Excitation wavelength dependent O2 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. 1260-3
Online
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Zugriff:
Irradiation of the copper(II)-superoxide synthetic complexes [(TMG3tren)Cu(II)(O2)](+) (1) and [(PV-TMPA)Cu(II)(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)Cu(I)](+) (3) and [(PV-TMPA)Cu(I)](+) (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.
| Titel: |
Excitation wavelength dependent O2 release from copper(II)-superoxide compounds: laser flash-photolysis experiments and theoretical studies.
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| Autor/in / Beteiligte Person: | Saracini, C ; Liakos, DG ; Zapata Rivera, JE ; Neese, F ; Meyer, GJ ; Karlin, KD |
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| Zeitschrift: | Journal of the American Chemical Society, Jg. 136 (2014-01-29), Heft 4, S. 1260-3 |
| Veröffentlichung: | Washington, DC : American Chemical Society ; <i>Original Publication</i>: Easton, Pa. [etc.], 2014 |
| Medientyp: | academicJournal |
| ISSN: | 1520-5126 (electronic) |
| DOI: | 10.1021/ja4115314 |
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