Dibenzophosphapentaphenes: Exploiting P Chemistry for Gap Fine-Tuning and Coordination-Driven Assembly of Planar Polycyclic Aromatic Hydrocarbons

A synthetic route to planar P-modified polycylic aromatic hydrocarbons (PAHs) is described. The presence of a reactive σ3,λ3-P moiety within the sp2-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 AuI ion.