Structural and electronic properties of oligo- and polythiophenes modified by substituents

Rittmeyer, Simon P.; Groß, Axel

doi:10.3762/bjnano.3.101

Cited by 44 publications

(45 citation statements)

References 47 publications

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“…Nevertheless, the spectra of the monomers of both polymers have shown a good match with the experimentally measured spectra ( figure 7). Interestingly, these results are supported by the previous study that studied the impact of extended conjugation on a substituted and non-substituted oligo-and polythiophenes [34]. One of the significant outcomes from this study has concluded that the width of the HOMO-LUMO gap (band gap) decreases with increasing size of the oligomer and the inclusion of electron-donating substituent.…”

Section: Effect Of the Length Of Conjugation On The Band Gapsupporting

confidence: 79%

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Investigation of the Electronic and pH-Sensing properties of Hydroxyl-Functionalized Imine-Linked Polymers via the UV-vis Absorption Spectra and the Density Functional Theory (DFT) Calculations

Aljaafreh

Altarawneh

Alomari

et al. 2017

J. Pure App. Chem. Res.

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In this report, a synergetic computational and experimental studies were demonstrated on examples of poly-imine polymers; P(PI-IPI) and P(PIOH-IPI) to explore the role of hydroxyl substituent on their sensing and electronic properties. The polymer P(PIOH-IPI) bearing the OH-group on the ortho-position to the imine-bond, while the structure of the polymer P(PI-IPI) reveal the imine-bond only. The sensing property of the polymers was investigated via the UV-vis absorption in different solvents, acidic and basic solutions. Both polymers have shown significant sensing behavior in the acidic medium, while unpronounced behavior was noticed in the case of the polymer P(PI-IPI) in basic medium. Upon the incorporation of the OH-group, the polymer P(PIOH-IPI) has indistinguishable sensing behavior, a similar blue-shift in the acidic and basic medium, which can be attributed to the presence and the position of OH-group. The optical band gap of the polymers was determined experimentally and theoretically from the UV-vis absorption spectra and DFT calculations in the DMSO solvent. Other factors that affect the band gap values such as the structural conformation and length of conjugation were explored theoretically. In general, as the length of the optimized chain increased, the spectrum is red-shifted and the band gap decreased, which is attributed to the possible loss of chain planarity and conjugation beyond the monomer structure. Interestingly, the UV-vis spectra of the monomer-optimized structures were in a good match with the experimental UV-vis spectra. However, the band gap difference can be attributed to the method of band gap determination.Key word: Sensing, Functionalization, conformation, Length of conjugation, DFT, UV-vis INTRODUCTIONImine-linked polymers (ILPs) are organic conjugated polymers that gained significant importance due to their vital applications in the fields of catalysis, sensing, gas sorption, electronic and optoelectronic devices, sensors and other more applications [1][2][3][4][5][6][7]. The multifunctional properties of ILPs are related to their selective structural design which, exhibit an extended conjugated backbone accessible for functionalization and free nitrogen sites available for protonation and metal ion-coordination [3,8,9].As example, ILPs-based polymers such as C3v-POF and Th-POF were synthesized as Cu-and Ir-coordinated polymers and used as catalysts in the hydrogenation and cyclopropanation reactions, while other ILPs were used as Suzuki coupling catalysts [9][10][11].

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Section: Effect Of the Length Of Conjugation On The Band Gapsupporting

confidence: 79%

“…This difference can be accredited to the inclusion of the OH-substituent in the polymer chain (figure 8). The presence of the OH-substituent leads to a significant change on the electronic structure of the polymer due the electrondelocalization (resonance effect) and lower the band gap [34,35]. …”

Section: Dft Calculations Resultsmentioning

confidence: 99%

Investigation of the Electronic and pH-Sensing properties of Hydroxyl-Functionalized Imine-Linked Polymers via the UV-vis Absorption Spectra and the Density Functional Theory (DFT) Calculations

Aljaafreh

Altarawneh

Alomari

et al. 2017

J. Pure App. Chem. Res.

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“…The electronic properties of a material is governed by the band gap and therefore it is essential to successfully design such oligomers and polymers to understand the changes in band gap of conjugated oligomers or polymers with respect to their chemical structure. Recently Rittmeyer and Grob [10] have studied the effect of substituents on polythiophenes (PT) and reported that the electronic properties of PTs are unaltered by strongly bonded substituents except for the phenyl group. Chou et al [11] investigated PTs and found that the band gaps are decreased with electron donating substituents and increased with electron withdrawing substituents.…”

Section: Introductionmentioning

confidence: 99%

Electronic structure of α-oligothiophenes with various substituents

Vikramaditya

Saisudhakar

Sumithra

2015

Journal of Molecular Structure

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“…Note that the modeling of a liquid requires the determination of free energies instead of just total energies, which means that computationally expensive statistical averages have to be performed in order to evaluate free-energy differences. Although electronic structure calculations based on density functional theory can reproduce the properties of planar arrangements of aromatic molecules satisfactorily [15–18], the large size of the considered systems and the requirement to perform thermal averages make first-principles electronic-structure calculations computationally prohibitively expensive. Therefore we employed classical force fields as included in the Forcite module of the Accelrys’ Materials Studio package to describe the interaction between adsorbate, substrate and solvent.…”

Section: Introductionmentioning

confidence: 99%

Influence of the solvent on the stability of bis(terpyridine) structures on graphite

Künzel

Groß

2013

Beilstein J. Nanotechnol.

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SummaryThe effect of solvation on the adsorption of organic molecules on graphite at room temperature has been addressed with force-field molecular dynamics simulations. As a model system, the solvation of a bis(terpyridine) isomer in water and 1,2,4-trichlorobenzene was studied with an explicit solvation model. The inclusion of solvation has a noticeable effect on adsorption energies. Although the results of the various considered force fields differ quite significantly, they all agree that the adsorption of BTP from the TCB solvent is almost thermoneutral. The substrate simply acts as a template to allow a planar arrangement of the network, which is stabilized by the intermolecular interaction. Using an atomic thermodynamics approach, the order of the stability of various network structures as a function of the chemical potential is derived yielding a sequence in agreement with the experiment.

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Structural and electronic properties of oligo- and polythiophenes modified by substituents

Cited by 44 publications

References 47 publications

Investigation of the Electronic and pH-Sensing properties of Hydroxyl-Functionalized Imine-Linked Polymers via the UV-vis Absorption Spectra and the Density Functional Theory (DFT) Calculations

Investigation of the Electronic and pH-Sensing properties of Hydroxyl-Functionalized Imine-Linked Polymers via the UV-vis Absorption Spectra and the Density Functional Theory (DFT) Calculations

Electronic structure of α-oligothiophenes with various substituents

Influence of the solvent on the stability of bis(terpyridine) structures on graphite

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