Stable, π-conjugated radical anions of boron-nitrogen dihydroindeno[1,2-b]fluorenes

We have recently reported the synthesis and application of boron-nitrogen dihydroindeno[1,2-b]fluorene derivatives as acceptors in organic photovoltaic (OPV) devices. Their modest observed efficiencies may be related to the properties of their reduced congeners. In this work, we report two new members of this family of compounds prepared via the electrophilic borylation of 2,5-di-p-tolylpyrazine followed by an arylation of the boron centre with ZnAr2 reagents. Two derivatives, 1 (Ar = 2,4,6-F3C6H2) and 2 (Ar = C6F5) were synthesized, and their radical anions, 1•− and 2•−, were formed via chemical reductions with CoCp*2 and CoCp2, respectively. Through comparison of structural parameters, as well as spectroscopic and computational data, the unpaired electron in the radical anions is localized in the planar core of the molecule, and dimerization is disfavored as a result. However, unlike the neutral starting materials, 1•− and 2•− are reactive towards ambient atmosphere. These observations suggest that the reduced compounds are stable towards intrinsic degradation pathways but subject to extrinsic degradation in device operation.