Stepwise Structural Transformations of Coordination Polymers Caused by Ligands Replacements and Solid-State Photoreaction

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-05-30 DOI:10.1021/acs.inorgchem.5c01464

Jun-Feng Wang, Shen-Shen Wang, Qi-Meng Liu, Xiao-Yan Tang, Dong Liu

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Abstract

The structural transformations of coordination polymers not only contribute to structural diversity but also provide design strategies at the molecular level for developing a new generation of smart materials. In this work, a photoinert olefin-containing coordination chain {[Zn(H₂O)(5-NO₂-1,3-BDC)(3,3′-dpe)]₂·H₂O}_n (1) was prepared by the hydrothermal reaction between Zn(NO₃)₂·6H₂O, 1,2-di(pyridin-3-yl)ethene (3,3′-dpe), and 5-nitro-1,3-benzenedicarboxylic acid (5-NO₂-1,3-H₂BDC). After replacing the 5-NO₂-1,3-H₂BDC ligand in the solution of 1 with 5-methyl-1,3-benzenedicarboxylic acid (5-Me-1,3-H₂BDC), a unique two-dimensional photoreactive coordination network [Zn(5-Me-1,3-BDC)(3,3′-dpe)]_n (2) was formed. When exposed to UV light, 2 can undergo a [2 + 2] photocycloaddition reaction to produce [Zn(5-Me-1,3-BDC)(rctt-3,3′-tpcb)_0.5]_n (3, 3,3′-tpcb = 1,2,3,4-tetra(pyridin-3-yl)cyclobutane) via single-crystal-to-single-crystal (SCSC) transformation. By replacing the 5-Me-1,3-BDC ligand in the solution of 3 with 5-NO₂-1,3-H₂BDC, a three-dimensional framework of {[Zn₂(5-NO₂-1,3-BDC)₂(rtct-3,3′-tpcb)]·2H₂O}_n (4) can be obtained. Accompanied by the in situ solid-state photoreaction, 2 exhibits intriguing photocontrolled fluorescence behavior, making it a promising smart material for applications in fluorescence sensors, super-resolution imaging, and optical anticounterfeiting.

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配体置换和固态光反应引起的配位聚合物的逐步结构转变

配位聚合物的结构转变不仅有助于结构多样性，而且为开发新一代智能材料提供了分子水平上的设计策略。本文以Zn(NO3)2·6H2O、1,2-二（吡啶-3-基）乙烯（3,3 ' -dpe）和5-硝基-1,3-苯二甲酸（5-NO2-1,3- h2bdc）为原料，通过水热反应制备了光惰性含烯烃配位链{[Zn(H2O)(5-NO2-1,3- bdc)(3,3 ' -dpe)]2·H2O}n(1)。用5-甲基-1,3-苯二甲酸（5- me -1,3- h2bdc）取代1溶液中的5- no2 -1,3- h2bdc配体后，形成独特的二维光反应配位网络[Zn(5- me -1,3- bdc)(3,3 ' -dpe)]n(2)。在紫外光照射下，2可发生[2 + 2]光环加成反应生成[Zn(5- me -1,3- bdc)(rct -3,3′-tpcb)0.5]n（3,3,3′-tpcb = 1,2,3,4-四（吡啶-3-基）环丁烷）。用5-NO2-1,3- h2bdc取代3溶液中的5- me -1,3- bdc配体，得到{[Zn2(5-NO2-1,3- bdc)2(rct -3,3′-tpcb)]·2H2O}n(4)的三维骨架。伴随着原位固态光反应，2表现出有趣的光控荧光行为，使其成为一种有前途的智能材料，用于荧光传感器，超分辨率成像和光学防伪。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.