Ir-catalyzed direct diborylation of anthracene produced a 1:1 mixture of 2,6- and 2,7-diborylanthracenes, which could be separated by recrystallization. The Suzuki-Miyaura cross-coupling using 2,7-diborylanthracene gave extended pi-conjugated 2,7-disubstituted anthracene derivatives as building blocks for macrocycles. A 1:1 mixture of 2,7-di(4-pyridyl)anthracene and [Pd(dppp)(OTf)(2)] self-assembled into a [3 + 3] macrocycle.