Synthesis of alkyl-substituted ethyl 2,2':5',2'':5'',2'''-quaterthiophene-5-and 5-(biphenyl-4-yl)thiophene-2-carboxylates

Kostyuchenko, Anastasia S.; Drozdova, Ekaterina A.; Fisyuk, A. S.

doi:10.1007/s10593-017-2026-8

Cited by 14 publications

(8 citation statements)

References 15 publications

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“…The experimental findings are confronted with the results of quantum chemical (DFT) calculations delivering a mechanistic interpretation of the trends observed. Ester precursors (compounds 7a-c) of p-conjugated 1,3,4oxadiazole-thiophene derivatives (1,(3)(4)(5)(6) were prepared by the method previously elaborated, [43][44][45][46][47] starting from thiophene, 2,2 0 -bithiophene and 2,2 0 :5 0 ,2 00 -terthiophene (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“…Heating the esters (7a-d) in an alcoholic solution of KOH or hydrazine hydrate led to carboxylic acids (12a-d) or hydrazides (13a, b, d), respectively (Scheme 3). [43][44][45][46][47] Diacylhydrazines (14a, b, d), being direct precursors of the target 1,3,4-oxadiazole derivatives, were prepared by reacting compounds (12a, b, d) and (13a, b, d) in the presence of N,N 0 -dicyclohexylcarbodiimide (DCC). Compound (14c) was synthesized in the reaction of hydrazine dihydrochloride in the presence of pyridine with the acid chloride, which was generated in situ from the carboxylic acid (12) by the action of chlorooxalyl chloride.…”

Section: Introductionmentioning

confidence: 99%

“…Compounds (3), (4) and (6) have been synthesized according to procedures presented in our previous published works. 39,[43][44][45][46][47] A detailed synthetic protocol towards compounds (1,2,5) is given in the ESI. †…”

Section: Introductionmentioning

confidence: 99%

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Effect of donor to acceptor ratio on electrochemical and spectroscopic properties of oligoalkylthiophene 1,3,4-oxadiazole derivatives

Kurowska

Zassowski

Kostyuchenko

et al. 2017

Phys. Chem. Chem. Phys.

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A structure-property study across a series of donor-acceptor-donor structures composed of mono- and bi-(1,3,4-oxadiazole) units symmetrically substituted with alkyl functionalized bi-, ter- and quaterthiophene segments is presented. Synthetically tailoring the ratio of electron-withdrawing 1,3,4-oxadiazole to electron-releasing thiophene units and their alkyl grafting pattern permitted us to scrutinize the impact of these structural factors on the redox, absorptive and emissive properties of these push-pull molecules. Contrasting trends of redox potentials were observed, with the oxidation potential closely following the donor-to-acceptor ratio, whereas the reduction potential being tuned independently by either the number of acceptor units or the conjugation length of the donor-acceptor system. Increasing the thiophene unit contribution delivered a shift from blue to green luminescence, while the structural rigidity afforded by intramolecular non-covalent interactions between 1,3,4-oxadiazole and the thiophene moieties has been identified as the prime factor determining the emission efficiency of these molecules. All six structures investigated electro-polymerize easily, yielding electroactive and electrochromic polymers. The polymer doping process is largely influenced by the length of the oligothiophene repeating unit and the alkyl chain grafting density. Polymers with relatively short oligothiophene segments are able to support polarons and polaron-pairs, whereas those with segments longer than six thiophene units could also stabilize diamagnetic charge carries - bipolarons. Increasing the alkyl chain grafting density improved the reversibility and broadened the working potential window of the p-doping process. Stable radical anions have also been investigated, bringing detailed information about the conjugation pattern of these electron-surplus species. This study delivers interesting clues towards the conscious structural design of bespoke frontier energy level oligothiophene functional materials and their polymers by incorporating a structurally matching 1,3,4-oxadiazole unit.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Effect of donor to acceptor ratio on electrochemical and spectroscopic properties of oligoalkylthiophene 1,3,4-oxadiazole derivatives

Kurowska

Zassowski

Kostyuchenko

et al. 2017

Phys. Chem. Chem. Phys.

