电子应变效应增强铕（III）配合物的圆偏振发光

Electronic strain effect on Eu(iii) complexes for enhanced circularly polarized luminescence.

作者信息

Tsurui Makoto, Kitagawa Yuichi, Fushimi Koji, Gon Masayuki, Tanaka Kazuo, Hasegawa Yasuchika

机构信息

Graduate School of Chemical Sciences and Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628, Japan.

Faculty of Engineering, Kita 13, Nishi 8, Kita-ku, Sapporo, 060-8628, Japan and Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo 001-0021, Japan.

出版信息

Dalton Trans. 2020 Apr 28;49(16):5352-5361. doi: 10.1039/d0dt00699h.

DOI:10.1039/d0dt00699h

PMID:32255114

Abstract

Luminescent Eu(iii) complexes with point-chiral phosphine oxide ligands, [Eu(hfa)3((R,R)-B2QPO)] (hfa: hexafluoroacetylacetonato, B2QPO: 2,3-bis(tert-butylmethylphosphine oxide)quinoxaline) and [Eu(hfa)3((R)-B3QPO)] (B3QPO: 2-tert-butylmethylphosphine oxide-3-(di-tert-butylphosphineoxide)quinoxaline), are reported for the investigation of the electronic strain effect on the coordination sphere. Single crystal X-ray crystallography reveals the strong structural strain of the hfa ligands in [Eu(hfa)3((R,R)-B2QPO)]. The emission quantum yields of [Eu(hfa)3((R,R)-B2QPO)] in solution (55%) and solid (63%) are comparable to those of previously reported bright luminescent Eu(iii) complexes. The chiroptical properties of [Eu(hfa)3((R,R)-B2QPO)] and [Eu(hfa)3((R)-B3QPO)] were characterized using circular dichroism (CD) and circularly polarized luminescence (CPL) spectra. The dissymmetry factor of [Eu(hfa)3((R,R)-B2QPO)] was estimated to be 0.08. The chiroptical phenomena of the Eu(iii) complexes are closely related to their structural (geometry) and electronic (LMCT: ligand-to-metal charge transfer) strains.

摘要

报道了具有点手性氧化膦配体的发光铕（III）配合物，即[Eu(hfa)3((R,R)-B2QPO)]（hfa：六氟乙酰丙酮，B2QPO：2,3-双（叔丁基甲基氧化膦）喹喔啉）和[Eu(hfa)3((R)-B3QPO)]（B3QPO：2-叔丁基甲基氧化膦-3-（二叔丁基氧化膦）喹喔啉），用于研究配位球上的电子应变效应。单晶X射线晶体学揭示了[Eu(hfa)3((R,R)-B2QPO)]中hfa配体的强烈结构应变。[Eu(hfa)3((R,R)-B2QPO)]在溶液（55%）和固体（63%）中的发射量子产率与先前报道的明亮发光铕（III）配合物相当。使用圆二色性（CD）和圆偏振发光（CPL）光谱对[Eu(hfa)3((R,R)-B2QPO)]和[Eu(hfa)3((R)-B3QPO)]的手性光学性质进行了表征。[Eu(hfa)3((R,R)-B2QPO)]的不对称因子估计为0.08。铕（III）配合物的手性光学现象与其结构（几何形状）和电子（配体到金属电荷转移：LMCT）应变密切相关。