Deazaflavins are well suited for reductive chemistry acting via a consecutive photo-induced electron transfer, in which their triplet state and semiquinone - the latter is formed from the former after electron transfer from a sacrificial electron donor - are key intermediates. Guided by mechanistic investigations aiming to increase intersystem crossing by the internal heavy atom effect and optimising the concentration conditions to avoid unproductive excited singlet reactions, we synthesised 5-aryldeazaflavins with Br or Cl substituents on different structural positions via a three-component reaction. Bromination of the deazaisoalloxazine core leads to almost 100 % triplet yield but causes photo-instability and enhances unproductive side reactions. Bromine on the 5-phenyl group in ortho position does not affect the photostability, increases the triplet yield, and allows its efficient usage in the photocatalytic dehalogenation of bromo- and chloroarenes with electron-donating methoxy and alkyl groups even under aerobic conditions. Reductive powers comparable to lithium are achieved.

Department of Inorganic Chemistry University of Chemistry and Technology Prague Technická 5 166 28 Prague 6 Czech Republic

Department of Organic Chemistry University of Chemistry and Technology Prague Technická 5 166 28 Prague 6 Czech Republic

Institute for Biophysics and Physical Biochemistry University of Regensburg D 93053 Regensburg Germany

Institute of Physical and Theoretical Chemistry University of Regensburg D 93053 Regensburg Germany

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A facile three-component route to powerful 5-aryldeazaalloxazine photocatalysts