Polythiophene derivatives as chemical sensors: a DFT study on the influence of side groups

Barboza, Bruno Hori; Gomes, Orisson Ponce; Batagin‐Neto, Augusto

doi:10.1007/s00894-020-04632-w

Cited by 16 publications

(10 citation statements)

References 78 publications

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“…In particular, the pronounced effects for the HOMOs (0.95, 1.28, 0.98, and 1.11 eV for PANI, PT, PPV, and PPy, respectively) can lead to non-equilibrium electrode/organic layer alignments in very stretched systems. The significant changes noticed on the FMOs are also supposed to have a profound effect on the performance of these materials in chemical sensors, given the relative position of the electronic gaps of the polymers and the FMO levels of the analytes [ 122 , 123 ].…”

Section: Resultsmentioning

confidence: 99%

Effects of Mechanical Deformation on the Opto-Electronic Responses, Reactivity, and Performance of Conjugated Polymers: A DFT Study

Cachaneski-Lopes

Batagin‐Neto

2022

Polymers

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The development of polymers for optoelectronic applications is an important research area; however, a deeper understanding of the effects induced by mechanical deformations on their intrinsic properties is needed to expand their applicability and improve their durability. Despite the number of recent studies on the mechanochemistry of organic materials, the basic knowledge and applicability of such concepts in these materials are far from those for their inorganic counterparts. To bring light to this, here we employ molecular modeling techniques to evaluate the effects of mechanical deformations on the structural, optoelectronic, and reactivity properties of traditional semiconducting polymers, such as polyaniline (PANI), polythiophene (PT), poly (p-phenylene vinylene) (PPV), and polypyrrole (PPy). For this purpose, density functional theory (DFT)-based calculations were conducted for the distinct systems at varied stretching levels in order to identify the influence of structural deformations on the electronic structure of the systems. In general, it is noticed that the elongation process leads to an increase in electronic gaps, hypsochromic effects in the optical absorption spectrum, and small changes in local reactivities. Such changes can influence the performance of polymer-based devices, allowing us to establish significant structure deformation response relationships.

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Section: Resultsmentioning

confidence: 99%

Effects of Mechanical Deformation on the Opto-Electronic Responses, Reactivity, and Performance of Conjugated Polymers: A DFT Study

Cachaneski-Lopes

Batagin‐Neto

2022

Polymers

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“…Such indexes describe how the electronic density of a given system varies when the total number of electrons is modified, allowing to evaluate which regions of the molecule are prone to the receive or donate electrons. These descriptors are especially relevant in predicting the position of reactive sites in polymers 12–14 …”

Section: Materials and Methodologymentioning

confidence: 99%

“…Besides presenting unique properties that allow their use in varied technological applications, polymeric materials also present reasonable chemical stability, ease of synthesis and low relative costs. In addition, a number of functionalizations can be made, allowing a wide range of optoelectronic responses for a variety of applications, 11 including as active layers of chemical sensors 12–14 …”

Section: Introductionmentioning

confidence: 99%

“…Previous works conducted by our group have shown the relevance of preliminary studies of the local reactivities to identify promising materials/sites for adsorption analysis 12–14 . In particular, density functional theory (DFT) based calculations and fully atomistic reactive molecular dynamics (FARMD) simulations have shown that the evaluation of the local reactivities and electrostatic potentials allows the identification of effective adsorption centers on the polymer structures 13 …”

Section: Introductionmentioning

confidence: 99%

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Polypyrrole derivatives for detection of toxic gases: A theoretical study

Coleone

Barboza

Batagin‐Neto

2021

Polymers for Advanced Techs

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Polypyrrole (PPy) based compounds have been considered interesting materials for several technological applications, mainly due to their unique optoelectronic properties and high versatility of synthesis. In particular, the sensitivity of their electrical properties to external stimuli defines these polymers as promising candidates for chemical sensor applications. However, the demanding processes involved in the synthesis of 3‐4 substituted PPy derivatives hinders the development of optimized systems. In this report, electronic structure calculations were conducted for a set of branched PPy derivatives aiming to identify promising compounds for chemical sensors. The calculations were carried out in the framework of the density functional theory (DFT), by considering oligomeric systems. The influence of the side groups on the local reactivities and adsorption centers of the compounds were evaluated via condensed‐to‐atoms Fukui indexes and molecular electrostatic potentials. DFT‐based adsorption studies and fully atomistic reactive molecular dynamics (FARMD) simulations were conducted for selected systems considering toxic gases as analytes. The results point out PPy, PPy‐CCH and PPy‐CN as promising candidates for chemical sensor applications, presenting high potential for the detection of Cl2 and SO2. FARMD results indicate that the analysis of local reactivities and electrostatic potentials can be used to identify relevant adsorption centers and possible degradation processes.

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“…Polythiophene (PT) and its derivatives are very promising conducting polymers due to their numerous remarkable properties such as environmental and thermal stability [1][2][3], high electrical conductivity [4][5][6] and interesting electronic and optical characteristics [7][8][9][10]. Thanks to these features, polythiophene offers several industrial applications in various fields, including electronic devices such as transistors [11][12][13], organic light-emitting diodes (OLEDs) [14,15], photovoltaic cells [16][17][18][19], electrochromic devices [20,21] and sensors [22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Electrodeposition of strictly alpha,alpha’-polythiophene chains on oxidizable metals in acidic concentrated aqueous media

Bouabdallaoui

Aouzal

Guerraf

et al. 2022

J. Electrochem. Sci. Eng.

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Electropolymerization of thiophene was performed in aqueous acidic media on various substrates, namely, titanium, nickel and SS steel. The films were successfully elaborated using voltamperometric, chronopotentiometric and chronoamperometric techniques. It was shown that concentrated acids increase the solubility of the monomer, lower its oxidation potential and inhibit the dissolution of the working electrode. Furthermore, the electrosynthesized polythiophene (PT) films are homogeneous and present similar properties to those obtained in organic media. On the other hand, analyses by X-ray photoelectron and infrared spectroscopies indicate the higher oxidation state of the polymers and the contribution of the supporting electrolyte in the doping process. In addition, IR spectra have demonstrated the strictly a, a’ linked polythiophene chains and an estimated degree of polymerization (DP) of about 40. Finally, scanning electron microscopy (SEM) has been used to characterize the morphology of the obtained coating. In this context, the nature of the films depends closely on the type of the electrode, the electrosynthesized mode and the electrolytic medium.

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Polythiophene derivatives as chemical sensors: a DFT study on the influence of side groups

Cited by 16 publications

References 78 publications

Effects of Mechanical Deformation on the Opto-Electronic Responses, Reactivity, and Performance of Conjugated Polymers: A DFT Study

Effects of Mechanical Deformation on the Opto-Electronic Responses, Reactivity, and Performance of Conjugated Polymers: A DFT Study

Polypyrrole derivatives for detection of toxic gases: A theoretical study

Electrodeposition of strictly alpha,alpha’-polythiophene chains on oxidizable metals in acidic concentrated aqueous media

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