Dithio-Fused Boron Dipyrromethenes: Synthesis and Impact of S-Heteroaromatic Annulation Mode

Three dithio-fused boron dipyrromethenes (BODIPYs), DTFB-1, DTFB-2, and DTFB-3, in which symmetrically S-heteroaromatic ring units fused at [a], zigzag, and [b] bonds of the parent BODIPY core, respectively, were prepared from the facile and efficient post-functionalization of tetra-halogenated BODIPYs through Pd-catalyzed cyclization. Dithio-fusion at various positions of BODIPY effectively tunes their photophysical properties and single-crystal structural packing arrangements. The single-crystalline microribbons of DTFB-2 exhibit commendable hole mobilities in air, reaching up to 0.03 cm2 V–1 s–1.