Photo Responsive Electron and Proton Conductivity within a Hydrogen‐Bonded Organic Framework

• Published in: Angewandte Chemie International Edition Vol. 62; no. 34; pp. e202308418 - n/a
• Main Authors: Chen, Shimin, Ju, Yan, Zhang, Hao, Zou, Yingbing, Lin, Si, Li, Yunbin, Wang, Shuaiqi, Ma, En, Deng, Weihua, Xiang, Shengchang, Chen, Banglin, Zhang, Zhangjing
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 21.08.2023
• Edition: International ed. in English
• Subjects: Absorption spectra; Conductivity; Coupled Proton-Electron Transfer; D-A π–π Stacking; Density functional theory; Electron transfer; Hydrogen bonding; Hydrogen-Bonded Organic Framework; Irradiation; Light irradiation; Naphthalene; Photoelectron spectroscopy; Photoelectrons; Porous materials; Protons; coupled proton-electron transfer; hydrogen-bonded organic framework; D-A π-π stacking
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202308418

Rational design of crystalline porous materials with coupled proton‐electron transfer has not yet been reported to date. Herein, we report a donor‐acceptor (D‐A) π‐π stacking hydrogen‐bonded organic framework (HOF; HOF‐FJU‐36) with zwitterionic 1,1′‐bis(3‐carboxybenzyl)‐4,4′‐bipyridinium (H2L2+) as acceptor and 2,7‐naphthalene disulfonate (NDS2−) as donor to form a two‐dimensional (2D) layer. Three water molecules were situated in the channels to connect with acidic species through hydrogen bonding interactions to give a 3D framework. The continuous π‐π interactions along the a axis and the smooth H‐bonding chain along the b axis provide the electron and proton transfer pathways, respectively. After 405 nm light irradiation, the photogenerated radicals could simultaneously endow HOF‐FJU‐36 with photoswitchable electron and proton conductivity due to coupled electron‐proton transfer. By single‐crystal X‐ray diffraction (SCXRD) analyses, X‐ray photoelectron spectroscopy (XPS), transient absorption spectra and density functional theory (DFT) calculations, the mechanism of the switchable conductivity upon irradiation has been demonstrated. A donor‐acceptor (D‐A) π–π stacking hydrogen‐bonded organic framework (HOF; HOF‐FJU‐36) is constructed from zwitterionic 1,1′‐bis(3‐carboxybenzyl)‐4,4′‐bipyridinium (H2L2+) as the acceptor and 2,7‐naphthalene disulfonate (NDS2−) as the donor. It exhibits photo‐responsive electron and proton conductivity due to coupled electron‐proton transfer.