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- Neutral, Heteroleptic [Cu(I)(PPh3)2(4H-imidazolato)] Complexes: Ligand Exchange Reactivity, Redox Properties, Excited-State Dynamics
Neutral, Heteroleptic [Cu(I)(PPh3)2(4H-imidazolato)] Complexes: Ligand Exchange Reactivity, Redox Properties, Excited-State Dynamics
in: Chemistry-A European Journal (2023)
Cu(I)4H-imidazolatecomplexesare rare examplesof Cu(I)complexeswithchelatinganionicligandsand arepotentphotosensitizerswithuniqueabsorptionand photo-redoxproperties.In this contribution,five novelheterolepticCu(I)complexeswithmonodentatetriphenylphosphineco-ligandsare investigated.As a consequenceof the anionic4H-imidazolateligandand in contrastto comparablecomplexeswithneutralligands,thesecomplexesare morestablethantheirhomolepticbis(4H-imidazolato)Cu(I)congeners.Here,the ligandexchangereactivitywas studiedby31P-,19F-, andvariabletemperatureNMRand the groundstatestructuralandelectronicpropertiesby X-raydiffraction,absorptionspectroscopy,andcyclicvoltammetry.Theexcited-statedynamicswereinvestigatedby femto-andnanosecondtransientabsorptionspectroscopy.The observeddifferences,withrespectto chelatingbisphosphinebearingcongeners,are oftendue to the increasedgeometricflexibilityof thetriphenylphosphines.Theseobservationsrenderthe inves-tigatedcomplexesinterestingcandidatesforphoto(redox)reactionsnot accessiblewithchelatingbisphos-phineligands.