Tan Bin, Wu Zhao-Feng, Jia Meng-Ze, Zhang Jie, Yang Guo-Yu
MOE Key Laboratory of Cluster Science, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, P. R. China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China.
Inorg Chem. 2023 May 1;62(17):6688-6695. doi: 10.1021/acs.inorgchem.3c00225. Epub 2023 Apr 19.
The photoinduced electron-transfer (ET) process plays an irreplaceable role in chemical and biological fields exemplified by enzymatic catalysis, artificial photosystems, solar energy conversion, and so forth. Searching for a new photoinduced ET system is of great importance for the development of functional materials. Herein, a series of host-guest compounds based on a magnesium metal-organic framework (Mg-MOF) as a host and pyridine derivatives as guests have been presented. Notably, strong O-H···N hydrogen bond between the oxygen atom of μ-HO and the nitrogen atom of pyridine enables proton delocalization between water molecule and pyridine guest. Despite the absence of photochromic modules in these host-guest compounds, long-lived charge-separated states with distinct color changes can be formed after UV-light irradiation. The substituents in pyridines and the proton delocalization ability between the host and guests have a great influence on their photoinduced ET process to endow the MOF materials with tunable photoinduced charge-separated states.
光致电子转移(ET)过程在化学和生物领域中发挥着不可替代的作用,例如酶催化、人工光系统、太阳能转换等。寻找新型光致电子转移体系对于功能材料的开发具有重要意义。在此,我们展示了一系列以镁基金属有机框架(Mg-MOF)为主客体、吡啶衍生物为客体的主客体化合物。值得注意的是,μ-HO的氧原子与吡啶的氮原子之间存在强O-H···N氢键,这使得质子能够在水分子和吡啶客体之间离域。尽管这些主客体化合物中没有光致变色模块,但在紫外光照射后可以形成具有明显颜色变化的长寿命电荷分离态。吡啶中的取代基以及主客体之间的质子离域能力对其光致电子转移过程有很大影响,从而使MOF材料具有可调谐的光致电荷分离态。