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“…We recently developed a simple three-step method for the preparation of 3-alkyl-(2,2′-bithiophene)-5-carboxylic acid esters 5 ,, (Scheme ). 3-Decyl(2,2′-bithiophene)-5-carboxylic acid 6 and hydrazide 7 , , which were prepared from compound 5 , we used as starting materials for the synthesis of bis([2,2′-bithiophen]-5-yl)-1,3,4-thiadiazole 1 , and substituted oligo-1,3,4-thiadiazoles 2–4 .…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Bis([2,2′-bithiophen]-5-yl)-Substituted Oligothiadiazoles: Effect of the Number of Acceptor Units on Electrochemical and Spectroscopic Properties

et al. 2019

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symmetrically disubstituted with 3-alkyl-(2,2′-bithiophen)-5-yl were synthesized by new procedures using readily available ethyl 3-alkyl-(2,2′-bithiophene)-5carboxylate as a convenient substrate. These new compounds with a fixed number of donor rings and increasing number of acceptor rings showed very interesting, tunable redox properties. In particular, they exhibited electron affinities (EAs) ranging from −3.06 to −3.83 eV, reaching EA values desired for air-operating n-type organic semiconductors. Their electrochemically determined ionization potentials were only moderately dependent on the number of thiadiazole rings, varying from 5.83 to 6.01 eV. Emission spectra of these compounds could also be tuned in a wide range (from 470 to 600 nm). Spectroscopic and electrochemical data were confirmed by density functional theory calculations demonstrating full consistency.

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“…[20][21][22][23][24][25] One of the possible, but unexplored, approaches to the synthesis of 4-azido-5arylthiophene-2-carboxylates is the Fiesselmann reaction of 2azido-3-chloro-3-phenylacrylaldehyde [26][27][28] with thioglycolic acid esters. [29][30][31] We used haloketones 6а-i as starting compounds, which were converted into azidoketones 7a-i in 67-94% yield by reaction with sodium azide 32 in a MeCN/H2O (3:1) mixture. The reaction of azidoketones 7a-i with the Vilsmeier reagent gave rise to 2-azido-3-chloro-3phenylacrylaldehydes 8a-i as a mixture of E/Z-isomers (1/5-1/33) with total yields of 40-76% (Table 1).…”

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Synthesis of New Fused 4H-Thieno[3,2-b]pyrrole Derivatives via Decomposition of Methyl 4-Azido-5-arylthiophene-2-carboxylates

et al. 2022

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This article focused on the development of practical approaches to the synthesis of 4-azido-5-arylthiophene-2-carboxylates and 4-amino-5-arylthiophene-2-carboxylates using the Fiesselmann reaction. The photochemical and thermal (including microwave assisted) decomposition of 4-azido-5-arylthiophene-2-carboxylates has been studied in order to synthesize fused 4H-thieno[3,2-b]pyrrole derivatives. The proposed approaches allow to obtain functionally substituted heteroacenes, which are of interest as building blocks for organic semiconductors

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Synthesis of alkyl-substituted ethyl 2,2':5',2'':5'',2'''-quaterthiophene-5-and 5-(biphenyl-4-yl)thiophene-2-carboxylates

Cited by 14 publications

References 15 publications

Effect of donor to acceptor ratio on electrochemical and spectroscopic properties of oligoalkylthiophene 1,3,4-oxadiazole derivatives

Effect of donor to acceptor ratio on electrochemical and spectroscopic properties of oligoalkylthiophene 1,3,4-oxadiazole derivatives

Synthesis of Bis([2,2′-bithiophen]-5-yl)-Substituted Oligothiadiazoles: Effect of the Number of Acceptor Units on Electrochemical and Spectroscopic Properties

Synthesis of New Fused 4H-Thieno[3,2-b]pyrrole Derivatives via Decomposition of Methyl 4-Azido-5-arylthiophene-2-carboxylates

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