Optically active polyalkylthiophenes: synthesis and polymerization of chiral, symmetrically substituted, quinquethiophene monomer

Andreani, F.; Angiolini, Luigi; Grenci, Valeria; Salatelli, Elisabetta

doi:10.1016/j.synthmet.2004.05.006

Cited by 14 publications

(11 citation statements)

References 28 publications

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“…This is indicative of opposite chirality assumed in the aggregated state by poly(DHDMBQT) and poly(DDDMBQT) with respect to poly(DMBTT). This behaviour parallels that observed for the same samples when their aggregation in solution is promoted by addition of a poor solvent [16,17]. It is known that the sign of optical activity of chiral polythiophene aggregates may be affected by a change of solvent [4,12,18] or even a change of composition of the solvent mixture [7].…”

Section: Fig 1 Uv Vis Spectra Of Poly(dhdmbqt) As Spin Coated Film supporting

confidence: 83%

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Characterization of thin films of regioregular poly(alkylthiophene)s bearing optically active substituents

et al. 2009

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Abstract:The spectroscopic behavior of thin films of regioregular poly(alkylthiophene)s bearing an optically active alkyl group has been investigated in the solid state under different sample preparation procedures. The experimental results are interpreted in terms of influence of the side-chain substituents on the extent of planarity of the polymeric chains and the formation of optically active chiral aggregates.

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Section: Fig 1 Uv Vis Spectra Of Poly(dhdmbqt) As Spin Coated Film supporting

confidence: 83%

“…Poly(DMBTT) [22], poly(DHDMBQT) [16] and poly(DDDMBQT) [17], were purified as described and characterized by the usual procedures. Several thin film samples were …”

Section: Methodsmentioning

confidence: 99%

Characterization of thin films of regioregular poly(alkylthiophene)s bearing optically active substituents

et al. 2009

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“…No endothermic peaks related to melting followed by recrystallization were observed, in agreement with the amorphous structure of these materials in the solid state. The T g values decrease with respect to those given by other ter-and quinque thiophenic alkyl substituted polymers, 5,6 as a consequence of the increase of steric hindrance and flexibility of the side-chain ethereal alkyl substituent, favoring a better mobility of the macromolecules and lower possibility of packing in the bulk.…”

Section: Synthesis and Characterization Of Poly(dmboett) And Poly(dmbmentioning

confidence: 80%

“…In the aggregated phase, chiral polythiophenes offer the possibility of studying the structural changes accompanying the transition from the disordered state by following the variation of their chiroptical properties by circular dichroism (CD) measurements. 3,4 Optically active polythiophenes with these characteristics have been recently prepared starting from a symmetrical teror quinquethiophene monomer 3,3 00 -di[(S)- (1) 6 or poly(DDDMBQT) 7 , respectively), by oxidative polymerization with iron(III) trichloride (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“…at 457 nm) 6 and poly(DDDMBQT) (42,900 L mol -1 cm -1 at 456 nm) 7 (Scheme 1), both of them derived from the polymerization of a quinquethiophene monomer, display higher e values in CHCl 3 , probably in consequence of different solvation conditions due to the presence of two C6 or C12 linear alkyl groups in each quinquethiophene repeating unit. Similar values of maximum wavelength are found in THF for poly(DMBOETT) and poly(DMBOEBT) (436 and 393 nm, respectively), but with significantly lower values of absorption coefficient (Table 3).…”

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Chirality induced by microaggregation of regioregular polythiophenes with side‐chain optically active substituent

2010

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Two novel optically active terthiophene and bithiophene monomers bearing at the C-β position of thiophene ring an enantiomerically pure chiral alkyl group, namely 3,3″-di[2-((S)-(+)-2-methylbutoxy)ethyl]-2,2':5',2″-terthiophene and 3,3'-di[2-((S)-(+)-2-methylbutoxy)ethyl]-2:2'-bithiophene, have been synthesized and characterized. Being symmetrically substituted, their polymerization adopting simple and economic method, such as the chemical oxidation with iron (III) trichloride, allowed to obtain regioregular macromolecules. The synthesized polymers have been investigated by CD in solution as well as in the microaggregated state upon gradual addition of a poor solvent. The results display different CD behaviors related to their chemical structure.

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Chiral Teleinduction in the Formation of a Macromolecular Multistate Chiroptical Redox Switch

et al. 2005

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Electroactive organic polymers are not only attractive from the viewpoint of their solid-state propertiesÐlike electrical conduction or electrochromism [1] Ðbut also as promising candidates in molecular electronics, [2] including as switches for information storage, an area dominated by smaller molecules.[3±5] While photochemically induced switching in polymers has received much attention, [6] other external stimuli like thermal treatment, [7] chemical or redox interactions, [8] and their combination to make multifunctional polymers [9] are also attractive. Motivated by this promise, one of our objectives is the preparation of chiral redox-polymer systems.[10]Tetrathiafulvalene (TTF) derivatives are good candidates as components of these polymers because of their reversible and tunable redox properties. [11,12] They show two reversible one-electron oxidation processes to form the cation radical and the dication. As a scaffold for these units we chose the poly(isocyanide)s, [13] which can assume chiral conformations and organize electroactive groups. [8,12,14] This manuscript describes a chiral TTF-substituted poly(isocyanide) [15] that shows reversible interconversion between three univalent and two very broad mixed-valence redox states ( Fig. 1) that have different chiroptical properties, behavior that is not shown by the monomer. The TTF derivative, 2 (Scheme 1), bearing a phenyl isocyanide group and two stereogenic centers to induce diastereoselectivity in the polymerization, acts as our monomer. Long alkyl chains are present to ensure the solubility of the resulting polymer. The synthesis of 2 was performed following a multistep synthetic route, [16] the last step of which is the conversion of the formamide 1 to the isocyanide 2 by dehydration with diphosgene. Treatment of 2 with NiCl 2´6 H 2 O as a catalyst in CH 2 Cl 2 gave poly(isocyanide) 3 in 85 % yield (Scheme 1). The conversion of the monomer into the polymer was confirmed analytically.The IR spectrum of 3 showed a broad band from the imine groups attached to the polymer backbone at approximately 1642 cm ±1 and no signal corresponding to the isocyanide moi-

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Optically active polyalkylthiophenes: synthesis and polymerization of chiral, symmetrically substituted, quinquethiophene monomer

Cited by 14 publications

References 28 publications

Characterization of thin films of regioregular poly(alkylthiophene)s bearing optically active substituents

Characterization of thin films of regioregular poly(alkylthiophene)s bearing optically active substituents

Chirality induced by microaggregation of regioregular polythiophenes with side‐chain optically active substituent

Chiral Teleinduction in the Formation of a Macromolecular Multistate Chiroptical Redox Switch

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