Divergent Synthesis of Alternant Bisanthenequinone and Nonalternant Heptalenodifluorenedione Ring Systems via a Concentration-Dependent Rearrangement.

Abstract

The synthesis of a diol containing a nonalternant aromatic core was investigated to access a nonalternant isomer of bisanthene with functional groups suitable for two-dimensional polymerization. An alternant diol and its nonalternant isomer were prepared in a short synthetic route from the same bifluorenylidene starting material. The bifluorenylidene reactant undergoes a Stone-Wales rearrangement in neat triflic acid, which unexpectedly provided both an alternant and nonalternant dione. The rearrangement was characterized by spectroscopy and single crystal X-ray diffraction of Grignard addition products of both isomers. The relative yield of the rearranged, alternant product increased along with the initial concentration of its polycyclic aromatic hydrocarbon (PAH) precursor, implicating a bimolecular rearrangement mechanism and enabling the divergent synthesis of both the nonalternant and alternant products. These findings offer convenient access to functional derivatives of two PAH classes of interest for their optoelectronic properties and serve as yet another warning about the importance of characterizing these materials with care, especially when insoluble products must be carried forward in a multistep synthetic route.