Structural and electronic properties of poly(3-thiophen-3-yl-acrylic acid)

Bertrán, Oscar; Armelín, Elaine; Torras, Juan; Estrany, Francesc; Codina, Mireia; Alemán, Carlos

doi:10.1016/j.polymer.2008.02.036

Cited by 12 publications

(33 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These results are fully consistent with the rotational profile predicted by quantum mechanical methods for the inter-ring dihedral angle, [45][46][47][48][49] which indicated that the syn conformation is severely destabilized when adjacent substituted thiophene rings show a head-head linkage but energetically accessible for head-tail and tail-tail linkages. From an electronic point of view, the distortion of the interring dihedral angle from anti to syn destroys the extent of the π -conjugation along the polymer chain.…”

Section: Molecular Dynamics Simulationssupporting

confidence: 86%

Sensitive thermal transitions of nanoscale polymer samples using the bimetallic effect: Application to ultra-thin polythiophene

Ahumada¹,

Pérez‐Madrigal

Ramı́rez

et al. 2013

Review of Scientific Instruments

View full text Add to dashboard Cite

A sensitive nanocalorimetric technology based on microcantilever sensors is presented. The technology, which combines very short response times with very small sample consumption, uses the bimetallic effect to detect thermal transitions. Specifically, abrupt variations in the Young's modulus and the thermal expansion coefficient produced by temperature changes have been employed to detect thermodynamic transitions. The technology has been used to determine the glass transition of poly(3-thiophene methyl acetate), a soluble semiconducting polymer with different nanotechnological applications. The glass transition temperature determined using microcantilevers coated with ultra-thin films of mass = 10 −13 g is 5.2• C higher than that obtained using a conventional differential scanning calorimeter for bulk powder samples of mass = 5 × 10 −3 g. Atomistic molecular dynamics simulations on models that represent the bulk powder and the ultra-thin films have been carried out to provide understanding and rationalization of this feature. Simulations indicate that the film-air interface plays a crucial role in films with very small thickness, affecting both the organization of the molecular chains and the response of the molecules against the temperature. © 2013 AIP Publishing LLC. [http://dx

show abstract

Section: Molecular Dynamics Simulationssupporting

confidence: 86%

Sensitive thermal transitions of nanoscale polymer samples using the bimetallic effect: Application to ultra-thin polythiophene

Ahumada¹,

Pérez‐Madrigal

Ramı́rez

et al. 2013

Review of Scientific Instruments

View full text Add to dashboard Cite

show abstract

“…It should be mentioned that the high stability of the head-to-tail sequence in large oligomers (n > 3) was corroborated in previous theoretical studies involving other 3-substituted thiophene units. [13][14][15][16] n-XTh (X = F, Cl and Br) oligomers with n = 5, 7, 9, 11, 13, 15 and 16 were constructed according to these principles and considering all the inter-ring dihedral angles initially arranged at 180.01. These structures were used as starting points for complete geometry optimizations at the B3LYP/ 6-31+G(d,p) level.…”

Section: Conformational Analysis: Influence Of the Halogen On The Mol...mentioning

confidence: 99%

“…acetic acid, acrylic acid and malonic acid hydrophilic substituents). [13][14][15][16][17][18] Poly(3-halidethiophene)s is another interesting family of PThs substituted with electron-withdrawing groups (Scheme 1). In these materials halogen atoms are directly attached to the polyconjugated main chain, which may produce a reduction in the electronic density of the thiophene rings.…”

Section: Introductionmentioning

confidence: 99%

Properties of poly(3-halidethiophene)s

Casanovas

Aradilla

Poater

et al. 2012

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

The influence of the halogen atom on the intrinsic properties of poly(3-halidethiophene)s has been investigated using experimental and theoretical methodologies. Specifically, the electrochemical, electrical, electronic and morphological properties of poly(3-bromothiophene) have been determined and compared with those recently reported for poly(3-chlorothiophene) [Aradilla et al., Polym. Chem., 2012, 3, 436.]. The electrochemical stability and porosity are smaller for poly(3-bromothiophene) than for poly(3-chlorothiophene) while the π-π* lowest transition energy is higher for the former than for the latter. Moreover, quantum mechanical calculations on model oligomers have evidenced that the conformational properties of poly(3-halidethiophene)s, where the halogen is fluorine, chloride or bromine, are dominated by steric interactions and, therefore, are significantly influenced by the size of the halogen atoms. Both the ionization potential and the π-π* lowest transition energy have been predicted to increase slightly when the π-donor character of the halogen atom decreases, in agreement with experimental observations.

