Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation

Niklas, Julie E.; Hunter, Katherine M.; Gorden, Anne E. V.

doi:10.1021/acs.inorgchem.9b01695

Title: Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation

Journal Article · Tue Nov 05 00:00:00 EST 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b01695· OSTI ID:1573133

Niklas, Julie E. ^[1]; Hunter, Katherine M. ^[1];

^[1]

Auburn Univ., Auburn, AL (United States)

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.

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Research Organization:: Auburn Univ., AL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0019177

OSTI ID:: 1573133

Journal Information:: Inorganic Chemistry, Vol. 58, Issue 22; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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CCDC 1918535: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22dd74 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1921460: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22hflm The current record is supplemented by this dataset	dataset	January 2019
CCDC 1918539: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22ddc8 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1918540: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22ddd9 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1918541: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22ddfb The current record is supplemented by this dataset	dataset	January 2019

Title: Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation

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