Charge Transfer Structure–Reactivity Dependence of Fullerene–Single-Walled Carbon Nanotube Heterojunctions

Charge transfer at the interface between single-walled carbon nanotubes (SWCNTs) of distinct chiral vectors and fullerenes of various molecular weights is of interest both fundamentally and because of its importance in emerging photovoltaic and optoelectronic devices. One approach for generating isolated, discretized fullerene–SWCNT heterojunctions for spectroscopic investigation is to form an amphiphile, which is able to disperse the latter at the single-SWCNT level in aqueous solution. Herein, we synthesize a series of methanofullerene amphiphiles, including derivatives of C<sub>60</sub>, C<sub>70</sub>, and C<sub>84</sub>, and investigated their electron transfer with SWCNT of specific chirality, generating a structure–reactivity relationship. In the cases of two fullerene derivatives, lipid–C<sub>61</sub>–polyethylene glycol (PEG) and lipid–C<sub>71</sub>–PEG, band gap dependent, incomplete quenching was observed across all SWCNT species, indicating that the driving force for electron transfer is small. This is further supported by a variant of Marcus theory, which predicts that the energy offsets between the nanotube conduction bands and the C<sub>61</sub> and C<sub>71</sub> LUMO levels are less than the exciton binding energy in SWCNT. In contrast, upon interfacing nanotubes with C<sub>85</sub> methanofullerene, a complete quenching of all semiconducting SWCNT is observed. This enhancement in quenching efficiency is consistent with the deeper LUMO level of C<sub>85</sub> methanofullerene in comparison with the smaller fullerene adducts, and suggests its promise as for SWCNT–fullerene heterojunctions.