Exploiting Charge-Transfer States for Maximizing Intersystem Crossing Yields in Organic Photoredox Catalysts
| Autor: | Steven M. Sartor, Ryan M. Pearson, Blaine G. McCarthy, Niels H. Damrauer, Garret M. Miyake |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Molecular Structure
010405 organic chemistry Quantum yield Charge (physics) General Chemistry 010402 general chemistry Photochemistry Photochemical Processes 01 natural sciences Biochemistry Catalysis Article 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry Intersystem crossing chemistry Excited state Organometallic Compounds Transition Elements Quantum Theory Phenoxazine Oxidation-Reduction |
| Zdroj: | Journal of the American Chemical Society. 140(14) |
| ISSN: | 1520-5126 |
| Popis: | A key feature of prominent transition-metal-containing photoredox catalysts (PCs) is high quantum yield access to long-lived excited states characterized by a change in spin multiplicity. For organic PCs, challenges emerge for promoting excited-state intersystem crossing (ISC), particularly when potent excited-state reductants are desired. Herein, we report a design exploiting orthogonal π-systems and an intermediate-energy charge-transfer excited state to maximize ISC yields (Φ(ISC)) in a highly reducing (E(0)* = −1.7 V vs SCE), visible-light-absorbing phenoxazine-based PC. Simple substitution of N-phenyl for N-naphthyl is shown to dramatically increase Φ(ISC) from 0.11 to 0.91 without altering catalytically important properties, such as E(0)*. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|