| Autor: |
Sartor SM; Department of Chemistry and Biochemistry , University of Colorado , Boulder , Colorado 80309 , United States., McCarthy BG; Department of Chemistry , Colorado State University , Fort Collins , Colorado 80523 , United States., Pearson RM; Department of Chemistry , Colorado State University , Fort Collins , Colorado 80523 , United States., Miyake GM; Department of Chemistry , Colorado State University , Fort Collins , Colorado 80523 , United States., Damrauer NH; Department of Chemistry and Biochemistry , University of Colorado , Boulder , Colorado 80309 , United States. |
| Abstrakt: |
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 *. |
