New P‐type of poly(4‐methoxy‐triphenylamine)s derived by coupling reactions: Synthesis, electrochromic behaviors, and hole mobility

Abstract

Methoxy‐substituted poly(triphenylamine)s, poly‐4‐methoxytriphenylamine (PMOTPA), and poly‐N,N‐bis(4‐methoxyphenyl)‐N′,N′‐diphenyl‐p‐phenylenediamine (PMOPD), were synthesized from the nickel‐catalyzed Yamamoto and oxidative coupling reaction with FeCl3. All synthesized polymers could be well characterized by 1H and 13C NMR spectroscopy. These polymers possess good solubility in common organic solvent, thermal stability with relatively high glass‐transition temperatures (Tgs) in the range of 152–273 °C, 10% weight‐loss temperature in excess of 480 °C, and char yield at 800 °C higher than 79% under a nitrogen atmosphere. They were amorphous and showed bluish green light (430–487 nm) fluorescence with quantum efficiency up to 45–62% in NMP solution. The hole‐transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. All polymers exhibited reversible oxidation redox peaks and Eonset around 0.44–0.69 V versus Ag/AgCl and electrochromic characteristics with a color change under various applied potentials. The series of PMOTPA and PMOPD also showed p‐type characteristics, and the estimated hole mobility of O‐PMOTPA and Y‐PMOPD were up to 1.5 × 10−4 and 5.6 × 10−5 cm2 V−1 s−1, respectively. The FET results indicate that the molecular weight, annealing temperature, and polymer structure could crucially affect the charge transporting ability. This study suggests that triphenylamine‐containing conjugated polymer is a multifunctional material for various optoelectronic device applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4037–4050, 2009

Synthesis and characterization of novel low‐bandgap triphenylamine‐based conjugated polymers with main‐chain donors and pendent acceptors for organic photovoltaics

“…1 and Schemes and ). These highly electron‐rich donor groups, including triphenylamine derivative ( M1 )21(c), 26 and electron‐donor blocks M2–M4 , in the backbones of the main‐chain copolymers endowed with strong and broad absorption spectra to obtain superior harvesting of sunlight and also suitable molecular energy levels to acquire good charge separations and transportations as well as high values of V oc . Solution‐processed BHJ PSC devices composed of an active layer of electron‐donor polymers blended with electron‐acceptor PC 61 BM or PC 71 BM were developed, and their photovoltaic properties were investigated as well.…”

Novel Starburst Triarylamine-Containing Electroactive Aramids with Highly Stable Electrochromism in Near-Infrared and Visible Light Regions

“…1 H NMR (DMSO-d 6 , δ, ppm): 3.72 (s, -OCH 3 ), 3.77 (s, -OCH 3 ), 6.69 (d, 4H), 6.77(d, 2H), 6.89 (d, 4H), 6.97À7.04 (m, 14H), 7.19 (d, 4H), 7.25 (d, 4H), 8.02 (d, 4H). 13 C NMR (DMSO-d 6 , δ, ppm): 55.40 (C 1 ), 55.54 (C 22 ),115.15,115.25,115.72,120.83,123.65,125.86,126.70,127.25,128.00,129.00,137.54,138.22,138.86,140.30,145.40,145.54,154.11,155.86,157.93. Anal.…”

Multichromic Polymers Containing Alternating Bi(3-Methoxythiophene) and Triphenylamine Based Units with Para-Protective Substituents

“…As a result of the presence of the dimer in polytriphenylamine, which usually show irreversible color changes during the dynamic electrochromic switches, polytriphenylamine (Poly(TPA)) cannot be used as ideal electrochromic materials [ 20 ]. The introduction of inactive substituent, e.g., methyl or cyano to one of the para-sites of TPA has been used for impeding the undesired side reactions, with the goal of promoting the formation of the linear, homogenous polymers, and finally enhancing the photoelectric properties of the polymers [ 21 , 22 ]. TPA-based conjugated polymers can be made by many methods.…”

“…At present, the Liou group have done much work on the TPA based polymers, including polyamides, polyimides and polyazomethines, most of which showed the multifunctional properties. Furthermore, as electrochromic materials, they usually showed P type doping process, and the colors of which were deepened from transmissive colorless state to coloring state as the potentials applied on the films increased gradually [ 21 , 22 ].…”