电子给体的同分异构策略调控萘二酰亚胺基配位聚合物的光致变色性能

doi:10.6023/A25110378

研究论文

电子给体的同分异构策略调控萘二酰亚胺基配位聚合物的光致变色性能

秦晋^a, 张士民^c, 郝朋飞^b,*, 申秋^b, 朱慧慧^b, 沈俊菊^b, 付云龙^b,*

^a山西师范大学材料科学与工程学院太原 030031;
^b山西师范大学化学与化工学院太原 030031;
^c运城学院应用化学系运城 044000

投稿日期:2025-11-19
通讯作者: *E-mail: haopengfei_2015@126.com, yunlongfu@sxnu.edu.cn
基金资助:
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）、山西省高等学校科技创新项目（2025L111）和优秀博士来晋专项经费（LJZX-2-202509）资助

The isomerization strategy of electron donors regulates the photochromic properties of naphthalenediimide coordination polymers

Qin Jin^a, Zhang Shimin^c, Hao Pengfei^b,*, Shen Qiu^b, Zhu Huihui^b, Shen Junju^b, Fu Yunlong^b,*

^aSchool of Materials Science and Engineering, Shanxi Normal University, Taiyuan 030031, China;
^bSchool of Chemistry and Chemical Engineering, Shanxi Normal University, Taiyuan 030031, China;
^cDepartment of Applied Chemistry, Yuncheng University, Yuncheng 044000, China

Received:2025-11-19
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),”LJ” Special Funds of Distinguished Doctorates (LJZX-2-202509).

文章分享

1. Supporting information-A25110378.pdf(809KB)

摘要/Abstract

电子给-受体（ED-EA）的界面关系是决定光致变色配位聚合物（PCCPs）光致变色性能的关键因素,然而界面关系的调控仍处于初级阶段并且面临着严峻的挑战。本文将N, N-二-(3-吡啶基)-1,4,5,8-萘二酰亚胺（3-DPNDI）和Zn(NO₃)₂分别与苯二甲酸的两个同分异构体[邻苯二甲酸（o-BDC）和间苯二甲酸（m-BDC）]进行组装,构筑了两个PCCPs,[Zn(3-DPNDI)(o-BDC)] (1)和[Zn(3-DPNDI)_0.5(m-BDC)(H₂O)]•2H₂O (2)。利用单晶X射线衍射（SCXRD）、粉末X射线衍射（PXRD）、傅里叶变换红外光谱（FT-IR）、热重（TG）、紫外-可见（UV-Vis）吸收光谱和电子顺磁共振（EPR）等技术对1和2进行了详细的表征。紫外光照射下,1和2呈现不同的光致变色性能,主要表现在颜色变化和光响应速率两个方面。尽管二者具有相同的变色时间,然而2吸光度的改变量Δ_abs远大于1,表明2具有更快的变色速率,这可以通过动力学曲线进一步证实。两个PCCPs光致变色性能的差异主要归因于同分异构电子给体的引入以及不同ED-EA间界面关系的形成。本文提出了一种通过引入同分异构电子给体调变CPs光致变色性能的策略,为构建具有可调的光响应功能材料奠定了坚实的基础。

关键词: 电子给-受体, 同分异构体, 萘二酰亚胺, 光致变色

The interfacial relationship between electron donors (ED) and acceptors (EA) is a key factor for determining the photochromic performance of photochromic coordination polymers (PCCPs). However, the regulation of the interfacial relationship is still in its infancy and continues to be a severe challenge. In this work, two PCCPs, [Zn(3-DPNDI)(o-BDC)] (1) and [Zn(3-DPNDI)_0.5(m-BDC)(H₂O)]•2H₂O (2), have been successfully obtained through the assembly of N, N-di-(3-pyridyl)-1,4,5,8-naphthalenedicarboximide (3-DPNDI) and zinc nitrate (Zn(NO₃)₂) with two isomers of terephthalic acids [o-phthalic acid (o-BDC) and m-phthalic acid (m-BDC)]. Compound 1 and 2 have been characterized in detail by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry (TG), ultraviolet-visible (UV-vis) absorption spectroscopy, and electron paramagnetic resonance (EPR). Upon ultraviolet light (~ 365 nm) irradiation, 1 and 2 exhibited different color change (from light brown to dark brown for 1 vs. from light brown to tan for 2) and photochromic response rates (color change time, 1 s for 1 vs. 1 s for 2; saturated time, 90 min for 1 vs. 30 min for 2). Although both 1 and 2 have the same color change time (1 s), the change of absorbance Δ_abs of 2 (0.07) is much larger than that of 1 (0.02), indicating that 2 has a faster photoresponse rate. Meanwhile, this result was further confirmed by the kinetic curves (1: 0.0078 s^-1 and 2: 0.0110 s^-1). The significantly different photochromic properties of the CPs are mainly attributed to the introduction of isomeric electron donors, which gives rise to different weak interactions between ED and EA, viz. intermolecular electron transfer (ET) channels, demonstrating the subtle modulation effect of isomeric electron donors on the interfacial relationship of ED-EA and photochromic properties. This paper proposes a strategy for modulating the photochromic performance of CPs by introducing isomeric electron donors, which lays a solid foundation for the construction of controllable photoresponsive functional materials.

