基于配体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. 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)为电子给体, 以Zn^2＋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. 为了更准确和有效地评估光响应速率, 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, 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. 本研究体现了配体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 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

引用此文

张士民, 郝朋飞, 申秋, 高敏霞, 杨海英, 沈俊菊, 付云龙. 基于配体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, 2026, 84(2): 208-213.

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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图/表 5

图1. 电子给体尺寸效应示意图(对苯二甲酸, 0.688 nm; 4,4'-联苯二甲酸, 1.141 nm)

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

图2. (a)不对称结构单元、(b)一维“之”字链、(c)二维层(内插图: 游离3-DPNDI分子的位置)和(d) 三维超分子网络

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

图3. (a)不对称结构单元、(b)二维层(菱形孔道: 2.556 nm×1.734 nm)、(c) 2重穿插二维骨架和(d) 三维超分子网络(内插图: 堆积方式示意图)

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)

图4. (a) 1的紫外-可见吸收光谱(内插图: 1的光致变色行为)、(b) 2的紫外-可见吸收光谱(内插图: 2的光致变色行为)、(c) 1和1P的电子顺磁共振谱、(d) 2和2P的电子顺磁共振谱、(e) 1的动力学曲线及(f) 2的动力学曲线

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

图5. (a) 1的电子转移通道I、(b) 1的电子转移通道II及(c) 2的电子转移通道

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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