π-Fused bis-BODIPY as a candidate for NIR dyes

Abstract

Benzene-fused bis-(borondipyrromethene)s (bis-BODIPYs) were synthesized by retro-Diels–Alder reaction of the corresponding bicyclo[2.2.2]octadiene-fused (BCOD-fused) bis-BODIPYs, which were, in turn, prepared from 4,8-ethano-4,8-dihydropyrrolo[3,4-f]isoindole derivatives. The π-fused bis-BODIPY chromophores were designed to show intensive absorption and strong fluorescence in the near-infrared region and not to have any strong absorption in the visible region. A 6,10-dibora-5a,6a,9a,10a-tetraaza-s-indaceno[2,3-b:6,5-b′]difluorene derivative (syn-bis-benzoBODIPY) obtained by a thermal retro-Diels–Alder reaction of the corresponding BCOD-fused BODIPY dimer has strong absorption and emission bands at 775 and 781 nm, respectively. The absolute quantum yield is 0.36. The absorption is more than 5.0 times stronger than other absorptions observed in the visible region. In the case of 6,15-dibora-5a,6a,14a,15a-tetraaza-s-indaceno[2,3-b:6,7-b′]difluorene derivatives (anti-bis-benzoBODIPY), the absorption and emission maxima exceed 840 nm.