对映纯 Eu2L4 复合物中不同寻常的溶剂调节金属立体中心反转：CPL 反转的新策略

IF 6.1 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers Pub Date : 2024-10-05 DOI:10.1039/D4QI02276A

Qing Ma, Sen Yin, Ziye Song, Ting Gao, Pengfei Yan, Yanyan Zhou and Hongfeng Li

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引用次数: 0

摘要

开发具有刺激响应螺旋反转功能的人工金属螺旋体是功能超分子化学领域的一项重大挑战。然而，大多数报道的螺旋反转都是基于 P/M 构象和金属中心的 Δ/Λ 构型的同步转变，需要克服巨大的能量障碍。在此，我们报告了第一个独立于 P/M 构象转换的金属中心 Δ/Λ 构象反转实例。保持恒定 P 螺旋构象的(NMe4)2[Eu2(LR)4]螺旋体，在增加 CH3CN 中 CHCl3 的含量时，会发生局部金属中心构型转换，从ΛΛ-(NMe4)2[Eu2(LR)4]→ΔΛ-(NMe4)2[Eu2(LR)4]→ΔΔ-(NMe4)2[Eu2(LR)4]。伴随着这种转换，圆极化发光（CPL）活性发生了反转，发光不对称因子（glum 值）从 -0.23 变为 +0.44。通过了解溶剂对局部手性反转的影响，可以设计出基于镧系元素螺旋体的 CPL 光学开关或传感器。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Unusual solvent-regulated inversion of a metal stereocenter in an enantiopure Eu2L4 helicate: a new strategy for CPL inversion†

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Unusual solvent-regulated inversion of a metal stereocenter in an enantiopure Eu2L4 helicate: a new strategy for CPL inversion†

Developing artificial metal helicates with stimuli-responsive helicity inversion is a significant challenge in functional supramolecular chemistry. However, most reported helicity inversions are based on the synchronous transformation of P/M conformation and the metal center's Δ/Λ configuration, requiring the overcoming of substantial energy barriers. Herein, we report the first example of Δ/Λ configurational inversion of metal centers independent of the P/M conformational conversion. The helicate (NMe₄)₂[Eu₂(L^R)₄], maintaining a constant P helical conformation, undergoes a local metal center configurational conversion from ΛΛ-(NMe₄)₂[Eu₂(L^R)₄] → ΔΛ-(NMe₄)₂[Eu₂(L^R)₄] → ΔΔ-(NMe₄)₂[Eu₂(L^R)₄] upon increasing the content of CHCl₃ in CH₃CN. Associated with the conversion, the inversion of circularly polarized luminescence (CPL) activity took place with the luminescence dissymmetry factor (g_lum value) changing from −0.23 to +0.44. The understanding thus gained as to the solvent's impact on local chirality inversion enabled the design of CPL optical switches or sensors based on lanthanide helicates.