2024-03-29T05:43:50Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/838252022-11-17T02:08:08Zhdl_2115_20045hdl_2115_139Coordination Geometrical Effect on Ligand-to-Metal Charge Transfer-Dependent Energy Transfer Processes of Luminescent Eu(III) Complexesda Rosa, Pedro Paulo FerreiraMiyazaki, ShioriSakamoto, Haruna1000090740093Kitagawa, YuichiMiyata, KiyoshiAkama, TomokoKobayashi, Masato1000020271645Fushimi, KojiOnda, KenTaketsugu, Tetsuya1000080324797Hasegawa, Yasuchikaopen accessThis 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.Coordination geometryLMCTEuropiumLuminescenceβ-diketonatePhotophysical 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.American Chemical Society2021-01-14engjournal articleAMhttp://hdl.handle.net/2115/83825https://doi.org/10.1021/acs.jpca.0c093371089-5639Journal of physical chemistry A1251209217https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/83825/1/Final%20version_revised2_paper.pdfapplication/pdf1.66 MB2021-01-14https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/83825/2/Supp%20Info_revised2.pdfapplication/pdf1.26 MB2021-01-14