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Dihydroxo-bridged diuranyl(VI) complexes with 2-((2-(6-chloropyridazin-3-yl)hydrazono)methyl)-4-R-phenols: Structural insight and visible light driven photocatalytic activities

Abstract

Two new dihyroxo-bridged diuranyl(VI) complexes of the molecular formula [(UO2)2(μ-OH)2(Ln)2] (1 and 2) were synthesized in good yields (~64%) by reacting equimolar amounts of [UO2(OAc)2]∙2H2O and 2-((2-(6-chloropyridazin-3-yl)hydrazono)methyl)-4-R-phenols (HLn where n = 1 and 2 for R = H and OMe, respectively) in dimethylformamide. Both complexes were characterized by elemental analysis, various spectroscopic and cyclic voltammetric measurements. X-ray crystal structures of the two complexes crystallized as solvated species showed the rare {(UO2)2(μ-OH)2}2+ core where each metal centre is in a distorted pentagonal-bipyramidal N2O5 coordination sphere assembled by the two axial oxo atoms, two equatorial bridging hydroxo-O atoms and the equatorial N,N,O-donor (Ln)-. The solvated complexes assemble through intermolecular bifurcated N-H∙∙∙(O,O) and simple O-H∙∙∙O and N-H∙∙∙O hydrogen bonding interactions and form supramolecular one-dimensional chain-like and three-dimensional network structures in the crystal lattices. Infrared and proton NMR spectroscopic characteristics of the two complexes corroborate their molecular structures. Electronic spectra of 1 and 2 display three strong absorptions in the range 405301 nm. A metal centred irreversible reduction having the Epc near -1.06 V (vs. Ag/AgCl) has been observed in the cyclic voltammograms of 1 and 2. Both complexes are photocatalytically active in degradation of rhodamine B (RhB) and methylene blue (MB) under visible light irradiation. Photodegradation of RhB up to a maximum of 96% and that of MB up to a maximum of 85% has been achieved in 150 and 180 min, respectively using 2 as catalyst.

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Publication details

The article was received on 04 Oct 2018, accepted on 28 Nov 2018 and first published on 28 Nov 2018


Article type: Paper
DOI: 10.1039/C8NJ05038D
Citation: New J. Chem., 2018, Accepted Manuscript
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    Dihydroxo-bridged diuranyl(VI) complexes with 2-((2-(6-chloropyridazin-3-yl)hydrazono)methyl)-4-R-phenols: Structural insight and visible light driven photocatalytic activities

    S. Ghosh, A. K. Srivastava and S. Pal, New J. Chem., 2018, Accepted Manuscript , DOI: 10.1039/C8NJ05038D

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