Enhancing Charge Transport Using Boron and Nitrogen Substitutions into Triphenylene-Based Discotic Liquid Crystals

The substitution of p-block heteroatoms into polyaromatic hydrocarbons offers the potential for introducing enhanced molecular properties and advancing material development for electro-optical applications. Using density functional theory, we characterize the substitution of boron and nitrogen atoms into a 2,3,6,7,10,11-hexakis(hexathiol)triphenylene (TTP) core, a precursor for a material with a discotic liquid crystal phase, to determine the strength of exciton dissociation and the influence doping has on the formation of a heterojunction with graphene. The substitution of nitrogen and boron into the TTP motif enables tunability of both electron and hole coupling between hetero- and homodyads. The coupling is found to far exceed that of TTP and varied transport behavior with different combinations of doped cores of nitrogen-TTP and boron-TTP is reported. Heterodyads of nitrogen-TTP with boron-TTP appear to be ambipolar in electron/hole coupling, whereas heterodyads of boron- or nitrogen-TTP with TTP form strong electron coupling dyads and homodyads of nitrogen-TTP and boron-TTP form strong hole coupling. Finally, we describe the heterojunction of nitrogen- or boron-TTP with monolayer graphene and observe Ohmic contacts with large hole transport barriers. The presence of induced dipoles occurs at the interface in all heterojunctions, suggesting the possibility of tuning the junction with external potentials and improving exciton dissociation.