Synthesis and Properties of Rubicene-Based Aromatic π-Conjugated Compounds as Five-Membered Ring Embedded Planar Nanographenes.

Polycyclic aromatic hydrocarbons consisting of two or three rubicene substructures were designed as π-conjugated compounds embedding five-membered rings. The target compounds with t-butyl groups were synthesized by the Scholl reaction of precursors consisting of 9,10-diphenylanthracene units, even though a partially precyclized precursor was required for the synthesis of the trimer. These compounds were isolated as stable and dark blue solids. Single-crystal X-ray analysis and DFT calculations revealed the planar aromatic framework of these compounds. In the electronic spectra, the absorption and emission bands were considerably red-shifted compared with those of the reference rubicene compound. In particular, the emission band of the trimer extended to the near-IR region while retaining the emissive property. The narrowed HOMO-LUMO gap with the extension of the π-conjugation was confirmed by cyclic voltammetry and DFT calculations.