Regulating the Photoresponsive Rate of Photochromic Coordination Polymers based on the Size Effect of Ligand

doi:10.6023/A25090306

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 min, 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, photoresponsive rates of 1 and 2 were further calculated 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 of ligand on the interfacial contacts of electron donors/acceptors, pho-toinduced intermolecular ET and the photoresponsive rate, which provides an effective strategy for the controllable construction of photochromic CPs.

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

Cite this article

Shimin Zhang, Pengfei Hao, Qiu Shen, Minxia Gao, Haiying Yang, Junju Shen, Yunlong Fu. Regulating the Photoresponsive Rate of Photochromic Coordination Polymers based on the Size Effect of Ligand[J]. Acta Chimica Sinica, 2026, 84(2): 208-213.

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Fig. & Tab. 5

Figure 1. Schematic diagram of size effect of electron donor (p-H2BDC, 0.688 nm; H2BPC, 1.141 nm)

Figure 2. (a) Asymmetric unit, (b) one-dimensional zigzag chain, (c) two-dimensional layer (Insert: position of free 3-DPNDI molecule), and (d) three-dimensional supramolecular network

Figure 3. (a) Asymmetric unit, (b) 2D layer (Rhombic channels: 2.556 nm×1.734 nm), (c) two-fold interpenetrated 2D framework, and (d) 3D supramolecular network (Insert: schematic diagram of stacking)

Figure 4. (a) Ultraviolet-visible absorption spectrum of 1 (Insert: photochromic behavior of 1), (b) Ultraviolet-visible absorption spectrum of 2 (Insert: photochromic behavior of 2), (c) EPR spectra of 1 and 1P, (d) EPR spectra of 2 and 2P, (e) Kinetic curve of 1, and (f) Kinetic curve of 2

Figure 5. (a) Electron transfer channel I of 1, (b) electron transfer channel II of 1, and (c) electron transfer channel of 2

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