Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation
Abstract
Uranyl complexes of aryl-substituted α-diimine ligands gbha (UO2-1a-f and phen-BIAN (UO2-2a-f) (gbha (1) = glyoxal bis(2-hydroxyanil); phen-BIAN (2) = N,N'-bis-(iminophenol)acenaphthene; R = OMe (a), t-bu (b), H (c), Me (d), F (e), and naphthyl (f)) were designed, prepared, and characterized by X-ray diffraction, FT-IR, NMR, UV-Vis, and electrochemical methods. Furthermore these ligand frameworks contain a salen-type O-N-N-O binding pocket, but are redox-non-innocent, leading to unusual metal complex behaviors. Here, we describe three solid-state structures of uranyl complexes UO2-1b, UO2-1c, and UO2-1f, and observe manifestations of ligand non-innocence for the U(VI) complexes UO2-1b and UO2-1c. The impacts of accessible π-systems and ligand substitution on the axial uranium-oxo interactions can be evaluated spectroscopically via the intraligand charge-transfer (ILCT) processes that dominate the absorption spectra of these complexes and through changes to the asymmetric (ν3) O=U=O stretching frequency. This, in combination with electrochemical data, reveals the effects of the inclusion of the conjugated acenaphthene backbone and the importance of ligand electronic structure on uranyl’s bonding interactions.
- Publication Date:
- Research Org.:
- Auburn Univ., AL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1573133
- Grant/Contract Number:
- SC0019177
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 22; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; uranium; electrochemistry; coordination
Citation Formats
Niklas, Julie E., Hunter, Katherine M., and Gorden, Anne E. V. Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation. United States: N. p., 2019.
Web. doi:10.1021/acs.inorgchem.9b01695.
Niklas, Julie E., Hunter, Katherine M., & Gorden, Anne E. V. Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation. United States. https://doi.org/10.1021/acs.inorgchem.9b01695
Niklas, Julie E., Hunter, Katherine M., and Gorden, Anne E. V. Tue .
"Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation". United States. https://doi.org/10.1021/acs.inorgchem.9b01695. https://www.osti.gov/servlets/purl/1573133.
@article{osti_1573133,
title = {Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation},
author = {Niklas, Julie E. and Hunter, Katherine M. and Gorden, Anne E. V.},
abstractNote = {Uranyl complexes of aryl-substituted α-diimine ligands gbha (UO2-1a-f and phen-BIAN (UO2-2a-f) (gbha (1) = glyoxal bis(2-hydroxyanil); phen-BIAN (2) = N,N'-bis-(iminophenol)acenaphthene; R = OMe (a), t-bu (b), H (c), Me (d), F (e), and naphthyl (f)) were designed, prepared, and characterized by X-ray diffraction, FT-IR, NMR, UV-Vis, and electrochemical methods. Furthermore these ligand frameworks contain a salen-type O-N-N-O binding pocket, but are redox-non-innocent, leading to unusual metal complex behaviors. Here, we describe three solid-state structures of uranyl complexes UO2-1b, UO2-1c, and UO2-1f, and observe manifestations of ligand non-innocence for the U(VI) complexes UO2-1b and UO2-1c. The impacts of accessible π-systems and ligand substitution on the axial uranium-oxo interactions can be evaluated spectroscopically via the intraligand charge-transfer (ILCT) processes that dominate the absorption spectra of these complexes and through changes to the asymmetric (ν3) O=U=O stretching frequency. This, in combination with electrochemical data, reveals the effects of the inclusion of the conjugated acenaphthene backbone and the importance of ligand electronic structure on uranyl’s bonding interactions.},
doi = {10.1021/acs.inorgchem.9b01695},
journal = {Inorganic Chemistry},
number = 22,
volume = 58,
place = {United States},
year = {2019},
month = {11}
}
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