Synthesis, photoluminescence, and electrochromism of polyamides containing (3,6‐di‐tert‐butylcarbazol‐9‐yl)triphenylamine units

Abstract

A new carbazole-derived, triphenylamine (TPA)containing aromatic dicarboxylic acid monomer, 4,4 0 -dicarboxy-4 00 -(3,6-di-tert-butylcarbazol-9-yl)TPA, was synthesized, and it led to a series of electroactive aromatic polyamides with main-chain TPA and pendent 3,6-bis(tert-butyl)carbazole units by reacting it with various aromatic diamines via the phosphorylation polyamidation technique. The polyamides were amorphous with good solubility in many organic solvents and could be solution-cast into flexible and strong films. They showed high glass-transition temperatures (282-335 C) and high thermal stability (10% weight loss temperatures >480 C). The electroactive polymer films had well-defined and reversible redox couples with good cycle stability in acetonitrile solutions. The polymer films also exhibited fluorescent and multielectrochromic behaviors. The anodically electrochromic polyamide films had moderate coloration efficiency ($100 cm 2 /C) and high optical contrast ratio of transmittance change (D%T) up to 47% at 813 nm and 48% at 414 nm for the green coloring. After hundreds of cyclic switches, the polymer films still retained good redox and electrochromic activity. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: [4775][4776][4777][4778][4779][4780][4781][4782][4783][4784][4785][4786][4787][4788][4789] 2010

Enhancing Redox Stability and Electrochromic Performance of Polyhydrazides and Poly(1,3,4‐oxadiazole)s with 3,6‐Di‐tert‐butylcarbazol‐9‐yltriphenylamine Units

“…The first oxidation wave can be due to the formation of triphenylamino radical cation and the second one is attributable to the oxidation of the carbazole moiety. [29] In addition, well-defined reduction waves for the formation of radical anion and dianion of the oxadiazole units [ Figure 2(b)] were observed in the negative side of the voltammogram at E 1/2 ¼ -1.10 and -1.33 V, respectively. The possible mechanisms of electrooxidation and reduction of the aryl amine and oxadiazole groups have been proposed in the previous publications.…”

“…¼ 364-366 8C] [29] and 4,4'-dicarboxy-4''-(carbazol-9-yl)triphenylamine (1') (m.p. ¼ 334-337 8C), [27] were synthesized according to the previously reported procedures.…”

Functional Aromatic Polyamides

“…The optical transmittance change between the neutral and the fully oxidized states was up to 83% (at 636 nm) [106]. -- [121] 3,6-dimethoxycarbazole [112,122] 3,6-di-tert-butylcarbazole [96,101,103] methyl, trifluoromethyl [104] 4-tert-butyl [99,[116][117][118] 2,4-dimethoxy [102] adamantylphenoxy [105] --ether-linked bis(triphenylamine) [106] piperidinyl [108] morpholinyl [97] TPA (pendant) -- [107,109,113] TPA or carbazole electrompolymerization [110,124,125] diphenylpyrenylamine [98] carbazole methoxy [114] carbazole (pendant) [119,120,123] N,N,N′,N′-tetraphenyl-1,4-phenylenediamine, TPPA tert-butyl [111] methoxy [100] bis(diphenylamino)naphthalene metoxy [126] diphenylfluorenylamine methyl [127] aniline pentamer/azo group…”

“…Main electroactive group Auxiliary EDG or EWG Comments [41] triphenylamine, TPA -hyperbranched [115] - [121] 3,6-dimethoxycarbazole [112,122] 3,6-di-tert-butylcarbazole [96,101,103] methyl, trifluoromethyl [104] 4-tert-butyl [99,[116][117][118] 2,4-dimethoxy [102] adamantylphenoxy…”

Carbazole based electrochromic polymers with benzoazole units: Effect of heteroatom variation on electrochromic performance

“…When applying higher potentials on the polymer, radical dications (bipolarons) are formed in the polymer system via removing another electron. For these reasons, electrochromic materials containing poly (3,6)carbazole derivatives have multielectrochromic behavior due to their district oxidation property in the anodic regime [21,22]. To understand the effect of heteroatom variation both on electro-optic properties of polymers and also on their electrochromic performance, we synthesized a series of donor-acceptor polymers based on N-(2-ethylhexyl)carbazole-3,6-bis(ethyleneboronate) (Cbz) and dibromobenzazole unit (BX)with different heteroatoms (N, S and Se) named as poly(4,7-(N-hexylbenzotriazole)-3,6-(N-(2-ethylhexyl)carbazole) (PCBN), poly(4,7-(2,1,3-benzothiadiazole)-3,6-(N-(2-ethylhexyl)carbazole) (PCBS) and poly(4,7-(2,1,3-benzoselenadiazole)-3,6-(N-(2-ethylhexyl)carbazole) (PCBSe).…”