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Tetrahydrosalen Uranyl(VI) Complexes: Crystal Structures and Solution Binding Study
Author(s) -
Zhao Xiao,
Zhang Di,
Yu Ren,
Chen Shusen,
Zhao Dahui
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201701401
Subject(s) - uranyl , chemistry , pentagonal bipyramidal molecular geometry , schiff base , crystallography , ligand (biochemistry) , bipyramid , monomer , tetracoordinate , molecule , crystal structure , coordination geometry , stereochemistry , hydrogen bond , organic chemistry , ion , biochemistry , receptor , computer graphics (images) , computer science , planar , polymer
A pair of uranyl complexes incorporating tetrahydrosalen and N , N ‐dimethyltetrahydrosalen ligands are synthesized and studied. These new ligands, with saturated secondary and tertiary amines, exhibit higher chemostability than the prototype Schiff base (salen) structure, especially under acidic conditions. As shown by X‐ray diffraction crystallography, the coordination geometry of uranium in these new complexes is a distorted pentagonal bipyramid. Interestingly, UO 2 ([H 4 ]‐salen), comprising the tetrahydrosalen ligand, forms a dimeric structure in the crystals, with two subunits held together by sharing one of the two phenoxy oxygen atoms from each subunit, whereas UO 2 ([H 2 Me 2 ]‐salen) with the N , N ‐dimethyltetrahydrosalen ligand is in the monomer state, with a solvent molecule coordinated to uranium to complete the penta‐coordination configuration. Moreover, as revealed by UV/Vis spectroscopy using the colorimetry method, these hydrogenated salen ligands exhibit comparable, or even higher, binding affinities toward uranyl than the prototype Schiff base salen ligand in weakly basic solution.