Influence of the regioregularity on the chiral supramolecular organization of poly(3-alkylsulfanylthiophene)s

Peeters, Helmuth; Couturon, Pauline; Vandeleene, Steven; Moerman, David; Leclère, Philippe; Lazzaroni, Roberto; Cat, Inge De; Feyter, Steven De; Koeckelberghs, Guy

doi:10.1039/c2ra22731b

Cited by 18 publications

(27 citation statements)

References 39 publications

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“…All these observations can be explained by an effect which was previously reported, namely that a small amount of irregularity can increase the chiral response. 9,20 Besides the effect of the nature and the position of the defect on the chiral expression, also the effect of mixing polymers with a defect in different positions was investigated. For the mixtures of the polymers with an HH defect, a weighted average of the signals of its constituents was obtained, indicating no significant influence.…”

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Effect of the Nature and the Position of Defects on the Chiral Expression in Poly(3-alkylthiophene)s

et al. 2019

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Polymers produced with the most used controlled polymerization method with the simplest initiators, namely the Kumada catalyst transfer condensation polymerization (KCTCP) with Ni 2+salts, all have one regiodefect distributed along the polymer backbones. The irregularity created by these defects can be split up into three components, i.e. the nature of the defect, the position of 2 the defect and the additional inhomogeneity created by mixing polymers with the defect at different positions. In this research, the influence of these three parameters on the chiral expression of poly(3-alkylthiophene)s (P3ATs) is investigated separately for the first time. Series of chiral P3ATs with one tail-to-tail (TT) or head-to-head (HH) defect in different positions are synthesized by means of the Pd(RuPhos) protocol and their chiral expression and that of their mixtures is studied via UV-vis and circular dichroism (CD) spectroscopy. For the polymers with an HH defect, it is found that the position at the very beginning of the polymer chain is the most optimal to obtain the largest chiral expression and the obtained signal is even the highest ever reported for PTs in chloroform and MeOH solutions. When a TT defect is incorporated into the polymer, the chiral expression is much weaker and the most optimal position of the defect is a little shifted toward the middle of the chain compared to their HH analogs. For the mixtures of the polymers with an HH defect, a weighted average of the signals of its constituents is obtained, but for the mixtures of the polymers with a TT defect different results are obtained. When 25% of each polymer is mixed, no chiral response is obtained and when more of the polymers with the defect more toward the chain ends are incorporated, a chiral response higher than that of any of the component polymers is recorded. This shows that not only the nature or the position of a defect influences the chiral expression, but also the mixing of polymers with a defect in different positions.

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Effect of the Nature and the Position of Defects on the Chiral Expression in Poly(3-alkylthiophene)s

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“…To date many functionalize polythiophenes have been synthesized consisting of thiophene monomers with various substituents at 3-position. While different alkyl substituents are the most commonly used, the use of esters (-COOR), 98,99 acetyl (-COR), 100 amide (-CONHR), 101 alkoxy (-OR), 102-105 alkylthio (-SR), [106][107][108] sulfonyl (-SO 3 R), 109 alkylamino (-NHR and NRR 0 ) 110 and uoroalkyl [111][112][113][114][115][116][117][118][119] groups have also been reported. It has now been established that functionalization of polythiophenes not only enhanced their solubility and processability, it also altered their optical and electronic properties.…”

Section: Effects Of Various Functional Groups On the Properties Of Pomentioning

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Recent developments in the synthesis of regioregular thiophene-based conjugated polymers for electronic and optoelectronic applications using nickel and palladium-based catalytic systems

et al. 2020

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“…For example, they could be used as circular polarized luminescent materials, chiral catalyst for asymmetric synthesis, chiral sensor, and nonlinear optics . The general approaches for inducing chirality in conjugated polymers include introducing a chiral group on the side chain, chiral building blocks incorporated on the polymer backbone, or helical macrostructure assembly induced by interaction between functionalized polymers with metal ions . Majority of the studies were focused on polythiophenes, and poly( p ‐phenylene ethynylene)s incorporated with chiral functional groups .…”

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Synthesis, characterization, and structure-property investigation of conformationally rigid regioisomers of poly(p-phenylene ethynylene)s

Sen

Valiyaveettil

2016

J. Polym. Sci. Part A: Polym. Chem.

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A series of rigid poly(p‐phenylene ethynylene)s (PPE1–PPE4) with biphenyl‐ (M1–M3) and phenyl‐ (M4) side groups is prepared from appropriately functionalized monomers. Herein, the solution and solid state absorption studies show the polymers have adopted twisted and rigid conformations, as supported by deep HOMO energy levels (−5.76 to −5.81 eV). The absorption maxima of PPE1–PPE3 are shifted to shorter wavelength (λmax = 375–381 nm) as compared to linear poly(p‐phenylene ethynylene)s (446 nm), implying a nonplanar conformation. The self‐assembly of polymers into fibers is examined using scanning electron microscopy. The fibers are not observed in PPE4 with short phenyl side group, suggesting the important role of the interplay between rigidity, position, and size of the side chains toward the formation of fibers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3652–3662

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Influence of the regioregularity on the chiral supramolecular organization of poly(3-alkylsulfanylthiophene)s

Cited by 18 publications

References 39 publications

Effect of the Nature and the Position of Defects on the Chiral Expression in Poly(3-alkylthiophene)s

Effect of the Nature and the Position of Defects on the Chiral Expression in Poly(3-alkylthiophene)s

Recent developments in the synthesis of regioregular thiophene-based conjugated polymers for electronic and optoelectronic applications using nickel and palladium-based catalytic systems

Synthesis, characterization, and structure-property investigation of conformationally rigid regioisomers of poly(p-phenylene ethynylene)s

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