Intercolumnar Interactions Control the Local Orientations within Columnar Stacks of Sumanene and Sumanene Derivatives

Density functional theory, symmetry-adapted perturbation theory, and classical molecular dynamics simulations were used to understand the local orientations within columnar stacks of sumanene, sumaneneone, sumanenedione, and sumanenetrione, which can impact the electronic properties of the resulting materials. Unlike sumanene and sumaneneone, which pack in staggered columnar arrangements, sumanenetrione adopts an eclipsed configuration in the solid state. Reliable quantum chemical computations on stacked dithers and trimers of these molecules reveal that all four systems prefer staggered configurations. The tendency of sumanenetrione to pack in an eclipsed configuration was explained based on repulsive intercolumnar O center dot center dot center dot O interactions that override the inherent tendency of stacked columns to be staggered. Sumanenedione, for which crystal structure data are not available, was predicted to exhibit,columnar packing with mixed staggered and eclipsed orientations.