Highly Stable Electrochromic Polyamides Based on N,N-Bis(4-aminophenyl)-N′,N′-bis(4-tert-butylphenyl)-1,4-phenylenediamine

A new triphenylamine-containing aromatic diamine monomer, N,N-bis (4-aminophenyl)-,N',N'-bis(4-tert-butylphenyl)-1,4-phenylenediamine, was synthesized by an established synthetic procedure from readily available reagents. A novel family of electroactive polyamides with di-tert-butyl-substituted N,N,N',N'-tetraphenyl-1,4-phenylenediamine units were prepared via the phosphorylation polyamidation reactions of the newly synthesized diamine monomer with various aromatic or aliphatic dicarboxylic acids. All the polymers were amorphous with good solubility in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N V-dimethylacetamide, and could be solution-cast into tough and flexible polymer films. The polyamides derived from aromatic dicarboxylic acids had useful levels of thermal stability, with glass-transition temperatures of 269-296 degrees C, 10% weight-loss temperatures in excess of 544 degrees C, and char yields at 800 degrees C in nitrogen higher than 62%. The dilute solutions of these polyamides in NMP exhibited strong absorption bands centered at 316-342 nm and photoluminescence maxima around 362-465 nm in the violet-blue region. The polyamides derived from aliphatic dicarboxylic acids were optically transparent in the visible region and fluoresced with a higher quantum yield compared with those derived from aromatic dicarboxylic acids. The hole-transporting and electrochromic properties were examined by electrochemical and spectro-electrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium-tin oxide-coated glass substrate exhibited two reversible oxidation redox couples at 0.57-0.60 V and 0.95-0.98 V versus Ag/AgCl in acetonitrile solution. The polyamide films revealed excellent elcterochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.0 to 1.2 V. These anodically coloring polymeric materials showed interesting electrochromic properties, such as high coloration efficiency (CE = 216 cm(2)/C for the green coloring) and high contrast ratio of optical transmittance change (Delta T%) up to 64% at 424 nm and 59% at 983 nm for the green coloration, and 90% at 778 nm for the blue coloration. The electroactivity of the polymer remains intact even after cycling 500 times between its neutral and fully oxidized states. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2330-2343, 2009