Key words: electron donors and acceptors, isomerization, naphthalenediimide, photochromic properties

引用此文

秦晋, 张士民, 郝朋飞, 申秋, 朱慧慧, 沈俊菊, 付云龙. 电子给体的同分异构策略调控萘二酰亚胺基配位聚合物的光致变色性能[J]. 化学学报, doi: 10.6023/A25110378.

Qin Jin, Zhang Shimin, Hao Pengfei, Shen Qiu, Zhu Huihui, Shen Junju, Fu Yunlong. The isomerization strategy of electron donors regulates the photochromic properties of naphthalenediimide coordination polymers[J]. Acta Chimica Sinica, doi: 10.6023/A25110378.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Yao H.; Cao W. Y.; Wang J. W.; Yang F. X.; Qin S. N.; Wei T. B.; Shi B. B.; Lin, Q. Chin. J. Chem.,2025, 43, 1487.
[2] Li N. Y.; Liu D.; Abrahams B. F.; Lang, J. P. Chem. Commun.,2018, 54, 5831.
[3] Han X. T.; Yi Z. H.; Gao Y. F.; Wang Z. P.; Su T.; Wu, J. B,; Liang, Z. Q.; Li, J. Y. Inorg. Chem.,2025, 64, 20415.
[4] Zhang Q. Q.; Wang Y.; Braunstein P.; Lang, J. P. Chem. Soc. Rev.,2024, 53, 5227.
[5] Hu F. L.; Wang H. F.; Guo D.; Zhang H.; Lang J. P.; Beves, J. E. Chem. Commun.,2016, 52, 7990.
[6] Li S. L.; Han M.; Li G. P.; Li M.; He G.; Zhang, X. M. J. Am. Chem. Soc.,2019, 141, 12663.
[7] 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.
[8] Yu B.; Xiu Y. Y.; Zhang S. M.; Wang, X. J. Am. Chem. Soc.2025, 147, 26626.
[9] Ovalle M.; Doellerer D.; Feringa, B. L. Angew. Chem. Int. Ed.,2025, 64, e202501872.
[10] Luo W. F.; Castán, J. M. A. C.; Mirani, D. Riquelme, A. J.; Sachan A. K.; Kurman O.; Kim S.; Faini F.; Zimmermann P.; Hinderhofer A.; Patel Y.; Frei A. T.; Moser J. E.; Ramirez D.; Schreiber F.; Maldivi P.; Seo J. Y.; Tress W.; Grancini G.; Demadrille R.; Milić J. V. Adv. Mater.,2025, 37, 2420143.
[11] 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, 83, 1356.
(inChinese).
(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, 83, 1356).
[12] Han S. D.; Hu J. X.; Wang, G. M. Coord. Chem. Rev.,2022, 452, 214304.
[13] Chen S. L.; Yang Q. T.; Shen X.; Cheng F. X.; Liu, J. J. Inorg. Chem.,2025, 64, 3008.
[14] Zhao G. Z.; Jia J. F.; Liu, J. J. Cryst. Growth Des.,2025, 25, 9507.
[15] Lang F. F.; Pang J. D.; Bu X. H. eScience,2024, 4, 100231
[16] Xue J. H.; Yang D. D.; Shi Y. S.; Yang Y. Y.; Ma Q.; Zheng, X. J. Inorg. Chem. Front.,2025, 12, 8315
[17] Di Y. M.; Song Y. P.; Zhang S. Q.; Lin, M. J. Inorg. Chem.,2025, 64, 6183.
[18] Zhang S. M.; Liu X. X.; Hao P. F.; Li G. P.; Shen J. J.; Fu, Y. L. Inorg. Chem.,2023, 62, 14912.
[19] Zhou B.; Cao L. H.; Huang M. F.; Yang Y.; Qi S. M.; Cao X. J.; Chen, X. Y. Angew. Chem. Int. Ed.,2025, 64, e202504645.
[20] Yu T. L.; Hao P. F.; Shen J. J.; Li H. H.; Fu, Y. L. Dalton Trans.,2016, 45, 16505.
[21] Sun C.; Wang M. S.; Li P. X.; Guo, G. C. Angew. Chem. Int. Ed.,2017, 56, 554.
[22] Gong T.; Yang X.; Fang J. J.; Sui Q.; Xi F. G.; Gao, E. Q. ACS Appl. Mater. Interfaces,2017, 9, 5503.
[23] Zhang J.; Yao Z. G.; Liao S. J.; Dai J. C.; Fu, Z. Y. J. Mater. Chem. A.,2013, 1, 4945.
[24] Liu J. J.; Xia S. B.; Liu D.; Hou J. Y.; Suo H. B.; Cheng, F. X. Dyes Pigm.,2020, 177, 108269.
[25] Hao P. F.; Gao B. H.; Li G. P.; Shen J. J.; Fu, Y. L. Inorg. Chem. Front.,2022, 9, 2852.
[26] Zhao W. N.; Yu G. J.; Xu L. P.; Han, L. Inorg. Chem. Comm.,2013, 34, 47.
[27] 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.
[28] Zhang S. M.; Hao P. F.; Yang H. Y.; Shen J. J.; Fu, Y. L. Inorg. Chem.,2025, 64, 12226.
[29] Wang Y.; Zhang Q. Q.; Huang X. Y.; Liu Q.; Lang, J. P. J. Am. Chem. Soc.,2025, 147, 22192.
[30] 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.)
[31] Zhu H. H.M.S. Thesis, Shanxi Normal University, Taiyuan, 2021 (in Chinese).
(朱慧慧, 硕士论文, 山西师范大学, 临汾, 2021.)