Functionalization of boron-doped tri(9,10-anthrylene)s

9,10-Dianthryl-9,10-dihydro-9,10-diboraanthracene derivatives bearing two peripheral chloro (3) or bromo (5) substituents have been synthesized. X-ray crystallography reveals a mutually perpendicular orientation of the individual planes within each of the molecules. The two bromo substituents in 5 can be replaced by NMe2 (6) or thiophen-2-yl (7) groups using Me3Sn–NMe2 or nBu3Sn–C4H3S and Pd-mediated C–N or C–C coupling protocols. Compounds 3, 5, and 7 show TICT photoluminescence and a pronounced positive solvatochromism in agreement with a charge-separated excited state.