6533b855fe1ef96bd12b1312
RESEARCH PRODUCT
Excited State N−H Tautomer Selectivity in the Singlet Energy Transfer of a Zinc(II)-Porphyrin-Truxene-Corrole Assembly
Paul-ludovic KarsentiClaude P. GrosPierre D. HarveyAdam LangloisHai-jun XuHai-jun Xusubject
chemistry.chemical_elementDexter energy transferZinccore-modified corroles010402 general chemistryPhotochemistry7. Clean energy01 natural sciencesmain-group elements[ CHIM ] Chemical SciencesCatalysisfree-base corroleschemistry.chemical_compoundmolecular-orbital methods[CHIM]Chemical SciencesSinglet stateCorrolecorrolesdensity-functional theoryvalence basis-setsphotophysical propertiestautomerization010405 organic chemistrytruxenesensitized solar-cellsOrganic ChemistryGeneral ChemistryTautomerPorphyrin0104 chemical scienceschemistrymesosubstituted corrolesExcited stateFRETextended basis-setsSelectivityLinkerdescription
International audience; An original corrole-containing polyad for S-1 energy transfer, in which one zinc(II)-porphyrin donor is linked to two free-base corrole acceptors by a truxene linker, is reported. This polyad exhibits a rapid zinc(II)-porphyrin*free-base corrole transfer (4.83x10(10)s(-1); 298K), even faster than the tautomerization in the excited state processes taking advantage of the good electronic communication provided by the truxene bridge. Importantly, the energy transfer process shows approximately 3-fold selectivity for one corrole N-H tautomer over the other even at low temperature (77K). This selectivity is due to the difference in the J-integral being effective in both the Forster and Dexter mechanisms. The data are rationalized by DFT computations.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2017-04-11 |