Near-Infrared Boron Difluoride Formazanate Dyes.

Near-infrared (NIR) dyes are sought after for their utility in light harvesting, bioimaging, and light-mediated therapies. Since long-wavelength photoluminescence typically involves extensive π-conjugated systems of double bonds and aromatic rings, it is often assumed that NIR dyes have to be large molecules that require complex syntheses. We challenge this assumption by demonstrating that facile incorporation of tertiary amine groups into readily available 3-cyanoformazans affords efficient production of relatively simple NIR-active BF formazanate dyes (λ =691-760 nm, λ =834-904 nm in toluene). Cyclic voltammetry experiments on these compounds reveal multiple reversible redox waves linked to the interplay between the tertiary amine and BF formazanate moieties. Density-functional calculations indicate that the NIR electronic transitions in BF formazanates are of π→π*-type, but do not always involve strong charge transfer.