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具有光调制手性光学性质的三链铕螺旋配合物的非对映选择性自组装。

Diastereoselective self-assembly of a triple-stranded europium helicate with light modulated chiroptical properties.

作者信息

Zhang Zhihui, Zhou Yanyan, Gao Ting, Yan Pengfei, Zou Xiaoyan, Li Hongfeng

机构信息

Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education; School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China.

出版信息

Dalton Trans. 2021 Apr 7;50(13):4604-4612. doi: 10.1039/d1dt00251a. Epub 2021 Mar 12.

Abstract

Chiroptical photoswitches are of increasing interest for their potential in advanced information technologies. Herein, an achiral bis-β-diketonate ligand (o-L) with a photoresponsive diarylethene moiety as a linker was designed, which co-assembled with Eu ions and R- and S-bis(diphenylphosphoryl)-1,10-binaphthyl (R/S-BINAPO) as chiral ancillaries to form dinuclear triple-stranded helicates, [Eu(o-L)(R/S-BINAPO)]. The helicates in the enantiopure form were confirmed by H, F, P NMR and DOSY NMR analyses. Furthermore, the mirror-image CD and CPL spectra also demonstrate the existence of stable ground- and excited-state chiralities in solution. When exposed to alternate ultraviolet and visible light, the helicates showed reversible color variations from colorless to purple, followed by the presence of light-triggered quadruple optical and chiroptical outputs, named CD, PL, CPL and g switches. With these light-modulated optical outputs, the possibility for the fabrication of IMPLICATION and INHIBIT logic gates was discussed.

摘要

手性光开关因其在先进信息技术中的潜力而越来越受到关注。在此,设计了一种非手性双β-二酮配体(o-L),其具有作为连接基的光响应性二芳基乙烯部分,该配体与铕离子以及作为手性辅助剂的R-和S-双(二苯基磷酰基)-1,10-联萘(R/S-BINAPO)共同组装形成双核三链螺旋配合物[Eu(o-L)(R/S-BINAPO)]。通过氢、氟、磷核磁共振和扩散排序核磁共振分析证实了对映体纯形式的螺旋配合物的存在。此外,镜像圆二色光谱和圆偏振发光光谱也证明了溶液中存在稳定的基态和激发态手性。当暴露于交替的紫外光和可见光下时,螺旋配合物显示出从无色到紫色的可逆颜色变化,随后出现光触发的四重光学和手性光学输出,即圆二色性(CD)、光致发光(PL)、圆偏振发光(CPL)和g开关。利用这些光调制光学输出,讨论了制造蕴含和抑制逻辑门的可能性。

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