse this author →KAKEN DB | | Onda, Ken Browse this author | | Taketsugu, Tetsuya Browse this author | | Hasegawa, Yasuchika Browse this author →KAKEN DB |
| Keywords: | Coordination geometry | | LMCT | | Europium | | Luminescence | | β-diketonate |
| Issue Date: | 14-Jan-2021 |
| Publisher: | American Chemical Society |
| Journal Title: | Journal of physical chemistry A |
| Volume: | 125 |
| Issue: | 1 |
| Start Page: | 209 |
| End Page: | 217 |
| Publisher DOI: | 10.1021/acs.jpca.0c09337 |
| Abstract: | 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 pi-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 pi-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 D-5(0) -> F-7(J) 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. |
| Rights: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of physical chemistry A, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpca.0c09337. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/83825 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 長谷川 靖哉
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