show abstract

“…However, it should be noted that this behavior is fully consistent with that found for model 2,2 0 -bithiophenes with substituents at the 3-and 3 0 -positions using ab initio quantum mechanical calculations, which shows two main minima syn-gauche and gauche-gauche conformations. [50][51][52] On the other hand, the average value of h 2 , which involves a tail-to-tail polymer linkage, is h 2 5 22.08 6 31.58 indicating also a preference towards the syn-gauche conformation. Thus, this angle dihedral oscillates around the two syn-gauche minima, i.e.…”

Section: Poly(thiophene)s Functionalized With Calix[4]arenementioning

confidence: 99%

“…28 6 19.38) indicates that the conformational preferences of this head-to-head polymer linkage are gauchegauche, which is consistent with that found for 2,2 0 -bitiophene with substituents at 3-and 3 0 -positions using ab initio quantum mechanical calculations. [50][51][52] Finally, the temporal evolution of the d e-e along the md3 simulation clearly shows that DP3 parameters, which a priori should provide the best results because of the combination of the potentials derived from bTph-c4a1 and bTph, is not able to describe the shape of the PT-c4a1 chain when Na 1 ions are electrostatically bounded to the oxygen-rich binding site. Thus, the molecule folds very rapidly given a coiled arrangement that is preserved during the last 7 ns of trajectory (d e-e 5 24.77 6 6.50 Å ).…”

Section: Poly(thiophene)s Functionalized With Calix[4]arenementioning

confidence: 99%

Parameterization of the torsional potential for calix[4]arene‐substituted poly(thiophene)s

et al. 2009

Self Cite

View full text Add to dashboard Cite

Three different strategies have been followed to develop the torsional force-field parameters of the inter-ring dihedral angles for calix[4]arene-substituted poly(thiophene)s, a family of highly sensitive ion receptors. These procedures, which are based on the rotational profiles calculated using quantum mechanical methods, differ in the complexity of the model compounds and the processing applied to the quantum mechanical energies before the fitting. The performance of the three sets of developed parameters, which are essentially compatible with the General Amber Force Field, has been evaluated by computing the potential of mean forces for the inter-ring rotation of 2,2'-bithiophene, and its substituted analog bearing a calix[4]arene group in different environments. Finally, the ability of the new sets of torsional parameters to describe a calix[4]arene-substituted poly(thiophene) in tetrahydrofuran solution has been checked using Molecular Dynamics simulations. Specifically, the molecular shape, the polymer conformation, and the effects of the Na(+) ions trapped in the cavity of the receptor have been examined. Although the potential derived from unsubstituted 2,2'-bithiophene is able to reproduce the experimental free energies of the minima, the overall results indicate that the parameters derived from the analog bearing a calix[4]arene group provide the best description of the systems under study. This should be attributed to the strong constraints found in complex substituted poly(thiophene)s, which require parameterization strategies able to capture all the interactions and phenomena involved in their inter-ring rotations.

show abstract

Structural and electronic properties of poly(3-thiophen-3-yl-acrylic acid)

Cited by 12 publications

References 36 publications

Sensitive thermal transitions of nanoscale polymer samples using the bimetallic effect: Application to ultra-thin polythiophene

Sensitive thermal transitions of nanoscale polymer samples using the bimetallic effect: Application to ultra-thin polythiophene

Properties of poly(3-halidethiophene)s

Parameterization of the torsional potential for calix[4]arene‐substituted poly(thiophene)s

Contact Info

Product

Resources

About