A light triggered optical and chiroptical switch based on a homochiral Eu2L3 helicate
A light triggered optical and chiroptical switch based on a homochiral Eu2L3 helicate
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DOI：
10.1039/d0tc01044h
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发表时间：
2020-05
影响因子：
6.4
通讯作者：
Jianpeng Zhang;Yanyan Zhou;Yuan Yao;Zhenyu Cheng;Ting Gao;Hongfeng Li;Pengfei Yan
中科院分区：
文献类型：
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作者：
Jianpeng Zhang;Yanyan Zhou;Yuan Yao;Zhenyu Cheng;Ting Gao;Hongfeng Li;Pengfei Yan
光学和光开关已经在先进的信息技术中找到了潜在的应用。本文设计并合成了一对手性三链螺旋体[Eu2(o-LRR)3](TOf)6和[Eu2(o-LSS)3](TOf)6，它们具有手性、发光和光刺激响应性质。o-LRR/SS配体由光致变色二乙烯基作为间隔基团和两个手性2,6-二吡啶酰胺作为配位单元组成。通过综合光谱特征，结合Sparkle/RM1模型的半经验几何优化，证实了配体末端修饰的(R/S)-1-苯乙胺成功地控制了螺旋体的立体选择性自组装。在紫外和可见光交替照射下，二乙烯经历了无色开环态和粉红色闭环态之间的可逆变化。这种光致变色过程引起了电子结构和配体构象的变化，并导致了光响应光学（UV和PL）和光致变色（ECD和CPL）开关特性的存在。因此，螺旋可以被认为是一个完全可逆的+/−ECD和开/关CPL开关。在此基础上，制作了抑制和蕴涵逻辑门。
Optical and chiroptical photoswitches have found potential applications in advanced information technologies. Herein, a pair of chiral triple-stranded helicates [Eu2(o-LRR)3](TOf)6 and [Eu2(o-LSS)3](TOf)6, which have chirality, luminescence and light stimuli-responsive properties, have been designed and synthesized. The ligands o-LRR/SS are composed of photochromic diarylethene moieties as spacers and two chiral 2,6-dipicolinic amides as coordination units. Through the comprehensive spectral characteristics in combination with semiempirical geometry optimization using the Sparkle/RM1 model, it was confirmed that (R/S)-1-phenylethanamines decorated at the terminals of ligands successfully controlled the stereoselective self-assembly of the helicates. Upon alternating UV and visible light irradiation, the diarylethene experienced a reversible change between a colorless open-ring state and a pink closed-ring state. This photochromic process caused variations in the electronic structure and ligand conformation, and led to the presence of light-responsive optical (UV and PL) and chiroptical (ECD and CPL) switching properties. The helicate may, therefore, be considered as a completely reversible +/− ECD and on/off CPL switch. Furthermore, on the basis of these light-switchable optical properties, the INHIBIT and IMPLICATION logic gates were fabricated.