An ambipolar behavior of novel ethynyl-bridged polythiophenes- A comprehensive study

Stanisław Krompiec , Michał Filapek , Iwona Grudzka , Sławomir Kula , Aneta Słodek , Łukasz Skórka , Witold Danikiewicz , Przemysław Ledwon , Mieczysław Łapkowski

Abstract

The article contains a comprehensive study regarding the synthesis and properties of novel polythiophenes, where bithiophene units are linked with either ethynyl or bisethynylarylenyl bridges. A convenient and selective method for lithiation of 2,2′-bithiophene, with the aid of n-butyllithium in dialkyl ether/n-hexane solution under mild conditions (-5 to 5 °C), is also presented. The lithiation, followed by the addition of iodine solution at room temperature constituted a robust method towards the synthesis of 5-iodo-2,2′-bithiophene, which was then used as a key substrate in the Sonogashira-type cross-coupling reactions. The coupling of 5-ethynyl-2,2′- bithiophene with 5-iodo-2,2′-bithiophene, mediated by [PdCl 2(PPh3)2]/CuI couple, resulted in the formation of 1,2-bis(2,2′-bithiophene-5-yl)ethyne. The synthesized monomers of Bt-A-Bt (where Bt = 2,2′-bithiophene-5-yl) type, namely: 1,2-bis(2,2′-bithiophene-5-yl)ethyne, 1,4-bis(2,2′-bithiophene-5-yl) buta-1,3-diyne and 1,4-bis(2,2′-bithiophene-5-ylethynyl)benzene were transformed into conducting polymers in an electrochemical oxidation process. The influence of the A bridge on the stability, luminescent and electrochemical behavior was thoroughly studied. The polymers present an extraordinary stability during multiple n- and p-doping. The experimental results were also investigated theoretically, using DFT approach. For each polymer calculations of the frontier orbital energies and the corresponding Eg value were done using periodic boundary conditions. For polythiophene derived from 1,2-bis-(2,2′-bitiophene-5-yl)ethyne the value of the band gap was also estimated using an oligomeric approximation. Furthermore, the presented compounds revealed an enhanced fluorescent activity, especially in the case of a monomer with bisethynylphenylene bridge and the corresponding polymer. (C) Elsevier
Author Stanisław Krompiec - [University of Silesia (UŚ)]
Stanisław Krompiec,,
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- Uniwersytet Śląski
, Michał Filapek - [University of Silesia (UŚ)]
Michał Filapek,,
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- Uniwersytet Śląski
, Iwona Grudzka - [University of Silesia (UŚ)]
Iwona Grudzka,,
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- Uniwersytet Śląski
, Sławomir Kula - [University of Silesia (UŚ)]
Sławomir Kula,,
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- Uniwersytet Śląski w Katowicach
, Aneta Słodek - [University of Silesia (UŚ)]
Aneta Słodek,,
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- Uniwersytet Śląski
, Łukasz Skórka (FC / CPCT) - [University of Silesia (UŚ)]
Łukasz Skórka,,
- Chair Of Polymer Chemistry And Technology
- Uniwersytet Śląski
, Witold Danikiewicz - [Institute of Organic Chemistry of the Polish Academy of Sciences]
Witold Danikiewicz,,
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, Przemysław Ledwon - [Silesian University of Technology (PolSL)]
Przemysław Ledwon,,
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- Politechnika Śląska
, Mieczysław Łapkowski - [Silesian University of Technology (PolSL)]
Mieczysław Łapkowski,,
-
- Politechnika Śląska
Journal seriesSynthetic Metals, ISSN 0379-6779
Issue year2013
Vol165
Pages7-16
Publication size in sheets0.5
Keywords in EnglishConducting polymers; DFT calculations for polymeric materials; Ethynyl-bridged polythiophenes
ASJC Classification2505 Materials Chemistry; 2506 Metals and Alloys; 2210 Mechanical Engineering; 2211 Mechanics of Materials; 3104 Condensed Matter Physics; 2504 Electronic, Optical and Magnetic Materials
DOIDOI:10.1016/j.synthmet.2012.12.030
URL http://www.sciencedirect.com/science/article/pii/S0379677912004481
Languageen angielski
File
1-s2.0-S0379677912004481-main.pdf 1.6 MB
Score (nominal)30
Score sourcejournalList
ScoreMinisterial score = 30.0, 09-01-2020, ArticleFromJournal
Ministerial score (2013-2016) = 30.0, 09-01-2020, ArticleFromJournal
Publication indicators Scopus Citations = 14; WoS Citations = 14; Scopus SNIP (Source Normalised Impact per Paper): 2014 = 0.943; WoS Impact Factor: 2013 = 2.222 (2) - 2013=2.256 (5)
Citation count*9 (2015-09-10)
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* presented citation count is obtained through Internet information analysis and it is close to the number calculated by the Publish or Perish system.
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