Oxidation of Weakly Interacting Diradicals: An Approach for Strong and Tunable Near-Infrared-Absorbing Dyes Based on Small Chromophores

Near-infrared (NIR)-absorbing dyes are valuable for various applications, such as bioimaging and electronic devices. This work introduces a novel approach for designing NIR dyes, oxidation of weakly coupled diradicals. Our approach features a weak exchange interaction in diradicals, which potentially leads to bonding/antibonding molecular orbitals with a small energy gap. We found that removing one of two singly occupied molecular orbital electrons of the diradicals results in an exceptionally narrow frontier orbital energy gap. We examined a series of Blatter radical dimers, and the most weakly coupled diradical prepared in this work (ΔEST ∼ 0.12 eV) with a molecular weight of 590 Da exhibited a strong NIR absorption band reaching 2200 nm upon one-electron oxidation. The optical band gaps of the radical cations strongly correlate to the exchange interaction in the precursor neutral species, offering prediction and fine-tuning of the optical band gap in the NIR region.