Polyaromatic assembly mechanisms and structure selection in carbon materials

This article reports on the interfacial behavior of large liquid-phase polycyclic aromatic hydrocarbons in pitches that are common precursors to carbon materials. Experiments were conducted to identify preferred angles of molecular orientation ("surface anchoring" states) and to measure contact angles on a variety of well-characterized substrates. The results show that the large disklike polyaromatic molecules exhibit anomalously weak noncovalent interactions with a variety of surfaces, a fact that we attribute to inhibition of dispersion forces due to geometric mismatch at the interface. It is further found that large polyaromatics prefer edge-on molecular orientation at most interfaces, a configuration that preserves internal aromatic pi-pi bonds at the expense of inhibited pi-surface bonds. A theory of pi-pi bond preservation is proposed to explain many aspects of wetting, adsorption, anchoring, and supramolecular assembly in this important class of compounds, including the formation mechanism for the classic bipolar Brooks-Taylor mesocarbon spheres. The results are used to discuss the mechanisms of structure selection in carbon materials prepared at high and low temperatures. The results are also used to demonstrate a new approach for molecular engineering of carbon that employs anchoring templates to synthesize new materials with preprogrammed patterns of graphene layer orientation.