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Enhanced Luminescence of Asymmetrical Seven-Coordinate Eu-III Complexes Including LMCT Perturbation

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Title: Enhanced Luminescence of Asymmetrical Seven-Coordinate Eu-III Complexes Including LMCT Perturbation
Authors: Yanagisawa, Kei Browse this author
Kitagawa, Yuichi Browse this author
Nakanishi, Takayuki Browse this author →KAKEN DB
Akama, Tomoko Browse this author
Kobayashi, Masato Browse this author
Seki, Tomohiro Browse this author →KAKEN DB
Fushimi, Koji Browse this author →KAKEN DB
Ito, Hajime Browse this author →KAKEN DB
Taketsugu, Tetsuya Browse this author →KAKEN DB
Hasegawa, Yasuchika Browse this author →KAKEN DB
Keywords: Lanthanides
Charge transfer
Structure elucidation
Density functional calculations
Issue Date: 1-Sep-2017
Publisher: Wiley-Blackwell
Journal Title: European journal of inorganic chemistry
Issue: 32
Start Page: 3843
End Page: 3848
Publisher DOI: 10.1002/ejic.201700815
Abstract: Luminescent mononuclear seven-coordinate Eu-III complexes, with monocapped-octahedral (point group: C-3v), monocapped-trigonal-prismatic (C-2v), and pentagonal-bipyramidal (D-5h) coordination structures, are reported. The complexes each consist of a Eu-III ion, three tetramethylheptanedionates, and a phosphine oxide derivative. Controlling steric hindrance by means of introducing methyl groups into the phosphine oxide ligands resulted in the formation of three types of coordination polyhedral structures. The coordination geometrical structures of the Eu-III complexes were evaluated by single-crystal X-ray diffraction analysis and shape-factor calculations. The radiative rate constant of the Eu-III complex with a monocapped-octahedral structure was larger than those with monocapped-trigonal-prismatic and pentagonal-bipyramidal structures. Characteristic photophysical properties of the seven-coordinate Eu-III complexes are discussed with TD-DFT calculations and Arrhenius analysis of the ligand-to-metal charge transfer.
Rights: This is the peer reviewed version of the following article: European journal of inorganic chemistry 32 3843-3848 2017-09-01 , which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
Type: article (author version)
Appears in Collections:総合化学院 (Graduate School of Chemical Sciences and Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 柳澤 慧

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