N-取代基对萘二酰亚胺基配位聚合物光致变色性能的调控作用

doi:10.6023/A25050166

摘要/Abstract

采用溶剂热法, 将N,N-二-(3-吡啶基)-1,4,5,8-萘二酰亚胺(3-DPNDI)/N,N-二-(3-吡啶酰胺基)-1,4,5,8-萘二酰亚胺(3-PANDI)、1,4-萘二羧酸(1,4-H₂NDA)和硝酸镉进行组装, 获得两例新型萘二酰亚胺(NDI)基配位聚合物(CPs), [Cd(3-DPNDI)(1,4-HNDA)(FA)]•DMF (1)和[Cd(3-PANDI)₂(1,4-HNDA)₂]•2DMF•2H₂O (2)(FA: 甲酸根, DMF: N,N-二甲基甲酰胺). 采用单晶X-射线衍射(SCXRD)、粉末X-射线衍射(PXRD)、热重(TGA)、紫外-可见吸收光谱(UV-Vis)和电子顺磁共振(EPR)等表征手段对1和2的单晶结构以及光致变色性能进行了详细的研究. 在约365 nm汞(Hg)灯照射下, 1在5 s内呈现由黄色到深棕色的颜色变化, 2在15 s内展现橙色到棕色的颜色转变, 二者的饱和时间均为30 min. 尽管2相对于1具有更短的电子转移通道(孤对电子-π相互作用: 1中的0.3471 nm和0.3650 nm相对于2中的0.3113 nm和0.3375 nm; π-π相互作用: 1中的0.3678 nm、0.3741 nm和0.3758 nm相对于2中的0.3550 nm和0.3725 nm), 然而1的光致变色性能优于2, 这主要归因于2中较强的电荷转移(CT)降低了电子受体接受电子的能力, 进而抑制了电子转移(ET)进程. 本研究体现了N-取代基对电子给受体间界面关系、分子间CT、光诱导分子间ET和光致变色性能的微妙调控作用, 为开发具有可控光致变色性能的配位聚合物提供了新思路.

关键词: 1,4,5,8-萘二酰亚胺, 配位聚合物, 光致变色, 电子转移, 电荷转移

In recent years, although the photochromic properties of photochromic coordination polymers (PCCPs) has been greatly improved, the regulation of photochromic performance still face tremendous challenges. Here, two photoresponsive 1,4,5,8-naphthalenediimide (NDI)-based coordination polymers (CPs), [Cd(3-DPNDI)(1,4-HNDA)(FA)]•DMF (1) and [Cd(3-PANDI)₂(1,4-HNDA)₂]•2DMF•2H₂O (2) (FA=formate, DMF=dimethyl formamide), have been designed (based on modulation effect of N-substituents) and obtained by assembly of N,N'-bis-(3-pyridyl)-1,4,5,8-naphthalenediimide (3-DPNDI)/N,N'-bis-(3-pyridinamide)-1,4,5,8-naphthalenediimide (3-PANDI), 1,4-naphthalene dicarboxylic acid (1,4-H₂NDA) and cadmium nitrate tetrahydrate (Cd(NO₃)₂•4H₂O), respectively. The structures and photochromic properties of 1 and 2 have been detailedly investigated by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), thermogravimetry (TGA), Fourier transform infrared (FT-IR) spectra, UV-Vis absorption spectroscopy (UV-vis), kinetics curves and electron paramagnetic resonance (EPR). Interestingly, although 1 and 2 have the same two-dimension (2D) framework, they exhibit completely different photochromic behaviors. Upon exposure to ca. 365 nm Hg lamp, 1 displays a prominent color change from yellow to brown within 5 s, while 2 shows a color transformation from orange to brown within 15 s, both of which saturation time is 30 min. This phenomenon indicates that 1 has more excellent photochromic properties compared with 2. To investigate the reason, the interface relationship was analyzed carefully. Although 2 has a shorter electron transfer pathway (lone pair-π interactions: 0.3471 nm and 0.3650 nm in 1 vs. 0.3113 nm and 0.3375 nm in 2; π-π interactions: 0.3678 nm, 0.3741 nm and 0.3758 nm in 1 vs. 0.3550 nm and 0.3725 nm in 2), the photochromic performance of 1 is superior to that of 2, which is mainly ascribed to the stronger charge transfer (CT) in 2 leading to the decrease of electron-accepting ability of electron acceptors and thereby inhibits the electron transfer (ET) process. This study demonstrates the subtle modulating effect of N-substituents on the interfacial relationship between electron donors and electon acceptors, intermolecular CT, photoinduced intermolecular ET and photochromic properties, which provides a new idea for the devel- opment of coordination polymers with controllable photochromic properties. Meanwhile, this work provides an effective strategy for the regulation of photochromic properties

