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Mediating Photochemical Reaction Rates at Lewis Acidic Rare Earths by Selective Energy Loss to 4f-Electron States.
Ruoff, Kevin P; Gish, Melissa K; Song, Ellen; Douair, Iskander; Pandey, Pragati; Steger, Mark; Johnson, Justin C; Carroll, Patrick J; Gau, Michael; Chang, Christopher H; Larsen, Ross E; Ferguson, Andrew J; Schelter, Eric J.
Affiliation
  • Ruoff KP; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Gish MK; Materials, Chemical, and Computational Science Directorate, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States.
  • Song E; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Douair I; Materials, Chemical, and Computational Science Directorate, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States.
  • Pandey P; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Steger M; Materials, Chemical, and Computational Science Directorate, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States.
  • Johnson JC; Materials, Chemical, and Computational Science Directorate, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States.
  • Carroll PJ; Renewable and Sustainable Energy Institute, University of Colorado Boulder, Boulder, Colorado 80309, United States.
  • Gau M; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Chang CH; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104, United States.
  • Larsen RE; Materials, Chemical, and Computational Science Directorate, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States.
  • Ferguson AJ; Materials, Chemical, and Computational Science Directorate, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States.
  • Schelter EJ; Renewable and Sustainable Energy Institute, University of Colorado Boulder, Boulder, Colorado 80309, United States.
J Am Chem Soc ; 145(30): 16374-16382, 2023 Aug 02.
Article in En | MEDLINE | ID: mdl-37467432
Manifesting chemical differences in individual rare earth (RE) element complexes is challenging due to the similar sizes of the tripositive cations and the corelike 4f shell. We disclose a new strategy for differentiating between similarly sized Dy3+ and Y3+ ions through a tailored photochemical reaction of their isostructural complexes in which the f-electron states of Dy3+ act as an energy sink. Complexes RE(hfac)3(NMMO)2 (RE = Dy (2-Dy) and Y (2-Y), hfac = hexafluoroacetylacetonate, and NMMO = N-methylmorpholine-N-oxide) showed variable rates of oxygen atom transfer (OAT) to triphenylphosphine under ultraviolet (UV) irradiation, as monitored by 1H and 19F NMR spectroscopies. Ultrafast transient absorption spectroscopy (TAS) identified the excited state(s) responsible for the photochemical OAT reaction or lack thereof. Competing sensitization pathways leading to excited-state deactivation in 2-Dy through energy transfer to the 4f electron manifold ultimately slows the OAT reaction at this metal cation. The measured rate differences between the open-shell Dy3+ and closed-shell Y3+ complexes demonstrate that using established principles of 4f ion sensitization may deliver new, selective modalities for differentiating the RE elements that do not depend on cation size.

Full text: 1 Collection: 01-internacional Database: MEDLINE Type of study: Prognostic_studies Language: En Journal: J Am Chem Soc Year: 2023 Document type: Article Affiliation country: United States Country of publication: United States

Full text: 1 Collection: 01-internacional Database: MEDLINE Type of study: Prognostic_studies Language: En Journal: J Am Chem Soc Year: 2023 Document type: Article Affiliation country: United States Country of publication: United States