苯二酰亚胺基配位聚合物的构筑及双功能光/电致变色性能研究

doi:10.6023/A26030084

化学学报 ›› 2026, Vol. 84 ›› Issue (6): 903-908.DOI: 10.6023/A26030084 上一篇下一篇

研究论文

苯二酰亚胺基配位聚合物的构筑及双功能光/电致变色性能研究

畅通^a, 郝朋飞^b^,^*(), 张士民^a^,^*(), 郭桂珍^a, 原舒婷^b, 高敏霞^b, 杨海英^a, 沈俊菊^b, 付云龙^b^,^*()

^a 运城学院应用化学系运城 044000
^b 山西师范大学化学与化工学院太原 030031

投稿日期:2026-03-25 发布日期:2026-05-28
基金资助:
山西省科技厅项目(20210302123324); 山西省科技厅项目(201901D111275); 山西省科技厅项目(202303021211188); 运城学院应用研究项目(YY-202510); 运城学院博士科研启动项目(YXBQ-202519); 山西省高等学校科技创新项目(2025L111); 优秀博士来晋专项经费(LJZX-2-202509); 资助和运城市科技局自由探索项目(YCKJ-2023049)

Construction and Bifunctional Photo-/Electrochromic Properties of a Pyromellitic diimide-based Coordination Polymer

Tong Chang^a, Pengfei Hao^b^,^*(), Shimin Zhang^a^,^*(), Guizhen Guo^a, Shuting Yuan^b, Minxia Gao^b, Haiying Yang^a, Junju Shen^b, Yunlong Fu^b^,^*()

^a Department of Applied Chemistry, Yuncheng University, Yuncheng 044000, China
^b School of Chemistry and Chemical Engineering, Shanxi Normal University, Taiyuan 030031, China

Received:2026-03-25 Published:2026-05-28
Contact: *E-mail: haopengfei_2015@126.com; zhangsm6511@163.com; yunlongfu@sxnu.edu.cn
Supported by:
Natural Science Foundation of Science and Technology Agency of Shanxi Province(20210302123324); Natural Science Foundation of Science and Technology Agency of Shanxi Province(201901D111275); Natural Science Foundation of Science and Technology Agency of Shanxi Province(202303021211188); Applied Research Project of Yuncheng University(YY-202510); Doctoral Research Start-up Project of Yuncheng University(YXBQ-202519); Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2025L111); “LJ” Special Funds of Distinguished Doctorates(LJZX-2-202509); Free exploration projects of Yuncheng Science and Technology Bureau(YCKJ-2023049)

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1. Supporting information-A26030084.pdf(601KB)

摘要/Abstract

近年来, 双功能光/电致变色配位聚合物(CPs)在智能窗、军事伪装、防眩目后视镜、显示及智能织物等领域展现重要的应用价值, 由于受缺电子配体类型的限制, 此类材料的定向设计与精准合成仍面临巨大挑战. 本工作以N,N-二-(羧甲基)-苯二酰亚胺(H₂CMPMD)为有机连接体, Mn²⁺为金属节点, 通过溶剂热法合成了一例具有双功能光/电致变色特性的配位聚合物[Mn(CMPMD)(DMF)](标记为CMPMD-Mn). 采用单晶X射线衍射(SC-XRD)、粉末X射线衍射(PXRD)、傅里叶变换红外光谱(FT-IR)以及热重(TG)等技术对结构进行表征, 并通过紫外-可见吸收光谱(UV-Vis)和电子顺磁共振谱(EPR)对光致变色性能和机理进行研究. 在365 nm紫外灯照射下, CMPMD-Mn在1 s内呈现由淡黄色到黄绿色的颜色转变, 主要归因于电子转移(ET)及[PMD]^•−自由基的形成. 有趣的是, 110 ℃热处理后, CMPMD-Mn仍表现出优异的光致变色性能, 性能几乎没有衰减, 这为极端情况下的实际应用提供了良好的前提. 当施加－1.5 V电压时, CMPMD-Mn表现出由淡黄色到蓝绿色的电致变色行为. 同时, 利用循环伏安(CV)和光谱电化学技术对电致变色行为和机理进行了研究. 本工作有效拓展了有机缺电子配体的类型, 丰富了双功能光/电致变色材料家族, 为此类材料的结构设计与性能优化提供了新的思路.

