Intercluster B-H and B-B aggregation in iso- and trans-[B20H18]2-. Spherical aromaticity in borane dimers.

ABSTRACT

The formation of molecular-based functional materials is a key step towards the development of technologies at the nanoscale. Recently, it has been shown that after oxidation of closo-[B10H10]2- anions, an induced aggregation of two cluster units is achieved, retaining their parent B10 backbones as persistent building blocks. Such characterization provides an interesting scenario to further understand relevant factors leading to aggregation in a minimal structure involving two units. Here, we explore the interaction between closo-[B10H10]2- units in two isomers, namely, iso- and trans-[B20H18]2-, involving different intercluster contacts based on B-B and B-H interactions, respectively. Our results show that the inherent spherical aromatic characteristics of the parent closo-[B10H10]2- cluster are persistent in both iso- and trans-[B20H18]2- isomers as an interplay between the spherical aromatic properties from both B10 motifs, leading to an overlap of the shielding regions from shielding cone properties, ascribed as a dual spherical-spherical aromatic cluster. From 11B-NMR features, it came out that trans-[B20H18]2- involves larger differences in comparison to closo-[B10H10]2-, owing to the variation of the B10-B10 backbone provided by the intercluster B-interaction, thus resulting in a more effective aggregation connecting such building units, towards boron-based cluster materials.