Key words: 1,4,5,8-naphthalenediimide, coordination polymers, photochromic property, electron transfer, charge transfer

引用此文

张士民, 郝朋飞, 于炜玉, 朱慧慧, 杨海英, 沈俊菊, 付云龙. N-取代基对萘二酰亚胺基配位聚合物光致变色性能的调控作用[J]. 化学学报, 2025, 83(11): 1356-1362.

Zhang Shimin, Hao Pengfei, Yu Weiyu, Zhu Huihui, Yang Haiying, Shen Junju, Fu Yunlong. The Modulation Effect of N-Substituents on Photochromic Properties of Naphthalenediimide-based Coordination Polymers[J]. Acta Chimica Sinica, 2025, 83(11): 1356-1362.

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图/表 6

图1. N-取代基对界面关系调控作用示意图

Figure 1. Schematic diagram of the modulation effect of N-substituents on interfacial contacts

图2. 配合物1的晶体结构. (a)非对称结构基元图; (b)金属离子的配位模式; (c) 3-DPNDI分子的配位模式; (d)辅助配体的配位模式; (e) 2D层状结构; (f) 3D超分子网络

Figure 2. The crystal structure of 1. (a) The asymmetric structure; (b) The coordination mode of metal ions; (c) The coordination mode of 3-DPNDI; (d) The coordination mode of auxiliary ligand; (e) The 2D layer; (f) The 3D supermolecular network

图3. 配合物2的晶体结构. (a)非对称结构基元图(内插图: 金属离子的配位环境); (b) 3-PANDI分子的配位模式; (c)辅助配体的配位模式; (d) 2D 层状结构; (e) 3D超分子网络

Figure 3. The crystal structure of 2. (a) The asymmetric structure (insert: the coordination environment of metal ions); (b) The coordination mode of 3-PANDI; (c) The coordination mode of auxiliary ligand; (d) The 2D layer; (e) The 3D supermolecular network

图4. 动力学曲线. (a)基于604 nm吸收峰, 配合物1的动力学曲线; (b)基于609 nm吸收峰, 配合物2的动力学曲线; (c)基于780 nm吸收峰, 配合物1的动力学曲线; (d)基于791 nm吸收峰, 配合物2的动力学曲线

Figure 4. The kinetics curves. (a) The kinetics of 1 (based on absorption peak at 604 nm); (b) The kinetics of 2 (based on absorption peak at 609 nm); (c) The kinetics of 1 (based on absorption peak at 780 nm); (d) The kinetics of 2 (based on absorption peak at 791 nm)

图5. 紫外-可见吸收光谱和电子顺磁共振谱. (a)配合物1的紫外-可见吸收光谱(内插图: 配合物1的光致变色行为); (b)配合物2的紫外-可见吸收光谱(内插图: 配合物2的光致变色行为); (c)配合物1和1P的电子顺磁共振谱; (d)配合物2和2P的电子顺磁共振谱

Figure 5. UV-vis and EPR pattern (a) UV-vis absorption spectra of 1 (insert: photochromic behaviors of 1); (b) UV-vis absorption spectra of 2 (insert: photochromic behaviors of 2); (c) EPR spectra of 1 and 1P; (d) EPR spectra of 2 and 2P

图6. 界面关系图. (a)配合物1的界面关系图; (b)配合物2的界面关系图

Figure 6. The interfacial contacts. (a) The interfacial contacts of 1; (b) The interfacial contacts of 2

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