All Donor Electrochromic Polymers Tunable across the Visible Spectrum via Random Copolymerization

Abstract

A series of conjugated, random terpolymers based on all donor repeat units are prepared via direct (hetero)arylation polymerization yielding cathodically colored electrochromic polymers that span the visible spectrum. The polymers are based on repeat units of a dialkylthiophene, a 3,4-propylenedioxythiophene, and dimers of 3,4-ethylenedioxythiophene. Using a tight feedback loop between computational and experimental chemistry, the colors of these polymers are controllably tuned to cover the visible spectrum by controlling the monomer ratios. Examinations via ultraviolet−visible−near-infrared spectroscopy, differential pulse voltammetry, spectroelectrochemistry, and colorimetry show that, while these systems can vary greatly in their spectral properties, their oxidation potentials are all low (<0.5 V vs Ag/AgCl). The color tunability allows for access to neutral state orange, red, pink, magenta, purple, and blue polymers of various hues with a* values ranging from 22 to 35 and b* values ranging from −44 to 45, while maintaining highly transmissive oxidized states. This approach allows access to a wide gamut of colors with only three monomers while affording materials with low oxidation potentials and high contrast.

Water-Processable Self-Doped Conducting Polymers via Direct (Hetero)arylation Polymerization

“…Unlike biphasic polymerization conditions, the use of a solvent miscible in water is very important to allow good mixing of organic-soluble and water-soluble reagents, otherwise, no reaction occurs. Scheme 2b presents a polymerization method adapted from Reynolds et al 37 While method (a) gave better results for polymers P2, P3, P4a-b, and P5, method (b) has given better results for polymers P1a-d and P6. The detailed polymerization methods can be found in the SI and the polymerization yields in Table 1.…”

Synergistically Improved Molecular Doping and Carrier Mobility by Copolymerization of Donor–Acceptor and Donor–Donor Building Blocks for Thermoelectric Application

“…Random copolymers are conventionally treated as irregular polymers with structural disorder along the backbone. Nevertheless, the large space for the adjustment of energy levels [29,30] and electrical properties [31][32][33] endows them with potentially enhanced TE behaviors. Herein, we introduce planar diketopyrrolopyrrole (DPP) as acceptor unit, thienothiophene and oligo ethylene glycol functionalized bithiophene as donor units, to synthesize a series of new random copolymers (Figure 1, bottom layer) consisting of DPP-TT (green shadow, abbreviated to DPP-TT in following text) and g 3 2T-TT building blocks (red shadow, abbreviated to g 3 2T-TT).…”

Twenty years of exceptional success: The molecular education and research consortium in undergraduate computational chemistry (MERCURY)

“…The faculty published 2 peer‐reviewed books, [ 238,239 ] 9 peer‐reviewed book chapters, [ 240–248 ] and 115 peer‐reviewed research papers. [ 249–363 ] This comes to 1.6 peer‐reviewed products/faculty/year during the 3‐year grant period, which is 3.2 times the rate of publication for natural science faculty at PUIs. [ 46 ]…”