Polymerization and Characterization of 4,4‘-Bis(alkylsulfanyl)-2,2‘-bithiophenes

Abstract

Regioregular polymers poly[4,4‘-bis(butylsulfanyl)-2,2‘-bithiophene] (P1) and poly[4,4‘-bis(octylsulfanyl)-2,2‘-bithiophene] (P2) were prepared from 4,4‘-bis(butylsulfanyl)- and 4,4‘-bis(octylsulfanyl)-2,2‘-bithiophene, by oxidative polymerization with FeCl3, and characterized by 1H and 13C NMR, FT-IR, and UV−vis spectroscopies, atomic force microscopy (AFM), electrical conductivity, and cyclic voltammetry measurements. They exhibit weight-average molecular weights of 8 and 70 kDa, respectively, and are both readily soluble in CHCl3, CH2Cl2, CS2, toluene, and THF. P1 has a lamellar structure, and P2 is a flexible and compact film that can be easily processed and manipulated. In the neutral state, they show UV−vis absorption maxima at about 470 nm in CHCl3 solution and exhibit marked solvatochromism and thermochromism. Furthermore, they can be cast from orange-red solution to form a violet film. The p-doping potentials have been determined, and the possibility of electrogenerating corresponding polymers has been checked. First comparative characterizations of the electrogenerated polymers have been carried out.

Optical and Electrochemical Transducers Based on Functionalized Conjugated Polymers

“…This intriguing effect has been extensively studied and has led to the development of various thermochromic polythiophene [4,5,[12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29], polysilane [30][31][32][33][34][35][36][37][38][39][40][41], and polydiacetylene [42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57] derivatives (Figure 2.1). As an example of thermochromism reported for some neutral conjugated polymers, Figure 2.2 shows the temperature-dependent UV-vis spectrum of sodium poly[2-(4-methyl-3-thienyloxy)ethanesulfonate] in...…”

New Developments in Electrochemical Sensors Based on Poly(3,4-ethylenedioxythiophene)-Modified Electrodes

“…Conducting polymers (CPs) have drawn considerable interest in recent years because of their potential applications in different fields such as in sensors, electrochemical displays, and in catalysis [16,17]. Among the organic conducting polymers, poly(thiophene) and its derivatives, such as poly(3,4-ethylenedioxythophene), (PEDOT), have attracted particular interest because these compounds appeared to be the most stable organic conducting polymers currently available [21][22][23][24][25][26][27][28]. Conducting polymers can be deposited as dense modifying layers on common electrode substrates, which is of importance to the development of many technologies, including electrochemical sensors technology.…”

Bidimensional Spectroelectrochemistry Applied to the Electrosynthesis and Characterization of Conducting Polymers: Study of Poly[4,4′-bis(butylthio)-2,2′-bithiophene]

“…Low values for the oxidation potential and regioregularity of the resulting polymers are among the factors that encouraged hard work on the synthesis and study of the properties of new poly(b,b'-disubstituted bithiophene)s. The regiochemistry of the resulting polymer strongly affects the relevant physical properties: as an example, conductivity is much higher in regioregular head-to-tail than in regiorandom polythiophenes. Furthermore, poly[4,4'-bis(alkylthio)-2,2'-bithiophene]s can be easily electrogenerated [11 ± 14] and proved to lead to quite stable electrode coatings, even over relatively long times and under polarization conditions [15 ± 17], thus allowing the attainment of reliable and repeatable voltammetric responses.Together with detailed studies on the physical, chemical, electronic, and electrochemical properties of polythiophenes [12] [13] [15] [18] [19], a number of studies have been carried out on the mechanism of the processes taking place at the electrode/ …”

“…Together with detailed studies on the physical, chemical, electronic, and electrochemical properties of polythiophenes [12] [13] [15] [18] [19], a number of studies have been carried out on the mechanism of the processes taking place at the electrode/…”

“…Together with detailed studies on the physical, chemical, electronic, and electrochemical properties of polythiophenes [12] [13] [15] [18] [19], a number of studies have been carried out on the mechanism of the processes taking place at the electrode/ solution interface during electrogeneration of these polymers [20 ± 27]. In the present paper, a novel experimental technique is presented and proposed to study processes simultaneously taking place in the solution and on the surface during electropolymerization.…”