Mechanistic insights into chemical photocatalysis are mainly the domain of UV/Vis spectroscopy, because NMR spectroscopy has been limited by the type of illumination so far. An improved LED-based illumination device can be used to obtain NMR reaction profiles of photocatalytic reactions under synthetic conditions and perform both photo-CIDNP and intermediate studies. Flavin-catalyzed photooxidations of alcohols show the potential of this setup. After identical initial photoreaction steps the stabilization of a downstream intermediate is the key to the further reaction mechanism and the reactivity. As a chemical photocatalyst flavin can act either as a one- or a two-electron mediator when the stability of the zwitterionic radical pair is moldulated in different solvents. This demonstrates the importance of downstream intermediates and NMR-accessible complementary information in photocatalytic reactions and suggests the control of photoorganic reactions by solvent effects.
A series of 10-arylflavins (10-phenyl-, 10-(2',6'-dimethylphenyl)-, 10-(2',6'-diethylphenyl)-, 10-(2',6'-diisopropylphenyl)-, 10-(2'-tert-butylphenyl)-, and 10-(2',6'-dimethylphenyl)-3-methylisoalloxazine (2 a-f)) was prepared as potentially nonaggregating flavin photocatalysts. The investigation of their structures in the crystalline phase combined with (1)H-DOSY NMR spectroscopic experiments in CD(3)CN, CD(3)CN/D(2)O (1:1), and D(2)O confirm the decreased ability of 10-arylflavins 2 to form aggregates relative to tetra-O-acetyl riboflavin (1). 10-Arylflavins 2 a-d do not interact by π-π interactions, which are restricted by the 10-phenyl ring oriented perpendicularly to the isoalloxazine skeleton. On the other hand, N3-H⋅⋅⋅O hydrogen bonds were detected in their crystal structures. In the structure of 10-aryl-3-methylflavin (2 f) with a substituted N3 position, weak C-H⋅⋅⋅O bonds and weak π-π interactions were found. 10-Arylflavins 2 were tested as photoredox catalysts for the aerial oxidation of 4-methoxybenzyl alcohol to the corresponding aldehyde (model reaction), thus showing higher efficiency relative to 1. The quantum yields of 4-methoxybenzyl alcohol oxidation reactions mediated by arylflavins 2 were higher by almost one order of magnitude relative to values in the presence of 1.
The transition to maximum photoluminescence of InGaN single quantum wells is a phenomena that has time constants in the range of few seconds. Using a systematic illumination/darkening procedure we found that these characteristics are related to previous stimulations as if the sample has a memory of past illumination events. Choosing opportune time sequences, time constants were observed to vary more than 100%. These facts suggest the presence of carrier trapping/de-trapping processes that act beyond the single illumination event, accumulating over time in a complex effect.
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