Affiliation: | 1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan Road, Shanghai, 200062 P. R. China Engineering Research Center for Nanophotonics and Advanced Instrument, School of Physics and Electronic Science, East China Normal University, 3663 North Zhongshan Road, Shanghai, 200062 P. R. China;2. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 North Zhongshan Road, Shanghai, 200062 P. R. China;3. Engineering Research Center for Nanophotonics and Advanced Instrument, School of Physics and Electronic Science, East China Normal University, 3663 North Zhongshan Road, Shanghai, 200062 P. R. China |
Abstract: | The assembly of two tripyridinium-tricarboxylate ligands and different metal ions leads to seven isostructural MOFs, which show novel 2D→2D supramolecular entanglement featuring catenane-like interlocking of tricyclic cages. The MOFs show tripyridinium-afforded and metal-modulated photoresponsive properties. The MOFs with d10 metal centers ( 1-Cd , 1-Zn , 2-Cd , 2-Zn ) show fast and reversible photochromism and concomitant fluorescence quenching, 1-Ni displays slower photochromism but does not fluoresce, and 1-Co and 2-Co are neither photochromic nor fluorescent. It is shown here that the network entanglement dictates donor-acceptor close contacts, which enable fluorescence originated from interligand charge transfer. The contacts also allow photoinduced electron transfer, which underlies photochromism and concomitant fluorescence response. The metal dependence in fluorescence and photochromism can be related to energy transfer through metal-centered d-d transitions. In addition, 1-Cd is demonstrated to be a potential fluorescence sensor for sensitive and selective detection of UO22+ in water. |