基于尺寸效应调控光致变色配位聚合物的光响应速率

doi:10.6023/A25090306

摘要/Abstract

电子转移型（ET）光致变色配位聚合物的光响应速率监测和调控对于优化光致变色性能至关重要,但仍然是一个巨大的挑战。本研究以N, N′-二-(3-吡啶基)-1,4,5,8-萘二酰亚胺（3-DPNDI）为电子受体,对苯二甲酸（p-H₂BDC）和4,4′-联苯二甲酸（H₂BPC）分别为电子给体,以Zn²⁺为金属节点,构筑了两例新的二维（2D）光致变色配位聚合物（PCCPs）,[Zn₂(3-DPNDI)₂(p-BDC)(p-HBDC)₂]•[3-DPNDI]₂ (1)和[Zn(3-DPNDI)(BPC)]•H₂O (2)。通过单晶X-射线衍射（SC-XRD）对其单晶结构进行分析,采用粉末X-射线衍射（PXRD）和热重（TG）对单晶样品的纯度和热稳定性进行评估,利用紫外-可见吸收光谱（UV-Vis）对光致变色性能进行研究,并使用电子顺磁共振谱（EPR）确定光致变色的机理。在紫外灯照射下（365 nm）,化合物1和2均呈现肉眼可识别的颜色变化。为了更准确和有效的评估光响应速率,我们发展了一种用于评估光响应速率的新方法（光响应速率=Δ_abs/时间,单位：s^-1）。计算表明,1的光响应速率比2的光响应速率快大约1个数量级。同时,我们采用动力学方程计算的光响应速率也符合1快于2的结论,进一步验证了上述光响应速率计算方法的准确性。本研究体现了尺寸效应对电子给受体间界面关系、光诱导分子间电子转移（PIET）和光响应速率的有效调控,为光致变色配位聚合物的可控构筑提供了一个有效的策略。

关键词: 电子转移, 配位聚合物, 萘二酰亚胺, 光响应速率

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

引用此文

张士民, 郝朋飞, 申秋, 高敏霞, 杨海英, 沈俊菊, 付云龙. 基于尺寸效应调控光致变色配位聚合物的光响应速率[J]. 化学学报, doi: 10.6023/A25090306.

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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参考文献

