Competition between Förster Resonance Energy Transfer and Electron Transfer in Stoichiometrically Assembled Semiconductor Quantum Dot–Fullerene Conjugates

Understanding how semiconductor quantum dots (QDs) engage in photoinduced energy transfer with carbon allotropes is necessary for enhanced performance in solar cells and other optoelectronic devices along with the potential to create new types of (bio)sensors. Here, we systematically investigate energy transfer interactions between C₆₀ fullerenes and four different QDs, composed of CdSe/ZnS (type I) and CdSe/CdS/ZnS (quasi type II), with emission maxima ranging from 530 to 630 nm. C₆₀-pyrrolidine tris-acid was first coupled to the N-terminus of a hexahistidine-terminated peptide <i>via</i> carbodiimide chemistry to yield a C₆₀-labeled peptide (pepC₆₀). This peptide provided the critical means to achieve ratiometric self-assembly of the QD-(pepC₆₀) nanoheterostructures by exploiting metal affinity coordination to the QD surface. Controlled QD-(pepC₆₀)_<i>N</i> bioconjugates were prepared by discretely increasing the ratio (<i>N</i>) of pepC₆₀ assembled per QD in mixtures of dimethyl sulfoxide and buffer; this mixed organic/aqueous approach helped alleviate issues of C₆₀ solubility. An extensive set of control experiments were initially performed to verify the specific and ratiometric nature of QD-(pepC₆₀)_<i>N</i> assembly. Photoinitiated energy transfer in these hybrid organic–inorganic systems was then interrogated using steady-state and time-resolved fluorescence along with ultrafast transient absorption spectroscopy. Coordination of pepC₆₀ to the QD results in QD PL quenching that directly tracks with the number of peptides displayed around the QD. A detailed photophysical analysis suggests a competition between electron transfer and Förster resonance energy transfer from the QD to the C₆₀ that is dependent upon a complex interplay of pepC₆₀ ratio per QD, the presence of underlying spectral overlap, and contributions from QD size. These results highlight several important factors that must be considered when designing QD-donor/C₆₀-acceptor systems for potential optoelectronic and biosensing applications