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  Excitation Wavelength Dependent O2 Release from Copper(II)–Superoxide Compounds: Laser Flash-Photolysis Experiments and Theoretical Studies

Saracini, C., Liakos, D. G., Zapata Rivera, J. E., Neese, F., Meyer, G. J., & Karlin, K. D. (2014). Excitation Wavelength Dependent O2 Release from Copper(II)–Superoxide Compounds: Laser Flash-Photolysis Experiments and Theoretical Studies. Journal of the American Chemical Society, 136(4), 1260-1263. doi:10.1021/ja4115314.

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 Creators:
Saracini, Claudio1, Author
Liakos, Dimitrios G.2, Author              
Zapata Rivera, Jhon E.3, Author
Neese, Frank2, Author              
Meyer, Gerald J.1, Author
Karlin, Kenneth D.1, Author
Affiliations:
1Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States, ou_persistent22              
2Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
3Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgili, c/Marcel·lí Domingo, s/n, 43007 Tarragona, Spain, ou_persistent22              

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 Abstract: Irradiation of the copper(II)–superoxide synthetic complexes [(TMG3tren)CuII(O2)]+ (1) and [(PV-TMPA)CuII(O2)]+ (2) with visible light resulted in direct photogeneration of O2 gas at low temperature (from −40 °C to −70 °C for 1 and from −125 to −135 °C for 2) in 2-methyltetrahydrofuran (MeTHF) solvent. The yield of O2 release was wavelength dependent: λexc = 436 nm, ϕ = 0.29 (for 1), ϕ = 0.11 (for 2), and λexc = 683 nm, ϕ = 0.035 (for 1), ϕ = 0.078 (for 2), which was followed by fast O2-recombination with [(TMG3tren)CuI]+ (3) and [(PV-TMPA)CuI]+ (4). Enthalpic barriers for O2 rebinding to the copper(I) center (∼10 kJ mol–1) and for O2 dissociation from the superoxide compound 1 (45 kJ mol–1) were determined. TD-DFT studies, carried out for 1, support the experimental results confirming the dissociative character of the excited states formed upon blue- or red-light laser excitation.

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Language(s): eng - English
 Dates: 2013-11-172014-01-152014-01-29
 Publication Status: Published in print
 Pages: 4
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja4115314
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 136 (4) Sequence Number: - Start / End Page: 1260 - 1263 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870