Molecular Graphene (MG) of a physical size and bonding character that render the molecule suitable as a channel material in an electronic device, such as a tunnel field effect transistor (TFET). The molecular graphene may be a large polycyclic aromatic hydrocarbon (PAH) employed as a discrete element, or as a repeat unit, within an active or passive electronic device. In some embodiments, a functionalized PAH is disposed over a substrate surface and extending between a plurality of through-substrate vias. Heterogeneous surfaces on the substrate are employed to direct deposition of the functionalized PAH molecule to surface sites interstitial to the array of vias. Vias may be backfilled with conductive material as self-aligned source/drain contacts. Directed self-assembly techniques may be employed to form local interconnect lines coupled to the conductive via material. In some embodiments, graphene-based interconnects comprising a linear array of PAH molecules are formed over a substrate.