Aromatic Trails. Persistence and Interplay Between Linked Spherical Aromatic Dicarboranes in Dimer to Hexamer Linear Arrays

Abstract

The consecutive crack-link between well-defined building blocks is a plausible strategy in developing molecularly conceived materials. Here, we evaluate the resulting behavior of dimer to hexamer linear arrays based on linking spherical aromatic para-[C2B10H10] clusters (1) as relevant motifs toward understanding the characteristics of extended linear materials. Our results exhibit the persistence of spherical aromatic properties from the parent building block as isolated spherical aromatic states within the overall structure. Under different orientations of the applied field, the multiple enabled shielding cones at each linked cluster can evolve from a perfectly parallel disposition to an enhanced overlap under rotation. In addition, large values of NICS isosurfaces serve to locate the independent spherical aromatic states, whereas the use of anisotropy (NICSaniso) recovers the resulting isotropic regions at such states within the overall linear structure. Such behavior is expected to be envisaged in extended linear arrays and non-covalently interacting scenarios, such as self-assembled monolayers. Our results encourage further quests for understanding the interplay between different linked aromatic states, envisaging and unraveling the overall behavior of extended architectures designed by connecting aromatic building units.