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Photo- and Electronically Switchable Spin-Crossover Iron(II) Metal-Organic Frameworks Based on a Tetrathiafulvalene
Hai-Ying Wang1, Jing-Yuan Ge1, Carol Hua2
1State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093, China.
Abstract:
A major challenge is the development of multifunctional metal-organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing the redox active ligand tetra(4-pyridyl)tetrathiafulvalene (TTF(py)4 ) and spin-crossover FeII centers. The materials exhibit redox activity, in addition to thermally and photo-induced spin crossover (SCO). A crystal-to-crystal transformation induced by I2 doping has also been observed and the resulting intercalated structure determined. The conductivity could be significantly enhanced (up to 3 orders of magnitude) by modulating the electronic state of the framework via oxidative doping; SCO behavior was also modified and the photo-magnetic behavior was switched off. This work provides a new strategy to tune the spin state and conductivity of framework materials through guest-induced redox-state switching.