Dye-sensitizedphotoanodesfor CH activationin organicsubstratesare assembledby vacuumsublimationof a commer-ciallyavailablequinacridone(QNC)dye in the form of nanosizedrods onto fluorine-dopedtin oxide(FTO),TiO2, and SnO2slides.The photoanodesdisplayextendedabsorptionin the visiblerange(450–600nm)andultrafastphotoinducedelectroninjection(<1 ps, as revealedby transientabsorptionspectro-scopy)of the QNCdye into the semiconductor.The proton-coupledelectron-transferreactivityof QNCis exploitedforgeneratinga nitrogen-basedradicalas its oxidizedform,whichis competentin CH bondactivation.The key reactivity parameteris the bond-dissociationfree energy(BDFE)associ-atedwiththe N·/NH couplein QNCof 80.5�2.3 kcalmol1,whichenableshydrogenatomabstractionfromallylicorbenzylicCH moieties.A photoelectrochemicalresponseisindeedobservedfor organicsubstratescharacterizedby CHbondswith BDFEbelowthe 80.5 kcalmol1threshold,such asγ-terpinene,xanthene,or dihydroanthracene.This workprovidesa rational,mechanisticallyorientedrouteto the designof dye-sensitizedphotoelectrodesfor selectiveorganictransforma-tions.

Photoelectrochemical C−H Activation Through a Quinacridone Dye Enabling Proton-Coupled Electron Transfer

Yang Y.;Volpato G. A.;Rossin E.;Peruffo N.;Tumbarello F.;Nicoletti C.;Bonetto R.;Paoloni L.;Umari P.;Colusso E.;Dell'Amico L.;Collini E.;Agnoli S.;Sartorel A.
2023

Abstract

Dye-sensitizedphotoanodesfor CH activationin organicsubstratesare assembledby vacuumsublimationof a commer-ciallyavailablequinacridone(QNC)dye in the form of nanosizedrods onto fluorine-dopedtin oxide(FTO),TiO2, and SnO2slides.The photoanodesdisplayextendedabsorptionin the visiblerange(450–600nm)andultrafastphotoinducedelectroninjection(<1 ps, as revealedby transientabsorptionspectro-scopy)of the QNCdye into the semiconductor.The proton-coupledelectron-transferreactivityof QNCis exploitedforgeneratinga nitrogen-basedradicalas its oxidizedform,whichis competentin CH bondactivation.The key reactivity parameteris the bond-dissociationfree energy(BDFE)associ-atedwiththe N·/NH couplein QNCof 80.5�2.3 kcalmol1,whichenableshydrogenatomabstractionfromallylicorbenzylicCH moieties.A photoelectrochemicalresponseisindeedobservedfor organicsubstratescharacterizedby CHbondswith BDFEbelowthe 80.5 kcalmol1threshold,such asγ-terpinene,xanthene,or dihydroanthracene.This workprovidesa rational,mechanisticallyorientedrouteto the designof dye-sensitizedphotoelectrodesfor selectiveorganictransforma-tions.
2023
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/3469234
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