The exploration of new open-framework polyoxometalates is very significant in structural chemistry and materials science. Herein, three new organic hybrid three-dimensional vanadium borophosphates (H3O)7(H2aeae)3{[Cd(H2O)3]2[H3O⊃(V2BP2O12)6]}·15H2O (1, aeae = 2-(2-aminoethylamino)ethanol) and (H3O)5(H2aeae)3{[TM(H2O)2.5(H2aeae)0.5]2[H3O⊃ (V2BP2O12)6]}·9H2O [TM = Mn(2), Co(3)] were hydrothermally prepared and structurally characterized. The three vanadium borophosphates contain similar 12-member ring crown-shaped clusters [(V2BP2O12)6]18− based on the linkage of six [V2O8] dimers and six [BP2O10] units. The [(V2BP2O12)6]18− cluster is further bridged by the unsaturated [Cd(H2O)3]2+ or [TM(H2O)2.5(H2aeae)0.5]3+ complexes to build new types of open-framework vanadium borophosphates with pores and cavities retained by the protonated H2aeae2+, H3O+ and free H2O. Surprisingly, the monodentate H2aeae2+ ligand coordinating with a metal center was observed in 2 and 3 for the first time as the aeae molecule acted as the trichelating ligand. Their optical absorption edges were determined to be in the range of 2.61–2.68 eV using solid-state UV-vis spectroscopy. 1–3 exhibited excellent photocatalytic activity towards methylene blue (MB) degradation under visible light irradiation, which presented the first example of organic hybrid open-framework vanadium borophosphates as the photo-catalysts for MB degradation.
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