Time-resolved electron paramagnetic resonance of radical pair intermediates in cryptochromes

2013 ◽  
Vol 111 (24) ◽  
pp. 3698-3703 ◽  
Author(s):  
Till Biskup
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Radical Pair ◽  
Paramagnetic Resonance ◽  
Time Resolved ◽  
Electron Paramagnetic

scholarly journals Copper Complexes of Benzoylacetone Bis-Thiosemicarbazones: Metal and Ligand Based Redox Reactivity

2021 ◽  
Vol 74 (1) ◽  
pp. 34 ◽  
Author(s):  
Jessica K. Bilyj ◽  
Jeffrey R. Harmer ◽  
Paul V. Bernhardt
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Cyclic Voltammetry ◽  
Copper Complexes ◽  
Atmospheric Oxygen ◽  
The Other ◽  
Oxidation Reactions ◽  
Paramagnetic Resonance ◽  
Time Resolved ◽  
Vis Spectroscopy ◽  
Electron Paramagnetic

Bis-thiosemicarbazones derived from the β-diketone benzoylacetone (H3banR, R=Me, Et, Ph) are potentially tetradentate N2S2 ligands whose coordination chemistry with copper is reported. In the absence of oxygen and in the presence of base they form anionic CuII complexes of the fully deprotonated ligands [CuII(banR)]–. Upon exposure to atmospheric oxygen they undergo a complex series of reactions leading to two types of products; one a ligand oxidised ketone complex [CuII(banRO)] and the other an unprecedented dimeric di-CuIII complex [(CuIII(banR))2] depending on the R substituent. Time-resolved UV-vis spectroscopy, cyclic voltammetry, spectroelectrochemistry, and electron paramagnetic resonance (EPR) spectroscopy have been used to identify intermediates on the way to stable products formed under both anaerobic and aerobic conditions. It is found that both ligand-centred and Cu-centred oxidation reactions are occurring in parallel leading to this unusually complicated mixture of products.

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