Zhou Yan, Yu Fei, Su Jian, Kurmoo Mohamedally, Zuo Jing-Lin
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210023, P. R. China.
Institute of Advanced Materials and Flexible Electronics (IAMFE), School of Chemistry and Materials Science, Nanjing University of Information Science & Technology, Nanjing, 210044, P. R. China.
Angew Chem Int Ed Engl. 2020 Oct 12;59(42):18763-18767. doi: 10.1002/anie.202008941. Epub 2020 Aug 18.
To activate electronic and optical functions of the redox-active metal-organic framework, (Me NH )[In (TTFTB)]⋅0.7 C H OH⋅DMF (Me NH @1, TTFTB=tetrathiafulvalene-tetrabenzoate, DMF=N,N-dimethylformamide), has been exchanged by tetrathiafulvalenium (TTF ) and N,N'-dimethyl-4,4'-bipyridinium (MV ). These cations provide electron carriers and photosensitivity. The exchange retains the crystallinity allowing single-crystal to single-crystal post-synthetic transformation to TTF@1 and MV@1. Both TTF and MV enhance the electrical conductivity by a factor of 10 and the visible light induced photocurrent by 4 and 28 times, respectively. EPR evidences synergetic effect involving charge transfer between the framework redox-active TTFTB bridges and MV . The results demonstrate that functionalization of MOF by cation exchange without perturbing the crystallinity extends possibilities to achieve switchable materials.
为激活氧化还原活性金属有机框架（(MeNH )[In (TTFTB)]⋅0.7 C H OH⋅DMF （MeNH @1，TTFTB = 四硫富瓦烯 - 四苯甲酸酯，DMF = N，N - 二甲基甲酰胺））的电子和光学功能，已用四硫富瓦烯鎓（TTF ）和N，N'-二甲基 - 4，4'-联吡啶鎓（MV ）进行了交换。这些阳离子提供电子载体和光敏性。该交换保留了结晶度，允许单晶到单晶的后合成转变为TTF@1和MV@1。TTF和MV分别将电导率提高了10倍，将可见光诱导的光电流提高了4倍和28倍。电子顺磁共振证明了涉及框架氧化还原活性TTFTB桥与MV之间电荷转移的协同效应。结果表明，通过阳离子交换对金属有机框架进行功能化而不干扰结晶度，扩展了实现可切换材料的可能性。
