Evolution of manganese low-energy photoredox catalysis from high-energy visible light photocatalysis.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41593059.
- Also identified by DOI 10.1038/s41467-026-68837-y and PMC identifier 12948992.
- No licence information is recorded for this record.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
Reducing the energy input of light in photocatalytic reactions is desirable yet challenging, as modifying the light-absorbing or catalytic properties of a photocatalyst typically requires tedious preparation, resulting in a lengthy development process. Here, we overcome this limitation by achieving manganese-based low-energy photoredox catalysis through the in-situ assembly of simple Mn salts with inexpensive coordinating chemicals, thereby bypassing the need for complex pre-preparation. Assembling Mn(acac)<sub>2</sub>, 2,2'-bipyridine-6,6'-diamine, and TMSN<sub>3</sub> in-situ forms a visible-light-absorbing system that, upon blue-light irradiation, generates azido radicals to drive an anti-Markovnikov hydroazidation of unactivated alkenes with H<sub>2</sub>O as the hydrogen source. Building on this assembly strategy, the combination of Mn(acac)<sub>3</sub> and TMSN<sub>3</sub> in CH<sub>3</sub>CN/HFIP yields a system with a light-absorption range extended to 850 nm; this feature is further leveraged to unlock the selective aerobic hydroxyazidation of alkenes in a single step. These findings pave the way for the development of in-situ-assembled, 3 d metal-based low-energy photochemistry.