Hole Transfer from Photoexcited Quantum Dots: The Relationship between Driving Force and Rate.

We have investigated the relationship between driving force and rate for interfacial hole transfer from quantum dots (QDs). This relationship is experimentally explored by using six distinct molecular hole acceptors with an 800 meV range in driving force. Specifically, we have investigated ferrocene derivatives with alkyl thiol moieties that strongly bind to the surface of cadmium chalcogenide QDs. The redox potentials of these ligands are controlled by functionalization of the cyclopentadiene rings on ferrocene with electron withdrawing and donating substituents, thus providing an avenue for tuning the driving force for hole transfer while holding all other system parameters constant. The relative hole transfer rate constant from photoexcited CdSe/CdS core/shell QDs to tethered ferrocene derivatives is determined by measuring the photoluminescence quantum yield of these QD-molecular conjugates at varying ferrocene coverage, as determined via quantitative NMR. The resulting relationship between rate and energetic driving force for hole transfer is not well modeled by the standard two-state Marcus model, since no inverted region is observed. Alternative mechanisms for charge transfer are posited, including an Auger-assisted mechanism that provides a successful fit to the results. The observed relationship can be used to design QD-molecular systems that maximize interfacial charge transfer rates while minimizing energetic losses associated with the driving force.