Electrophilic borylation using BCl3 and benzothiadiazole to direct the C–H functionalisation of an adjacent aromatic unit produces fused boracyclic materials with minimally changed HOMO energies but significantly reduced LUMO energies.

A synthetic route to planar P-modified polycylic aromatic hydrocarbons (PAHs) is described. The presence of a reactive σ(3),λ(3)-P moiety within the sp(2)-carbon scaffold allows the preparation of a new family of PAHs displaying tunable optical and redox properties. Their frontier molecular orbitals (MOs) are derived from the corresponding phosphole MOs and show extended conjugation with the entire π framework. The coordination ability of the P center allows the coordination-driven assembly of two molecular PAHs onto a Au(I) ion.

The incorporation of boron into the core structure of fused polycyclic aromatics generates compounds with highly attractive properties that have recently received significant attention. Embedding boron into the backbone of ladder or 2D poly aromatic hydrocarbons is an underexplored approach to modulate optoelectronic properties, with tricoordinate boron representing a novel acceptor moiety for organic optoelectronic applications. Furthermore, the incorporation of boron into polycyclics containing other heteroatoms (e.g., chalcogens or pnictogens) leads to more extensive structural diversity and considerable ability to modify the frontier orbital energies and character, often in a controlled manner, to fine tune material properties for specific applications. This feature article summarizes the recent key developments in this field.