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

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

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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.

Authors:

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

^[1]

Auburn Univ., Auburn, AL (United States)

Publication Date:: 2019-11-05

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & 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.

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                    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.  doi:10.1021/acs.inorgchem.9b01695.

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                    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.  doi:10.1021/acs.inorgchem.9b01695.  https://www.osti.gov/servlets/purl/1573133.

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@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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DOI: 10.1021/acs.inorgchem.9b01695

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