萘二亚胺基 Cd(II) 配合物的溶剂调节自组装和构象异构化可控光致变色,Inorganic Chemistry

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萘二亚胺基 Cd(II) 配合物的溶剂调节自组装和构象异构化可控光致变色
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-09-29 , DOI: 10.1021/acs.inorgchem.2c02249
Yong-Sheng Shi ₁ , Dong-Dong Yang ₁ , Han-Wen Zheng ₁ , Qiong-Fang Liang ₁ , Yu-Hui Fang ₂ , Tong Xiao ₁ , Xiang-Jun Zheng ₁

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合理调控光致变色材料的性能是一项具有挑战性和意义的工作。在目前的工作中，基于NDI的配合物，即[Cd _0.5 (NDI)(HBDC)]·H ₂ O ( 1 )和一系列构象异构体{[Cd(NDI) _0.5 (BDC)]·MeCN} _n ( 2 ) 是通过改变溶剂条件（H ₂ BDC = 对苯二甲酸，NDI = N，N'-双（3-吡啶基羰基肼）-1,4,5,8-萘二亚胺）合成的。由于萘二亚胺部分的不良共轭，配合物 1 呈现出 0D 单核结构，没有光致变色行为。络合物的构象异构体图2显示了一个3D网络，在X射线、紫外线和可见光下显示出超快的光诱导分子间电子转移光致变色行为。然而，它们在光辐照下表现出不同的光致变色率和着色对比度，这源于它们的孤对(COO)···π(NDI)距离不同。这是通过控制反应体系中的溶剂比例来实现的。此外，与 UV/X 射线相比，2对可见光表现出更高的敏感性，是一种具有光调制发光的有机-无机杂化材料。基于卓越的性能，复2可应用于滤纸，显示出作为无墨印刷介质的潜在应用，并通过不同的视觉颜色变化选择性感知固态氨和胺蒸气。

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Solvent-Modulated Self-Assembly of Naphthalenediimide-Based Cd(II) Complexes and the Controllable Photochromism via Conformational Isomerization

Rational regulation of the properties of photochromic materials is a challenging and meaningful work. In the present work, NDI-based complexes, namely, [Cd_0.5(NDI)(HBDC)]·H₂O (1) and a series of conformational isomers of {[Cd(NDI)_0.5(BDC)]·MeCN}_n (2), were synthesized by varying the solvent conditions (H₂BDC = terephthalic acid, NDI = N,N′-bis(3-pyridylcarbonylhydrazine)-1,4,5,8-naphthalene diimide). Complex 1 exhibits a 0D mononuclear structure without photochromic behavior due to the bad conjugation of the naphthalene diimide moiety. The conformational isomers of complex 2 manifest a 3D network, showing ultra-fast photo-induced intermolecular electron transfer photochromic behavior under X-ray, UV, and visible light. However, they show different photochromic rates and coloring contrast upon photoirradiation, which originates from their difference in the distances of lone pair(COO)···π(NDI). This was realized via controlling the solvent ratio in the reaction system. In addition, compared to UV/X-ray light, 2 exhibits greater sensitivity to visible light and is an organic–inorganic hybrid material with photomodulated luminescence. Based on the excellent performance, complex 2 can be applied to filter paper, showing potential applications as an inkless printing medium and selective perception of ammonia and amine vapors in the solid state via different visual color changes.

更新日期：2022-09-29

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