Based on the newly designed ligand 4'-(3,5-dicarboxyphenyl)-4,2':6',4''-terpyridine (DCTP), a unique semi-conductive 3D framework {[Cu(Ι)Cu(ΙΙ)2(DCTP)2]NO3⋅1.5 DMF}n (1) with a narrow band gap of 2.1 eV, was obtained and structurally characterized. DFT calculations with van de Waals correction employed to explore the electronic structure of 1, clearly revealed its semi-conductive behavior. Furthermore, we found that 1 exhibits a superior band alignment with water to produce hydrogen and degrade organic pollutants. Without adding any photosensitizers, 1 displays an efficiently photocatalytic hydrogen production in water based on the photo-generated electrons under UV/Vis light. 1 also exhibits excellent photo-degradation of methyl blue under visible-light owing to the strong oxidization of excited holes. It is the first example of MOFs with doubly photocatalytic activities related to photo-generated electrons and holes, respectively.
Two multifunctional metal-organic frameworks based on cubane-like tetrahedron Tb clusters as nodes have been synthesized and characterized. Compound 1 exhibits a 2D lanthanide-organic framework with Tb clusters as nodes, and compound 2 possesses a 3D framework with Tb clusters and Mn as nodes. Interestingly, luminescent investigations on them reveal that the two compounds can act as recyclable luminescent probes for chromium(VI) anion species and the corresponding detection limit can reach 10 mol/L. Furthermore, 1 and 2 own efficient catalytic activity for the chemical fixation of CO with epoxides under mild conditions. Importantly, they both can be recycled at least three times without compromising the activity.
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