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0 2025110702

DOI: https://doi.org/10.6023/A25090306

Article

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

  • Zhang Shimin ,
  • Hao Pengfei ,
  • Shen Qiu ,
  • Gao Minxia ,
  • Yang Haiying ,
  • Shen Junju ,
  • Fu Yunlong
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  • aDepartment of Applied Chemistry, Yuncheng University, Yuncheng 044000;
    bSchool of Chemistry and Chemical Engineering, Shanxi Normal University, Taiyuan 030031, China

Revised date: 2025-09-11

  Online published: 2025-11-07

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).

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Abstract

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 = Δabs/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

Cite this article

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, 0 : 2025110702 . DOI: 10.6023/A25090306

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