Click synthesis and reversible electrochromic behaviors of novel polystyrenes bearing aromatic amine units

Abstract

Novel electrochromic polymers were prepared by the click postfunctionalization of poly(4‐azidomethylstyrene) with alkyne‐containing aromatic amine units in the presence of Cu(I) catalysts. Two kinds of aromatic amine units, tris(4‐alkoxyphenyl)amine and N,N,N′,N′‐tetraphenyl‐p‐phenylenediamine, were introduced into polystyrene side chains, which were completely characterized by gel permeation chromatography–multiangle light scattering, nuclear magnetic resonance, and infrared spectroscopies, and elemental analysis. Thermal analyses demonstrated the high stability with the decomposition temperatures exceeding 300 °C even after postfunctionalization. The UV–vis absorption spectra of the polymer thin films revealed negligible absorption in the visible region, as reasonably confirmed by visual observation. The polymer thin films were prepared by spray‐coating on an indium tin oxide‐coated glass plate. Cyclic voltammograms of these films exhibited anodic peaks ascribed to the oxidation of the side‐chain aromatic amine moieties. The tris(4‐alkoxyphenyl)amine unit displayed one‐step oxidation at 0.287 V (vs. Ag/AgCl), while the N,N,N′,N′‐tetraphenyl‐p‐phenylenediamine unit showed two‐step oxidations at 0.297 and 0.641 V. These oxidation processes produced new colors of the polymer films. The former triarylamine‐based chromophore provided a blue color after the oxidation, while the latter phenylenediamine‐based chromophore showed a potentially controlled green and dark blue colors. The reversibility and switching behaviors of these color changes were also comprehensively investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Tröger's Base‐Containing Aromatic Polymers with Unexpected Properties Endowed by the Insertion of Alkyne Spacers

“…Thus, the first oxidation of P4 was caused by the triphenylamine units. The observed potential is consistent with previous reports of similar triphenylamine polymers …”

“…The observed potential is consistent with previous reports of similar triphenylamine polymers. [27][28][29][30] The redox activity of the selected P2 and P4 samples was also investigated by spectroelectrochemistry. When the potential of 1.5 V was applied to the polymer fi lms, their absorption peak intensities gradually decreased ( Figure S5, Supporting Information).…”

Electrochemical fluorescence switching properties of conjugated polymers composed of triphenylamine, fluorene, and cyclic urea moieties

“…In addition, TAAs usually show good hole‐transporting properties so that they are frequently adopted in the hole‐transporting layers in organic electroluminescent devices. Furthermore, TAAs usually demonstrate a noticeable change of coloration upon electrochemical redox processes so that they can be applied in electrochromic devices 27–39. In addition, most of these polymers show good solubility in organic solvents due to their nonplanar propeller‐shaped triarylamine units that disrupt the packing of aromatic rings in solid state; this leads to a relatively low crystallinity of the materials so that they can form homogeneous amorphous films in large‐area thin‐film devices, either by thermal vacuum deposition or by spin‐coating methods.…”

Polymeric Chemosensors: A Conventional Platform with New Click Chemistry

“…However, since CuAAC features high efficiency and no side reactions, the post-functionalization approach made possible the synthesis of side-chain type polymeric sensors. 39 The 1,2,3-triazole ring itself did not show any remarkable optical spectral changes in response to metal ion complexation. However, the conjugated substitution at the 1-and/or 4-positions enabled the formation of a fluorophore.…”