Meta-B-entacenes: new polycyclic aromatics incorporating two fused borepin ringsElectronic supplementary information (ESI) available: Experimental procedures, 1H and 13C NMR spectra, UV-Vis and PL spectra, crystallographic data, and theoretical data. See DOI:10.1039/c2cc32500dThis article is part of the ChemComm 'Aromaticity' web themed issue

The synthesis of new boron-containing acenes ( meta-B -entacenes) is reported. These compounds exhibit slightly non-planar core geometries with blue-shifted spectral properties and more negative electrochemical reduction potentials relative to known para isomers. Polarizable π-extended architectures were realized via cross-coupling procedures with chloro-functionalized precursors. New, curved boron-containing acenes have been synthesized, demonstrating cathodic electrochemistry, strong photoluminescence, and facile cross-coupling to give π-extended scaffolds.