Enhancement of NIR-Absorbing Ability of Bis(diarylmethylium)-Type Dicationic Dyes Based on an Ortho-Substitution Strategy.

ABSTRACT

Electrochromic systems capable of switching near-infrared (NIR) absorption are fascinating from the viewpoint of applications in the materials and life sciences. Although 11,11,12,12-tetraaryl-9,10-anthraquinodimethanes (AQDs) with a folded form undergo one-stage two-electron oxidation to produce twisted dicationic dyes exhibiting NIR absorption, there is a need to establish a design strategy that can enhance the NIR-absorbing abilities of the corresponding dicationic dyes. In this study, we designed and synthesized a series of AQD derivatives with various substituents introduced at the ortho-position(s) of the 4-methoxyphenyl group. X-ray and spectroscopic analyses revealed that NIR-absorbing properties can be changed by introduction of the ortho-substituents. Thus, control of the steric and electronic effects of the ortho-substituents on the 4-methoxyphenyl groups was demonstrated to be an effective strategy for fine-tuning of the HOMO and LUMO levels for neutral AQDs and twisted dications, respectively, resulting in the modification of electrochemical and spectroscopic properties under an "ortho-substitution strategy".