| Popis: |
Incorporation of heteroatoms into polyarenes has been developed as an effective approach to alter their intrinsic structures and properties. Herein, we designed and synthesized two PO-containing dibenzopentaarene isomers (5a and 5b) and studied their structures and properties, along with those of dibenzopentaarenes containing six-membered Si- and B-heterocycles (3 and 4). These heterocyclic polyarenes have similar frameworks to well-known heptazethrene, and thus can be regarded as members of the heteroatom-doped zethrene system. The heterocycles greatly affect not only the molecular and packing structures but also the electronic structures and properties. Notably, while compounds 3 and 4 adopt almost planar geometries, 5a possesses a clearly curved conformation, leading to its brick-type slipped and dense π-π stacking mode. Moreover, the electron-withdrawing PO groups endow 5a and 5b with simultaneously lowered lowest unoccupied molecular orbital (LUMO)/highest occupied molecular orbital (HOMO) levels, whereas the p-π conjugation of the B atoms in 4 leads to its smaller energy gap and thus remarkably red-shifted absorption and fluorescence bands by over 80 nm, though all of these molecules possess similar closed-shell structures. This study thus deepens the understanding of heteroatom-doping effects, which may be expanded to develop other heteroatom-doped zethrene materials. |
