Tuning the Coupling in Single‐Molecule Heterostructures: DNA‐Programmed and Reconfigurable Carbon Nanotube‐Based Nanohybrids

: Herein a strategy is presented for the assembly of both static and stimuli-responsive single-molecule heterostructures, where the distance and electronic coupling between an individual functional nanomoiety and a carbon nanostructure are tuned via the use of DNA linkers. As proof of concept, the formation of 1:1 nanohybrids is controlled, where single quantum dots (QDs) are tethered to the ends of individual carbon nanotubes (CNTs) in solution with DNA interconnects of different lengths. Photoluminescence investigations-both in solution and at the single-hybrid level-demonstrate the electronic coupling between the two nanostructures; notably this is observed to progressively scale, with charge transfer becoming the dominant process as the linkers length is reduced. Additionally, stimuli-responsive CNT-QD nanohybrids are assembled, where the distance and hence the electronic coupling between an individual CNT and a single QD are dynamically modulated via the addition and removal of potassium (K+) cations; the system is further found to be sensitive to K+ concentrations from 1 pM to 25 × 10-3 m. The level of control demonstrated here in modulating the electronic coupling of reconfigurable single-molecule heterostructures, comprising an individual functional nanomoiety and a carbon nanoelectrode, is of importance for the development of tunable molecular optoelectronic systems and devices.