Ligand-Controlled Electrochromic Diversification with Multilayer Coated Metallosupramolecular Polymer Assemblies

Designing surface-confined molecular systems capable of expressing changes in functional properties as a result of slight variations in chemical structure under the influence of an external stimulus is of contemporary interest. In this context, we have designed three tetraterpyridine ligands with variations in their core architecture (phenyl vs tetraphenylethynyl vs bithiophene) to create spray-coated electrochromic assemblies of iron(II)-based metallosupramolecular polymer network films on transparent conducting oxide substrates. These assemblies exhibited molecular permeability and spectroelectrochemical properties that are in turn dictated by the ligand structure. Electrochromic films with high coloration efficiencies (up to 1050 cm²/C) and superior optical contrast (up to 76%) with a concomitant color-to-color redox transition were readily achieved. These functional switching elements were integrated into sandwich-type electrochromic cells (CE up to 641 cm²/C) that exhibited high contrast ratios of up to 56%, with attractive ON-OFF ratios, fast switching kinetics, and high operational stability. Every measurable spectroelectrochemical property of the films and devices is an associated function of the ligand structure that coordinates the same metal ion to different extents. While exhibiting a ligand-structure induced differential metal coordination leading to porosity and spectroelectrochemical diversification, these assemblies allow the creation of electrochromic patterns and images by a simple spray-coating technique.