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基于硼整合腙配合物的可见光激活的联萘酚衍生的手性光学开关。

Visible light activated BINOL-derived chiroptical switches based on boron integrated hydrazone complexes.

作者信息

van Vliet Sven, Alachouzos Georgios, de Vries Folkert, Pfeifer Lukas, Feringa Ben L

机构信息

Stratingh Institute for Chemistry, Zernike Institute for Advanced Materials, University of Groningen Nijenborgh 4 Groningen 9747 AG Netherlands

EPFL CH G1 614 (Bâtiment CH), Station 6 Lausanne CH-1015 Switzerland.

出版信息

Chem Sci. 2022 Aug 10;13(33):9713-9718. doi: 10.1039/d2sc03518a. eCollection 2022 Aug 24.

Abstract

Chiral optical switches, which use light to control chirality in a reversible manner, offer unique properties and fascinating prospects in the areas of molecular switching and responsive systems, new photochromic materials and molecular data processing and storage. Herein, we report visible light responsive chiroptical switches based on tetrahedral boron coordination towards an easily accessible hydrazone ligand and optically pure BINOL. Upon instalment of a non-planar dibenzo[,]-cycloheptene moiety in the hydrazone ligand's lower half, the enantiopure boron complex shows major chiroptical changes in the CD read-out after visible light irradiation. The thermal isomerization barrier in these chiroptical switching systems showed to be easily adjustable by the introduction of substituents onto the olefinic bond of the cycloheptene ring, giving profound control over their thermal stability. The control over their thermal stability in combination with excellent reversibility, photochemical properties and overall robustness of the complexes makes these BINOL-derived chiroptical switches attractive candidates for usage in advanced applications, photonic materials and nanotechnology.

摘要

手性光学开关能够以可逆方式利用光来控制手性,在分子开关与响应系统、新型光致变色材料以及分子数据处理与存储等领域展现出独特性质和迷人前景。在此,我们报道了基于四面体硼与易于获取的腙配体及光学纯联萘酚(BINOL)配位的可见光响应型手性光学开关。在腙配体下半部分引入非平面的二苯并[,] - 环庚烯部分后,对映体纯的硼配合物在可见光照射后的圆二色性(CD)读数中显示出主要的手性光学变化。通过在环庚烯环的烯烃键上引入取代基,这些手性光学开关系统中的热异构化势垒易于调节,从而对其热稳定性进行深度控制。对其热稳定性的控制,结合出色的可逆性、光化学性质以及配合物的整体稳健性,使得这些源自联萘酚的手性光学开关成为先进应用、光子材料和纳米技术中颇具吸引力的候选者。

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