Characterization and Electrocatalytic Activity of Poly(4-thienylacetyl-oxy-2,2,6,6-tetramethylpiperidin-1-yloxy) Prepared by Electrochemical Polymerization

Wang, Xi; Ma, Jiaqi; Song, Dandan; Shen, Zhenlu; Li, Meichao; Ma, Chao

doi:10.1149/2.008406eel

Cited by 13 publications

(8 citation statements)

References 18 publications

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“…One feasible way to synthesize polythiophene-organic radical polymers is through FeCl 3 -aided oxidative polymerization; however, polymerization is uncontrolled, and the products are intractable, preventing solution processing and characterization. 31 Electropolymerization of thiophene monomers bearing pendant nitroxide radicals has been reported; 33,48,49 however, only one type of such polymer was reported due to the limited commercial availability of monomers. The physical properties of polythiophene-organic radical polymers is even less well understood and remains an intriguing topic.…”

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confidence: 99%

Electropolymerized Polythiophenes Bearing Pendant Nitroxide Radicals

Zhang

Kwon

et al. 2016

ACS Macro Lett.

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We report a facile way to synthesize polythiophenes carrying pendant 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) radicals, here called PTATs, by electropolymerization in boron trifluoride diethyl etherate (BFEE). The spacing between the TEMPO radical and the polythiophene backbone is varied by an alkyl spacer (n = 2, 4, 6), and the electronic and electrochemical properties are examined using UV–vis spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Film morphologies are also studied via scanning electron microscopy (SEM) and atomic force microscopy (AFM), which show that the longer octyl chain placed between thiophene and TEMPO effectively suppresses aggregation. The highest conductivity and electroactivity are observed for n = 4 and n = 6, respectively. Such morphology differences provide an opportunity to better understand the charge transport and energy storage properties in electronic materials.

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confidence: 99%

Electropolymerized Polythiophenes Bearing Pendant Nitroxide Radicals

Zhang

Kwon

et al. 2016

ACS Macro Lett.

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“…1350 cm –1 for nitroxide radicals and ca. 1600 cm –1 for oxoammonium cations , ). The position of ν(N–O) at 1015–963 cm –1 in [M(tacn)(tfo)] + complexes is indicative of a single nitrogen–oxygen bond, while the mixed valency of the ligand would result in a much higher frequency (intermediate between hydroxylamine and nitroxide radical or oxoammonium cation).…”

Section: Resultsmentioning

confidence: 99%

Revealing the Structure of Transition Metal Complexes of Formaldoxime

et al. 2021

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Aerobic reactions of iron(III), nickel(II), and manganese(II) chlorides with formaldoxime cyclotrimer (tfoH 3 ) and 1,4,7-triazacyclononane (tacn) produce indefinitely stable complexes of general formula [M(tacn)(tfo)]Cl. Although the formation of formaldoxime complexes has been known since the end of 19th century and applied in spectrophotometric determination of Dmetals (formaldoxime method), the structure of these coordination compounds remained elusive until now. According to the X-ray analysis, [M(tacn)(tfo)] + cation has a distorted adamantane-like structure with the metal ion being coordinated by three oxygen atoms of deprotonated tfoH 3 ligand. The metal has a formal +4 oxidation state, which is atypical for organic complexes of iron and nickel. Electronic structure of [M(tacn)(tfo)] + cations was studied by XPS, NMR, cyclic (CV) and differential pulse (DPV) voltammetries, Mossbauer spectroscopy, and DFT calculations. Unusual stabilization of high-valent metal ion by tfo 3− ligand was explained by the donation of electron density from the nitrogen atom to the antibonding orbital of the metal−oxygen bond via hyperconjugation as confirmed by the NBO analysis. All complexes [M(tacn)(tfo)]Cl exhibited high catalytic activity in the aerobic dehydrogenative dimerization of p-thiocresol under ambient conditions.

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“…Meanwhile, three negative-going bands at 1685, 1360, and 1267 cm −1 were detected, which were attributed to C=O stretching vibration, C-H deformation vibration in the methyl group, and skeleton vibration of acetophenone, respectively [62]. Moreover, a weak but important upward band of N-O stretching vibration, showing the participation of ABNO in this reaction, was observed at 1369 cm −1 [49]. The other band located at 1129 cm −1 was assigned to ClO 4 − ions of supporting electrolyte [63,64].…”

Section: Resultsmentioning

confidence: 99%

“…However, the primary alcohols substituted with strong electron-withdrawing group, such as -nitro and some of secondary alcohols gave low product yields. Lately, we prepared a series of TEMPO-modified polymer electrodes, which could be used successfully for the selective oxidation of alcohols to aldehydes [48,49,50]. It is well known that the detailed information of the electrochemical behaviour of organic compounds is crucial for electrochemical synthesis.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Performance of ABNO for Oxidation of Secondary Alcohols in Acetonitrile Solution

et al. 2018

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The ketones was successfully prepared from secondary alcohols using 9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO) as the catalyst and 2,6-lutidine as the base in acetonitrile solution. The electrochemical activity of ABNO for oxidation of 1-phenylethanol was investigated by cyclic voltammetry, in situ Fourier transform infrared spectroscopy (FTIR) and constant current electrolysis experiments. The resulting cyclic voltammetry indicated that ABNO exhibited much higher electrochemical activity when compared with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) under the similar conditions. A reasonable reaction mechanism of the electrocatalytic oxidation of 1-phenylethanol to acetophenone was proposed. In addition, a series of secondary alcohols could be converted to the corresponding ketones at room temperature in 80–95% isolated yields.

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Characterization and Electrocatalytic Activity of Poly(4-thienylacetyl-oxy-2,2,6,6-tetramethylpiperidin-1-yloxy) Prepared by Electrochemical Polymerization

Cited by 13 publications

References 18 publications

Electropolymerized Polythiophenes Bearing Pendant Nitroxide Radicals

Electropolymerized Polythiophenes Bearing Pendant Nitroxide Radicals

Revealing the Structure of Transition Metal Complexes of Formaldoxime

Electrochemical Performance of ABNO for Oxidation of Secondary Alcohols in Acetonitrile Solution

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