通过配位溶剂控制吡咯并二亚胺锆基金属有机框架的光致变色性

IF 3.2 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Molecular Systems Design & Engineering Pub Date : 2024-09-12 DOI:10.1039/D4ME00104D
Youcong Li, Jiahao Dong, Yue Zhao, Lei Gao, Yu-Hao Gu and Shuai Yuan
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引用次数: 0

摘要

金属有机框架(MOFs)具有结构多变性和可调特性,是设计光致发光材料的理想平台。然而,在保持 MOFs 高稳定性的同时对其光响应行为进行微调仍是一项挑战。在本研究中,我们合成了一种含有氧化还原活性的吡咯烷二亚胺(PMDI)基团和不饱和 Zr6 簇合物(命名为 Zr-PMDI-DMF)的 MOF,并通过交换 Zr 位点上的配位溶剂分子对其光致变色特性进行了微调。与传统的双齿羧酸配位 Zr6 团簇不同,Zr-PMDI-DMF 具有单齿羧酸配位,暴露的 Zr 位点被溶剂分子占据。我们在合成后用 2-(二甲基氨基)乙醇(DMAE)、N-甲基四氢吡咯(NMP)和二甲基亚砜(DMSO)交换了配位的 N,N-二甲基甲酰胺(DMF)溶剂分子,并使用单晶 X 射线衍射测定了配位溶剂分子的结构。通过光致变色和漂白循环实验、电子顺磁共振光谱和密度泛函理论计算,我们发现配位溶剂起着电子供体的作用。相反,PMDI 配体作为电子受体,导致框架内电子转移和光致变色。光致变色反应的速率与溶剂的电子供体能力相关,其趋势依次为 DMAE > NMP > DMSO > DMF。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Controlling the photochromism of zirconium pyromellitic diimide-based metal–organic frameworks through coordinating solvents†

Metal–organic frameworks (MOFs) are promising platforms for designing photoresponsive materials due to their structural versatility and tunable properties. However, challenges remain in fine-tuning the photoresponsive behavior while maintaining the high stability of MOFs. In this study, we synthesized a MOF containing redox-active pyromellitic diimide (PMDI) groups and unsaturated Zr6 clusters named Zr-PMDI-DMF and fine-tuned its photochromic properties by exchanging the coordination solvent molecules on the Zr sites. Unlike traditional Zr6 clusters with bidentate carboxylate coordination, Zr-PMDI-DMF features monodentate carboxylate coordination with the exposed Zr sites occupied by solvent molecules. We post-synthetically exchanged the coordinated N,N-dimethylformamide (DMF) solvent molecules with 2-(dimethylamino)ethanol (DMAE), N-methyltetrahydropyrrole (NMP), and dimethyl sulfoxide (DMSO) and determined the structures of the coordinated solvent molecules using single-crystal X-ray diffraction. Through photochromic and bleaching cycle experiments, electron paramagnetic resonance spectroscopy, and density functional theory calculations, we found that the coordinated solvents act as electron donors. In contrast, PMDI ligands act as electron acceptors, causing intra-framework electron transfer and photochromism. The rate of the photochromic response correlated with the electron-donating ability of the solvents, following the trend of DMAE > NMP > DMSO > DMF.

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来源期刊
Molecular Systems Design & Engineering
Molecular Systems Design & Engineering Engineering-Biomedical Engineering
CiteScore
6.40
自引率
2.80%
发文量
144
期刊介绍: Molecular Systems Design & Engineering provides a hub for cutting-edge research into how understanding of molecular properties, behaviour and interactions can be used to design and assemble better materials, systems, and processes to achieve specific functions. These may have applications of technological significance and help address global challenges.
期刊最新文献
Back cover Back cover Dual responsive fluorescence switching of organohydrogel towards base/acid† Back cover Graph-based networks for accurate prediction of ground and excited state molecular properties from minimal features†
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