The Modulation Effect of N-Substituents on Photochromic Properties of Naphthalenediimide-based Coordination Polymers

doi:10.6023/A25050166

Abstract

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

Cite this article

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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Fig. & Tab. 6

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

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

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

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)

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

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

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