Regulating the photoresponsive rate of photochromic coordination polymers based on the size effect

doi:10.6023/A25090306

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基于尺寸效应调控光致变色配位聚合物的光响应速率

张士民^a, 郝朋飞^b,*, 申秋^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

修回日期:2025-09-11
基金资助:
项目受山西省科技厅项目（20210302123324、201901D111275）、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）和山西省高等学校科技创新项目（2025L111）资助。

Regulating the photoresponsive rate of photochromic coordination polymers based on the size effect

Zhang Shimin^a, Hao Pengfei^b,*, Shen Qiu^b, Gao Minxia^b, Yang Haiying^a, Shen Junju^b, Fu Yunlong^b,*

^aDepartment of Applied Chemistry, Yuncheng University, Yuncheng 044000;
^bSchool of Chemistry and Chemical Engineering, Shanxi Normal University, Taiyuan 030031, China

Revised:2025-09-11
Contact: ^* E-mail: haopengfei_2015@126.com, yunlongfu@sxnu.edu.cn
Supported by:
Natural Science Foundation of Science and Technology Agency of Shanxi Province (20210302123324, 201901D111275), Applied Research Project of Yuncheng University (YY-202510), Doctoral Research Start-up Project of Yuncheng University (YXBQ-202519), Scientific and Technologial Innovation Programs of Higher Education Institutions in Shanxi (2025L111).

The monitoring and regulation of the photoresponsive rate of electron transfer (ET)-based photochromic coordination polymers is of great importance for optimizing photochromic performances, but remain a huge challenge. In this work, two novel two-dimension (2D) CPs, [Zn₂(3-DPNDI)₂(p-BDC)(p-HBDC)₂]•[3-DPNDI]₂ (1) and [Zn(3-DPNDI)(BPC)]•H₂O (2) have been constructed through the integration of N, N′-di-(3-pyridyl)-1,4,5,8-naphthalene diimide (3-DPNDI, electron acceptor), Zn(NO₃)₂ (metal node) and terephthalic acid/4,4′-biphenylphthalic acid (p-H₂BDC/H₂BPC, electron donor). The single-crystal structures of 1 and 2 were confirmed and analyzed by single-crystal X-ray diffraction (SC-XRD), the purity and thermal stability of the single-crystal samples were evaluated by powder X-ray diffraction (PXRD) and thermogravimetry (TGA), the photochromic properties were studied by ultraviolet-visible absorption spectroscopy (UV-Vis), and the mechanism of photochromism was determined using electron paramagnetic resonance spectroscopy (EPR). Under ultraviolet lamp irradiation (Hg lamp, 365 nm), 1 can undergo a fast color change from pale brown to black within 1 s and reached saturation in 10 minutes, while 2 displays a slow color transformation from yellow to brown within 5 s and saturated time is about 1 h. To evaluate the photoresponsive rate more accurately and effectively, a new method was proposed (i.e. photoresponsive rate = Δ_abs/time, unit, s^-1). By means of above equation, the photoresponsive rate of 1 is 0.02 s^-1, while that of 2 is only 0.0024 s^-1. The photoresponsive rate of 1 is approximately one order of magnitude faster than that of 2. Meanwhile, we further calculated photoresponsive rates of 1 and 2 using the kinetic equations. The kinetic constant k₁ for 1 is 0.13 s^-1, which is much greater than that of 2 (0.003 s^-1), further confirming the accuracy of the above-mentioned calculation method. This study demonstrates the significant influence of size effect on the interfical contacts of electron donors/acceptors, photoinduced intermolecular ET and the photoresponsive rate, which provides an effective strategy for the controllable construction of photochromic CPs.

Key words: electron transfer, coordination polymers, naphthalenediimide, photoresponsive rate

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Zhang Shimin, Hao Pengfei, Shen Qiu, Gao Minxia, Yang Haiying, Shen Junju, Fu Yunlong. Regulating the photoresponsive rate of photochromic coordination polymers based on the size effect[J]. Acta Chimica Sinica, doi: 10.6023/A25090306.

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基于尺寸效应调控光致变色配位聚合物的光响应速率

Regulating the photoresponsive rate of photochromic coordination polymers based on the size effect

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