Theoretical Studies of Furan and Thiophene Nanothreads: Structures, Cycloaddition Barriers, and Activation Volumes.

This theoretical study examines the formation, structure, and stability of two of the most ordered nanothreads produced yet, those derived from furan and thiophene. The energetic consequences and activation barriers of the first two steps of oligomerization via a Diels-Alder mechanism were examined. The ca. 20 GPa difference in the synthetic pressures (lower for furan) is explainable in terms of the greater loss of aromaticity by the thiophene. The effects of pressure on the reaction profiles, operating through a volume decrease along the reaction coordinate, are illustrated. The interesting option of polymerization proceeding in one or two directions opens up the possibility of polymers with opposing, cumulative dipole moments. The computed activation volumes are consistently more negative for furan, in accordance with the lower onset pressure of furan polymerization. The energetics of three ordered polymer structures were examined. The polymer, with all O/S atoms on the same side, if not allowed to distort, is at a high energy relative to the other two due to the O/S lone pair repulsion, understandably greater for S than for O at the 2.8/2.6 Å separation. Set free, the isomers curve or arch in two- or three-dimensional (helical) ways, whose energetics are traced in detail. The polymer can also stabilize itself by twisting into zig-zag or helical energy minima. The release of strain in a linear thread as the pressure is relaxed to 1 atm, with consequent thread curving, is a likely mechanism for the observed loss of the crystalline order in the polymer as it is returned to ambient pressure.