Theoretical investigation of electrochromic mechanism in D–A conjugated polymers in visible and infrared bands

Electrochromic materials have been widely-applied in military camouflage and intelligent materials, in consideration of the multicolor display and infrared absorption. However, most of them have a narrow width of absorption spectra, and the electrochromic mechanism is still not well understood, especially in materials based on a copolymer structure in visible and infrared bands. Therefore, based on the polaron model, in order to enhance polarizability, we designed an “electronic donors–electronic acceptor” (D–A) type π-conjugated electrochromic polymer, which has an abundant color (wavelengths from 450 nm to 750 nm) with voltage range (from −0.2 V to 1.0 V). Employing first-principle calculations, we investigated the electrochromism of the polymer, which has a strong connection with the introduced new molecular orbital in the polaron (or cation), comparing with those in the neutral molecule. This study addressed the underlying mechanism for the electrochromic phenomenon and the behavior of the cation. It indicated the polaron molecular orbitals provide the photon absorption, whose energies are in the visible range and result in the electrochromic abundant color. In this work, we provide a molecular design for the adjustment of visible and infrared band absorption, which could have broad application in multicolor and infrared electrochromic materials.