Two Chiral EuIII Enantiomeric Pairs with Significantly Enhanced Photophysical and Third-Harmonic Generation Performances through the Coordination Roles of Enantiopure Bi- and Tridentate N-Donors

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-06-03 DOI:10.1021/acs.inorgchem.5c01372

Xiaodi Du, Chunyang Li, Congli Gao, Xiaoyu Cai, Jinying Huang, Qianrong Li, Tao Wu, Xi-Li Li

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Abstract

For inserting enantiopure bi- and tridentate N-donors (¹L_R/¹L_S and ²L_R/²L_S) into the precursor Eu(hfac)₃(H₂O)₂ to replace two H₂O molecules, respectively, two pairs of chiral eight- and nine-coordinate Eu^III enantiomers Eu(hfac)₃(¹L_R)/Eu(hfac)₃(¹L_S) (D-1/L-1) and Eu(hfac)₃(²L_R)/Eu(hfac)₃(²L_S) (D-2/L-2) were isolated, in which hfac^– = hexafluoroacetylacetonate, ¹L_R/¹L_S = (−)/(+)-4,5-pinene-2,2′-bipyridine, and ²L_R/²L_S = (−)/(+)-2,6-bis(4′,5′-pinene-2′-pyridyl)pyridine. Compared with Eu(hfac)₃(H₂O)₂, two chiral Eu^III enantiomeric pairs not only show significant improvements in their photophysical performances but also display highly boosted third-harmonic generation (THG) effects, and the THG strengths of D-1/L-1 and D-2/L-2 are more than 14 and 27 times that of Eu(hfac)₃(H₂O)₂, respectively. Especially, D-2 and L-2 with symmetric tridentate N-donors only have strong THG effects, while D-1 and L-1 with asymmetric bidentate N-donors simultaneously hold THG and SHG (second-harmonic generation) responses. More notably, from Eu(hfac)₃(H₂O)₂ to eight-coordinate D-1 and L-1, and further to nine-coordinate D-2 and L-2, their THG strengths present successive considerable enhancements as degrees of π-electron conjugation of their ligands continue to rise. Furthermore, the circularly polarized luminescence (CPL) properties of two chiral Eu^III enantiomeric pairs were also examined.

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两个手性EuIII对映体通过对映纯双和三齿n给体的配位作用显著增强光物理和三次谐波产生性能

为了在Eu(hfac)3(H2O)2前体中分别插入双、三叉对映体n给体（1LR/1LS和2LR/2LS）以取代2个H2O分子，分离出2对手性8位和9位EuIII对映体Eu(hfac)3(1LR)/Eu(hfac)3(1LS) （D-1/L-1）和Eu(hfac)3(2LR)/Eu(hfac)3(2LS) (D-2/L-2)，其中hfac - =六氟乙酰丙酮，1LR/1LS =(−)/(+)-4,5-蒎烯-2,2 ' -吡啶，2LR/2LS =(−)/(+)-2,6-双（4 ',5 ' -蒎烯-2 ' -吡啶）吡啶。与Eu(hfac)3(H2O)2相比，两对手性EuIII对映体不仅光物理性能得到显著改善，而且三次谐波产生（THG）效应得到显著增强，其中D-1/L-1和D-2/L-2的THG强度分别是Eu(hfac)3(H2O)2的14倍和27倍以上。其中，对称三齿氮供体的D-2和L-2仅具有较强的THG效应，而非对称双齿氮供体的D-1和L-1同时具有THG和SHG（二次谐波产生）响应。更值得注意的是，从Eu(hfac)3(H2O)2到八坐标的D-1和L-1，再到九坐标的D-2和L-2，它们的THG强度随着配体π-电子共轭度的不断提高而显著增强。此外，还研究了两种手性EuIII对映体的圆偏振发光（CPL）性质。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.