Near-Infrared Boron Difluoride Formazanate Dyes

Authors

Francis L. Buguis
Ryan R. Maar
Viktor N. Staroverov
Joe GilroyFollow

Document Type

Article

Publication Date

Winter 11-2-2020

Journal

Chemistry - A European Journal

Volume

27

First Page

2854

Abstract

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 p-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 BF₂ formazanate dyes (λ_abs = 691−760 nm, λ_PL = 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 BF₂ formazanate moieties. Density-functional calculations indicate that the NIR electronic transitions in BF₂ formazanates are of p®p*-type, but do not always involve strong charge transfer.