Guiding synthetic targets of anodically coloring electrochromes through density functional theory

Electrochromic devices offer many technological applications, including flexible displays, dimmable mirrors, and energy-efficient windows. Additionally, adsorbing electrochromic molecular assemblies onto mesoporous metal-oxide surfaces facilitates commercial manufacturing potential (i.e., screen-printing and/or roll-to-roll processing). These systems also demonstrate synthetic versatility, thus making a wide array of colors accessible. In this work, using Time-Dependent Density Functional Theory (TD-DFT), we investigated ten different bi-aryl type molecules 3,4-ethylendioxythiophene (EDOT) conjugated to various phenyl derivatives as anodically coloring electrochromes (ACEs). The non-substituted phenylene, hexylthiol-EDOT-phenyl-phosphonic acid, PA1, was synthesized characterized means model validity. PA1 absorbs in the UV region its neutral state upon oxidation within visible, hence showcasing an ACE chromophore. properties inspired designs other nine structural where number position methoxy groups on phenylene were varied. Using our DFT treatment, assessed impact these modifications electronic structures, geometries, excited-state properties. particular, examined stabilization intermolecular interactions (S–O O–H) they aid molecule planarization, facilitating charge transport devices. destabilizing O–O forces observed, thereby some chromophores less desirable. A detailed excited analysis performed, which linked simulated UV-Vis spectra dominant transitions their corresponding orbitals. Based results, ranked ergo providing ordered list targets.