Excitation Wavelength Dependent O2Release from Copper(II)–Superoxide Compounds: Laser Flash-Photolysis Experiments and Theoretical Studies,Journal of the American Chemical Society

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Excitation Wavelength Dependent O2Release from Copper(II)–Superoxide Compounds: Laser Flash-Photolysis Experiments and Theoretical Studies
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2014-01-15 , DOI: 10.1021/ja4115314
Claudio Saracini ₁ , Dimitrios G Liakos , Jhon E Zapata Rivera , Frank Neese , Gerald J Meyer , Kenneth D Karlin

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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.

中文翻译：

铜 (II)-超氧化物化合物中的激发波长相关的 O2 释放：激光闪光-光解实验和理论研究

铜 (II)-超氧化物合成复合物 [(TMG3tren)Cu(II)(O2)](+) (1) 和 [(PV-TMPA)Cu(II)(O2)](+) (2) 的辐照用可见光在 2-甲基四氢呋喃 (MeTHF) 溶剂中在低温下直接光生 O2 气体（1 从 -40 °C 到 -70 °C，2 从 -125 到 -135 °C）。O2 释放量取决于波长：λexc = 436 nm，φ = 0.29（对于 1），φ = 0.11（对于 2），λexc = 683 nm，φ = 0.035（对于 1），φ = 0.078（对于 2） )，然后是与 [(TMG3tren)Cu(I)](+) (3) 和 [(PV-TMPA)Cu(I)](+) (4) 的快速 O2 复合。确定了 O2 重新结合到铜 (I) 中心 (~10 kJ mol(-1)) 和 O2 从超氧化物化合物 1 (45 kJ mol(-1)) 解离的焓势垒。TD-DFT 研究，进行了 1，

更新日期：2014-01-15

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