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Dynamic Phosphonic Bridges in Aqueous Uranyl Clusters
Author(s) -
Oliveri Anna F.,
Pilgrim Corey D.,
Qiu Jie,
Colla Christopher A.,
Burns Peter C.,
Casey William H.
Publication year - 2016
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.201600036
Subject(s) - chemistry , heteronuclear molecule , uranyl , aqueous solution , heteronuclear single quantum coherence spectroscopy , actinide , nuclear magnetic resonance spectroscopy , conformational isomerism , spectroscopy , crystallography , computational chemistry , inorganic chemistry , stereochemistry , molecule , organic chemistry , ion , physics , quantum mechanics
The uranyl cage clusters (UO 2 ) 22 (O 2 ) 15 (PHO 3 ) 20 (H 2 O) 10 26– ( U 22 ) and (UO 2 ) 28 (O 2 ) 20 (PHO 3 ) 24 (H 2 O) 12 32– ( U 28 ) can be probed in aqueous solutions by using a combination of 1 H Diffusion‐Ordered Spectroscopy (DOSY) and 1 H‐ 31 P Heteronuclear‐Single Quantum Coherence (HSQC) spectroscopy. This class of clusters is ideal for 1 H NMR analysis in D 2 O because of the covalent character of the H–P bond in the phosphonic bridges. 1 H DOSY indicates that the clusters are stable in solution and provides hydrodynamic radii of 9.8 ± 0.4 Å for the U 22 and 12.3 ± 0.5 Å for the U 28 clusters. Furthermore, 1 H‐ 31 P HSQC delivers unequivocal signal assignment for both nuclei, which enables solution dynamics to be monitored by variable‐temperature experiments, and reveals the presence of phosphonic‐bridge conformers. The results provide some of the first dynamic information about steady conformational changes in these enormous actinide macroions.