Excitation Wavelength Dependent O<subscript>2</subscript> Release from Copper(II)-Superoxide Compounds: Laser Flash-Photolysis Experiments and Theoretical Studies.
In: Journal of the American Chemical Society, Jg. 136 (2014-01-29), Heft 4, S. 1260-1263
Online
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Zugriff:
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. [ABSTRACT FROM AUTHOR]
| Titel: |
Excitation Wavelength Dependent O<subscript>2</subscript> Release from Copper(II)-Superoxide Compounds: Laser Flash-Photolysis Experiments and Theoretical Studies.
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| Autor/in / Beteiligte Person: | Saracini, Claudio ; Liakos, Dimitrios G. ; Zapata Rivera, Jhon E. ; Neese, Frank ; Meyer, Gerald J. ; Karlin, Kenneth D. |
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| Zeitschrift: | Journal of the American Chemical Society, Jg. 136 (2014-01-29), Heft 4, S. 1260-1263 |
| Veröffentlichung: | 2014 |
| Medientyp: | academicJournal |
| ISSN: | 0002-7863 (print) |
| DOI: | 10.1021/ja4115314 |
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