Electrochromism of Nanographenes in the Near-Infrared Region.

Nanographene (NG) is a potential candidate for organic EC materials because of its large π-conjugated system, chemical stability, absorption band covering the visible region, and tunable optical properties by postsynthetic modification. We show that NGs carrying redox-active triphenylamine (TPA) units covalently linked to the NG edge function as EC materials in the NIR region. The hybrid materials can be obtained by the installation of TPA units onto the NG edge and display changes in the absorption spectrum in the NIR region extending to a wavelength of over 2000 nm upon one-electron oxidation and reduction at low potentials (<1.1 V). Time-dependent unrestricted density functional theory calculation of a model NG at the UB3LYP/6-31G(d,p) level of theory suggests that a narrow energy gap between the basal plane and the oxidized TPA unit is responsible for the observed EC function in the NIR region.