[1] Peng H. C.; Chen S.; Yan, B. Acta Chim. Sin.,2024, 82, 797 (in Chinese).(彭红超, 陈胜, 阎斌. 化学学报, 2024, 82, 797)
[2] Xu H.; Han P. B.; Qin A. J.; Tang, B. Z. Acta Chim. Sin.,2023, 81, 1420 (in Chinese).(徐赫, 韩鹏博, 秦安军, 唐本忠. 化学学报, 2023, 81, 1420)
[3] Zhang Q. Q.; Wang Y.; Braunstein P.; Lang, J. P. Chem. Soc. Rev.,2024, 53, 5227.
[4] Liu Q.; Braunstein P.; Lang, J. P. Acc. Mater. Res.,2025, 6, 183.
[5] Yonekawa I.; Mutoh K.; Kobayashi, Y. J. Am. Chem. Soc.,2018, 140, 1091.
[6] Yang P.; Zhu F.; Zhang, Z. B. Chem. Soc. Rev.,2021, 50, 8319.
[7] Lee W.; Kim D.; Lee S. Nano Today,2018, 23, 97.
[8] Wang Y. Y.; Zhang Y. M.; Zhang, S. X. A. Acc. Chem. Res.,2021, 54, 2216.
[9] Wang Y.; Shen R.; Wang S. Chem,2021, 5, 1308.
[10] Han S. D.; Hu J. X.; Wang, G. M. Coord. Chem. Rev.,2022, 452, 214304.
[11] Yu B.; Xiu Y. Y.; Zhang S. M.; Wang X. J. Am. Chem. Soc.,2025, 147, 26626.
[12] Bao Y. W.; Zhou Y. Q.; Qiu Z. X.; Zhang J. X.; Zhang J. P.; Du J. R.; Lian, S. X. Sci. China Mater.,2025, 68, 1064.
[13] Chen C. D.; Li Z. Q.; Xiao Y. H.; Ye C. H.; Wei J. W.; Zeng R. S.; Pang Q.; Luo, B. B. Chem. Sci.,2025, 16, 13731.
[14] Li L.; Li S. H.; Jiang H. Y.; Zeng J. G.; Liu, C. J. ACS Appl. Mater. Interfaces,2025, 29, 42293.
[15] Shen Y.; Zhao C. Y.; Huang L.; Hua Y.; Cui W. B.; Huang K.; Zhang H. Inorg. Chem.,2025, 64, 16856.
[16] Zhang M.; Liu L. H.; Song Y. Z.; Hou M. M.; Sun L.; Ma, P. T. Inorg. Chem.,2025, 64, 8524.
[17] Zhang S. M.; Hao P. F.; Zhang Y. F.; Li G. P.; Shen J. J.; Yang H. Y.; Fu, Y. L. Inorg. Chem. Front.,2025, 12, 3919.
[18] Li Y. D.; Ma L. F.; Yang G. P.; Wang, Y. Y. Angew. Chem., Int. Ed.,2025, 64, e202421744.
[19] Xue J. H.; Yang D. D.; Shi Y. S.; Yang Y. Y.; Ma Q.; Zheng X. J.Inorg. Chem. Front., 2025, doi.org/10.1039/D5QI01641J.
[20] Di Y. M.; Song Y. P.; Zhang S. Q.; Lin, M. J. Inorg. Chem.,2025, 64, 6183.
[21] Chen S. L.; Yang Q. T.; Shen X.; Cheng F. X.; Liu, J. J. Inorg. Chem.,2025, 64, 3008.
[22] Hao P. F.; Liu X.; Fu, Y. L. Chin. J. Inorg. Chem.,2022, 38, 198 (in Chinese).(郝朋飞, 刘兴, 付云龙. 无机化学学报, 2022, 38, 198-210).
[23] Li S. L.; Han M.; Li G. P.; Li M.; He G.; Zhang, X. M. J. Am. Chem. Soc.,2019, 141, 12663.
[24] Zhang S. M.; Hao P. F.; Gao M. X.; Yang H. Y.; Shen J. J.; Fu, Y. L. J. Mol. Struct.,2026, 1349, 143851.
[25] Wang J. F.; Hao P. F.; Zhang S. M.; Xu Y.; Qin J.; Shen J. J.; Fu, Y. L. Chem. Eng. J.,2025, 519, 165131.
[26] Zhang X. J.; Kang M.; Zhang S. M.; Wang J. F.; Zhang Y. F.; Hao P. F.; Shen J. J.; Fu, Y. L. Inorg. Chem. Front.,2025, 12, 6686.
[27] Zhang S. M.; Hao P. F.; Li G. P.; Shen J. J.; Fu, Y. L. Dyes Pigm.,2023, 220, 111677.
[28] Hao P. F.; Gao B. H.; Li G. P.; Shen J. J.; Fu, Y. L. Inorg. Chem. Front.,2022, 9, 2852.
[29] Zhang S. M.; Liu X. X.; Hao P. F.; Li G. P.; Shen J. J.; Fu, Y. L. Inorg. Chem.,2023, 62, 14912.
[30] Pan Q. Y.; Sun M. E.; Zhang C.; Li L. K.; Liu H. L.; Li K. J.; Li H. Y.; Zang, S. Q. Chem. Commun.,2021, 57, 11394.
[31] Yu X. Q.; Wang M. S.; Guo, G. C. Adv. Funct. Mater.,2023, 33, 2212907.
[32] Hao P. F.; Zhu H. H.; Pang Y.; Shen J. J.; Fu Y. L. CrystEngComm,2020, 22, 3371.
[33] Li G. P.; Xie H. F.; Hao P. F.; Fu Y. L.; Zhang K.; Shen J. J.; Wang, Y. Y. Inorg. Chem.,2022, 61, 6403.
[34] Zhang S. M.; Hao P. F.; Yu W. Y.; Zhu H. H.; Yang H. Y.; Shen J. J.; Fu, Y. L. Acta Chim. Sin.,2025, 10.6023/A25050166 (in Chinese).(张士民, 郝朋飞, 于炜玉, 朱慧慧, 杨海英, 沈俊菊, 付云龙. 化学学报, 2025, 10.6023/A25050166).
[35] Zhang S. M.; Hao P. F.; Yang H. Y.; Shen J. J.; Fu, Y. L. Inorg. Chem.,2025, 64, 12226.
[36] Castaldelli E.; Jayawardena K. D.G. I.; Cox, D. C.Nat Commun., 2017, 8, 2139.
[37] Wu Z.; Sun C.; Dong S.; Jiang X. F.; Wu S. P.; Wu H. B.; Yip H. L.; Huang F.; Cao Y.J. Am. Chem. Soc., 2016, 138, 2004.
[38] Deng Y. H.; Abrahams B. F.; Lang, J. P. J. Am. Chem. Soc.,2025, 147, 18219.
[39] Guha S.; Saha, S. J. Am. Chem. Soc.2010, 132, 17674.
[40] Li G. P.; Hao P. F.; Shen J. J.; Yu T. L.; Li H. H.; Fu, Y. L. Inorg. Chem.,2019, 55, 11342.
[41] Wang Y.; Zhang Q. Q.; Huang X. Y.; Liu Q.; Lang, J. P. J. Am. Chem. Soc.,2025, 147, 22192.
[42] Bai Y. J.; Zhang S. P.; Wang Y. X.; Zeng F. L.Principles and Analysis of Spectroscopy (fourth edition).(白银娟, 张世平, 王云霞, 曾凡龙. 波谱原理及解析(第四版))
[43] Shen Q. M.S. Thesis, Shanxi Normal University, Taiyuan, 2023 (in Chinese).(申秋, 硕士论文, 山西师范大学, 太原, 2023.)