Cha-Wen Chang

Highly stable anodic green electrochromic aromatic polyamides: synthesis and electrochromic properties

A 4-methoxy-substituted triphenylamine containing the aromatic diamine, 4,4′-diamino-4″-methoxytriphenylamine (2), was synthesized by the caesium fluoride-mediated condensation of p-anisidine with 4-fluoronitrobenzene, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediate. A series of new polyamides with pendent 4-methoxy-substituted triphenylamine (TPA) units having inherent viscosities of 0.27–1.39 dL g−1 were prepared via the direct phosphorylation polycondensation of various dicarboxylic acids and the diamine (2). All the polymers were readily soluble in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc), and could be solution-cast into tough and flexible polymer films. These aromatic polyamides had useful levels of thermal stability associated with their relatively high softening temperature (242–282 °C), 10% weight-loss temperatures in excess of 470 °C, and char yields at 800 °C in nitrogen higher than 60%. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium-tin oxide (ITO)-coated glass substrate exhibited reversible oxidation at 0.73–0.79 V versus Ag/AgCl in acetonitrile solution, and revealed excellent stability of electrochromic characteristics with a color change from colorless to green at applied potentials ranging from 0.00 to 1.05 V. These anodically polymeric electrochromic materials not only showed excellent reversible electrochromic stability with good green coloration efficiency (CE = 374 cm2 C−1) but also exhibited high contrast of optical transmittance change (ΔT %) up to 85% at 787 nm and 30% at 391 nm. After over 1000 cyclic switches, the polymer films still exhibited excellent stability of electrochromic characteristics.

Novel anodic electrochromic aromatic polyamides with multi-stage oxidative coloring based on N,N,N′,N′-tetraphenyl-p-phenylenediamine derivatives

A series of novel aromatic polyamides with pendent 4,4′-dimethoxy-substituted triphenylamine (TPA) units were prepared via the direct phosphorylation polycondensation from a new dicarboxylic acid monomer, N,N-bis(4-carboxyphenyl)-N′,N′-di(4-methoxyphenyl)-1,4-phenylenediamine (4), and various aromatic diamines. These polyamides were amorphous with good solubility in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc), and could be solution-cast into flexible polymer films. They had excellent levels of thermal stability associated with their relatively high glass-transition temperatures (233–308 °C). These polymers exhibited strong UV-vis absorption bands at 351–363 nm in NMP solution. Their photoluminescence spectra showed maximum bands around 450–504 nm. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide 6g prepared from the dicarboxylic acid monomer (4) with a structurally similar diamine monomer N,N-bis(4-aminophenyl)-N′,N′-di(4-methoxyphenyl)-1,4-phenylenediamine (5g) exhibited four reversible oxidation redox couples in acetonitrile solution at Eonset = 0.35, E1/2 = 0.64, 0.84, and 0.99 V, respectively. After over 3000 cyclic switches for green color, the films of polyamide 6g still showed excellent continuous cyclic stability of electrochromism.