Pathways to the polymerization of boron monoxide dimer to give low-density porous materials containing six-membered boroxine rings.

Density functional theory has been used to examine the key mechanistic details of the polymerization of boron monoxide (BO) via its O≡B-B≡O dimer to give ultimately low-density porous polymeric (BO)n materials. The structures of such materials consist of planar layers of six-membered boroxine (B3O3) rings linked by boron-boron bonds. Initial cyclooligomerization of B2O2 leads to a B4O4 dimer with a four-membered B2O2 ring, a B6O6 trimer containing a six-membered B3O3 (boroxine) ring, a B8O8 tetramer containing an eight-membered B4O4 ring, and even a B10O10 pentamer containing a ten-membered B5O5 ring. However, an isomeric B10O10 structure containing two boroxine rings linked by a B-B bond is a much lower energy structure by ∼31 kcal/mol owing to the special stability of the aromatic boroxine rings. Rotation of the boroxine rings around the central B-B bond in this B10O10 structure has a low rotation barrier suggesting that further oligomerization to give products containing either perpendicular or planar orientations of the B3O3 rings is possible. However, the planar oligomers are energetically more favorable since they have fewer high-energy external BO groups bonded to the network of boroxine rings. The pendant boronyl groups are reactive sites that can be used for further polymerization. Mechanistic aspects of the further oligomerization of (BO)x systems to give a B24O24 oligomer with a naphthalene-like arrangement of boroxine rings and a B84O84 structure with a coronene-like arrangement of boroxine rings have been examined. Further polymerization of these intermediates by similar processes is predicted to lead ultimately to polymers consisting of planar networks of boroxine rings. The holes between the boroxine rings in such polymers suggests that they will be porous low-density materials. Applications of such materials as absorbents for small molecules are anticipated.