关键词: 苯二酰亚胺, 光致变色性能, 电致变色性能, 配位聚合物

In recent years, bifunctional photo/electrochromic coordination polymers (CPs) have shown significant potential or practical application value in fields such as smart windows, military camouflage, anti-glare rearview mirrors, displays, and smart fabrics. However, due to the limitations of the types of organic electron-deficient acceptors, the targeted design and precise synthesis of such materials continues to be a huge challenge. In this work, a CP with bifunctional photo-/electro- chromic properties, [Mn(CMPMD)(DMF)] (labeled as CMPMD-Mn), was synthesized by solvothermal method using N,N-di-(carboxymethyl)-pyromellitic diimide (H₂CMPMD) as the organic linker and metal Mn²⁺ ion as the metal node. The structure of single-crystal was characterized by single-crystal X-ray diffractometer (SC-XRD), the purity of single-crystals was confirmed by powder X-ray diffractometer (PXRD), the thermal stability of samples was studied by thermogravimetric (TG), and the photochromic properties and mechanisms were discussed by ultraviolet-visible absorption spectroscopy (UV-Vis) and electron paramagnetic resonance spectroscopy (EPR). Upon the irradiation of 365 nm ultraviolet lamp, CMPMD-Mn exhibited a obvious color change from light yellow to green, which should be ascribed to electron transfer and the generation of [PMD]^•− radical. Furthermore, the fast photoresponse mainly attributed to the formation of π-π interactions and the large overlap degree between PMD ligands. Interestingly, after heat treatment, the compound still exhibits excellent photochromic properties with almost no degradation in performance, which provides a good prerequisite for practical applications in extreme situations. Meanwhile, when a voltage of －1.5 V is applied, CMPMD-Mn exhibits preliminary electro-chromic behavior (from light yellow to bluish green). The electrochromic behavior and mechanism of the sample were characterized by cyclic voltammetry (CV) and spectroelectrochemistry. This work effectively expands the types of organic electron-deficient acceptors, enriches the family of dual-functional photo/electrochromic materials, and provides new ideas for the structural design and performance optimization of such materials.

Key words: pyromellitic diimide, photochromism, electrochromism, coordination polymers

引用此文

畅通, 郝朋飞, 张士民, 郭桂珍, 原舒婷, 高敏霞, 杨海英, 沈俊菊, 付云龙. 苯二酰亚胺基配位聚合物的构筑及双功能光/电致变色性能研究[J]. 化学学报, 2026, 84(6): 903-908.

Tong Chang, Pengfei Hao, Shimin Zhang, Guizhen Guo, Shuting Yuan, Minxia Gao, Haiying Yang, Junju Shen, Yunlong Fu. Construction and Bifunctional Photo-/Electrochromic Properties of a Pyromellitic diimide-based Coordination Polymer[J]. Acta Chimica Sinica, 2026, 84(6): 903-908.

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图/表 7

图1. 具有电子接受能力的CMPMD有机配体

Figure 1. Organic ligands of CMPMD with electron-accepting capability

图2. (a) CMPMD-Mn的非对称结构单元(内插图: 金属离子的配位环境); (b) CMPMD配体的配位模式(μ4-η1:η1:η1:η1); (c) 1D链; (d) 沿ac平面无限延伸的2D层; (e) 堆积图

Figure 2. (a) Asymmetric unit of CMPMD-Mn (Insert: the coordination environment of metal ions); (b) coordination mode of CMPMD (μ4-η1:η1:η1:η1); (c) 1D chains; (d) 2D layer extending infinitely along the ac plane; (e) Packing diagram

图3. CMPMD-Mn在不同光照时间下(0 s、1 s、3 s和120 s)的颜色变化

Figure 3. The color changes of CMPMD-Mn under different light irradiation times (0 s, 1 s, 3 s and 120 s)

图4. (a) CMPMD-Mn的紫外-可见吸收光谱; (b) 光照前后, 单晶样品的EPR谱; (c) CMPMD-Mn的两阶段一级动力学曲线; (d) 800 nm附近CMPMD-Zn和CMPMD-Mn光照前后吸光度的改变量

Figure 4. (a) Ultraviolet-visible absorption spectrum of CMPMD-Mn; (b) EPR spectra of single crystal samples before and after light irradiation; (c) The two-stage first-order kinetic curve of CMPMD-Mn; (d) The changes in absorbance of CMPMD-Zn and CMPMD-Mn before and after light irradiation (near 800 nm)

图5. (a) CMPMD-Mn和CMPMD-Mn-H的PXRD谱; (b) CMPMD-Mn-H的紫外-可见吸收光谱; (c) CMPMD-Mn-H的两阶段一级动力学曲线; (d) CMPMD-Mn和CMPMD-Mn-H的动力学常数对比图

Figure 5. (a) The PXRD patterns of CMPMD-Mn and CMPMD-Mn-H; (b) The ultraviolet-visible absorption spectrum of CMPMD-Mn-H; (c) The two-stage first-order kinetic curve of CMPMD-Mn-H; (d) Comparison chart of kinetic constants between CMPMD-Mn and CMPMD-Mn-H

图6. 电子转移通道 (a) π-π相互作用; (b) PMD配体之间的重叠程度

Figure 6. Electron transfer channel (a) π-π interaction; (b) The degree of overlap between PMD ligands

图7. (a) CMPMD-Mn薄膜的循环伏安曲线(内插图: CMPMD-Mn薄膜电致变色行为); (b) CMPMD-Mn薄膜的光谱电化学

Figure 7. (a) Cyclic voltammetry curve of CMPMD-Mn film (inner inset: electrochromic behavior of CMPMD-Mn film); (b) Spectroelectrochemistry of CMPMD-Mn thin films

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苯二酰亚胺基配位聚合物的构筑及双功能光/电致变色性能研究

Construction and Bifunctional Photo-/Electrochromic Properties of a Pyromellitic diimide-based Coordination Polymer

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