Probing effects of molecular conformation on the electronic and charge transport properties in two- and three-dimensional small molecule hole-transporting materials: a theoretical investigation.

Thiophene/benzene-fused π-conjugated systems are normally employed as the core units of two- and three-dimensionally expanded small molecule hole-transporting materials (HTMs) to improve their electronic and charge transport properties, whereas comparison studies between two-dimensional and three-dimensional core conformations are less reported. To further find useful clues for the design of highly-efficient small molecule HTMs and to find new core units, in this work, four HTM molecules are designed by employing triphenylene, benzotrithiophene, triptycene, and thiophenetriptycene as the core units, and simulated with density functional theory combined with the Marcus hopping model. Our results show that all the considered HTMs display appropriate molecular energy levels, less optical absorption in the visible light region and large Stokes shifts, and high hole mobilities (9.80 × 10-2 cm2 V-1 s-1). Compared with the two-dimensional core structures, the three-dimensional cores exhibit evident superiorities with the same chemical components. Meanwhile, we also find that the quasi-degenerate HOMO energy levels will be helpful to enlarge the transfer integrals between adjacent molecules, and further to promote the hole transport in HTMs. By considering the various elements simultaneously, these investigated HTMs (S-1-S-4) with thiophene- and benzene-fused cores can be expected as potential promising candidates to help create more efficient solar cells.