Premium
Uranyl(VI) Complexation by Sulfonate Ligands: A Relativistic Density Functional and Time‐Resolved Laser‐Induced Fluorescence Spectroscopy Study
Author(s) -
Kremleva Alena,
Zhang Yun,
Shor Aleksey M.,
Krüger Sven,
Joseph Claudia,
Raditzky Bianca,
Schmeide Katja,
Sachs Susanne,
Bernhard Gert,
Rösch Notker
Publication year - 2012
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.201200207
Subject(s) - chemistry , uranyl , sulfonate , benzenesulfonic acid , fluorescence spectroscopy , fluorescence , spectroscopy , density functional theory , ligand (biochemistry) , inorganic chemistry , computational chemistry , organic chemistry , ion , biochemistry , physics , receptor , quantum mechanics , sodium
To study the role of sulfonate functional groups of humic substances in uranyl(VI) complexation, all‐electron density functional calculations and time‐resolved laser‐induced fluorescence spectroscopy (TRLFS) were applied using small sulfonate ligands as models. A thiolate ligand was explored for comparison. As in an earlier experiment, 4‐hydroxybenzenesulfonic acid (HBSA) and benzenesulfonic acid (BSA) were examined and compared to methylsulfonic acid (MSA). Structural parameters as well as energetic aspects of uranyl complexes by BSA and HBSA ligands were determined to be rather similar, in contrast to earlier experimental findings. The present TRLFS measurements show complexation of uranyl by both ligands, which is in agreement with the computational results. Overall, the combined computational and experimental results also indicate that sulfonate groups play only a minor role in uranyl complexation of humic substances because of the rather low stability constants.