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Tuning Electrical- and Photo-Conductivity by Cation Exchange within a Redox-Active Tetrathiafulvalene-Based Metal–Organic Framework |
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| Authors: | Yan Zhou Dr Fei Yu Dr Jian Su Prof Dr Mohamedally Kurmoo Prof Dr Jing-Lin Zuo |
| Institution: | 1. 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
These authors contributed equally to this work.;2. 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 These authors contributed equally to this work.;3. 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;4. Institut de Chimie de Strasbourg, CNRS-UMR 7177, Université de Strasbourg, 4 rue Blaise Pascal, 67008 Strasbourg, France |
| Abstract: | To activate electronic and optical functions of the redox-active metal–organic framework, (Me2NH2)InIII(TTFTB)]⋅0.7 C2H5OH⋅DMF (Me2NH2@ 1 , TTFTB=tetrathiafulvalene-tetrabenzoate, DMF=N,N-dimethylformamide), has been exchanged by tetrathiafulvalenium (TTF.+) and N,N′-dimethyl-4,4′-bipyridinium (MV2+). 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 MV2+ enhance the electrical conductivity by a factor of 102 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 MV2+. The results demonstrate that functionalization of MOF by cation exchange without perturbing the crystallinity extends possibilities to achieve switchable materials. |
| Keywords: | methylviologen post-synthetic modification redox-active species single-crystal to single-crystal transformation tetrathiafulvalene |