Photo Responsive Electron and Proton Conductivity within a Hydrogen-Bonded Organic Framework.
Photo Responsive Electron and Proton Conductivity within a Hydrogen-Bonded Organic Framework.
复制标题
氢键有机框架内的光响应电子和质子电导率。
DOI：
10.1002/anie.202308418
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发表时间：
2023
影响因子：
--
通讯作者：
Zhangjing Zhang
中科院分区：
文献类型：
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作者：
Shimin Chen;Yan;Hao Zhang;Yingbing Zou;Siou;Yunbin Li;Shuaiqi Wang;En Ma;W. Deng;S. Xiang;Banglin Chen;Zhangjing Zhang
具有耦合质子-电子转移的结晶多孔材料的合理设计迄今尚未报道。本文报道了一种以两性离子1，1 '-双（3-羧基苄基）-4，4'-联吡啶（H2 L2+）为受体，2，7-萘二磺酸盐（NDS 2-）为供体的π-π堆积氢键有机骨架（霍夫; HOF-FJU-36）。三个水分子位于通道中，通过氢键相互作用与酸性物质连接，得到3D框架。沿着a轴的连续π-π相互作用和沿着B轴的光滑氢键链分别提供了电子和质子转移途径。在405 nm光照射后，由于耦合的电子-质子转移，光生自由基可以同时赋予HOF-FJU-36光开关电子和质子导电性。通过单晶X射线衍射（SCXRD）、X射线光电子能谱（XPS）、瞬态吸收光谱和密度泛函理论（DFT）计算，对辐照后电导率可切换的机理进行了研究。
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.