Synthesis and characterization of thienylene–phenylene copolymers with oligo(ethylene oxide) side chains

“…Regioregular poly(3‐alkylthiophenes) are the most notable class of π‐conjugated materials because they exhibit excellent chain planarity and extended conjugation lengths, owing to their head‐to‐tail regiochemistry, thus leading, in some cases, to highly conjugated sheets with high field‐effect mobilities 2. 3 More recently, highly regioregular thienylene‐2,5‐dialkoxyphenylene copolymers have been recognized for their high conjugation over the π system along their backbone, owing to the presence of polar dialkoxy chains, which are favorable for high‐quality homogeneous thin‐film coatings on glass with very low band‐gaps and low oxidation potentials 4. Ordering of the polymer chains can result from coating them onto an oriented Teflon deposit to achieve polarized fluorescence5 or from the self‐organization of macromolecular chains into lamellar structures, which can be tuned by privileged π‐stacking interactions 4.…”

Section: Introductionmentioning

confidence: 99%

“…3 More recently, highly regioregular thienylene‐2,5‐dialkoxyphenylene copolymers have been recognized for their high conjugation over the π system along their backbone, owing to the presence of polar dialkoxy chains, which are favorable for high‐quality homogeneous thin‐film coatings on glass with very low band‐gaps and low oxidation potentials 4. Ordering of the polymer chains can result from coating them onto an oriented Teflon deposit to achieve polarized fluorescence5 or from the self‐organization of macromolecular chains into lamellar structures, which can be tuned by privileged π‐stacking interactions 4. Oligo(phenylenethienylenes) have been revealed to be good transport materials because interesting mobilities can be achieved in organic field‐effect transistors with these stable and easily processable compounds 6.…”

Section: Introductionmentioning

confidence: 99%

Comprehensive Analysis of Fragment Orbital Interactions to Build Highly π‐Conjugated Thienylene‐Substituted Phenylene Oligomers

Florès

Lacour

Sallenave

et al. 2013

Chemistry A European J

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π-Conjugated thienylene-phenylene oligomers with fluorinated and dialkoxylated phenylene fragments have been designed and prepared to understand the interactions in fragment orbitals, the influence of the substituents (F, OMe) on the HOMO-LUMO gap, and the role of intramolecular non-covalent cumulative interactions in the construction of π-conjugated nanostructures. Their strong conjugation was also evidenced in the gas phase by UV photoelectron spectroscopy and theoretical calculations. These results can be explained by the crucial role of the relative energetic positions of the π orbitals of the dimethoxyphenylene, which was used to model the dialkoxyphenylene entity, in determining the π/π(*) orbital levels of the fluorinated phenylene entity. Dialkoxyphenylenes raise the HOMO orbitals, whereas fluorinated phenylenes lower the LUMO orbitals in the oligomers. In addition, the presence of S⋅⋅⋅F and H⋅⋅⋅F interactions in the fluorinated phenylene-thienylene compounds add to the S⋅⋅⋅O interactions in the mixed targets and contribute to the full conjugation in the oligomer, inducing weak inter-ring angles between the involved aromatic cycles. These results, which showed extended conjugation of the π system, were corroborated by a narrow HOMO-LUMO gap (according to DFT calculations) and by a relatively strong maximum wavelength (as obtained by TD-DFT calculations and experimental UV/Vis measurements). The crystallographic data of two mixed thienylene-(fluorinated and dialkoxylated phenylene) five-ring oligomers agree with the above results and show the formation of quasi-planar conformations with non-covalent S⋅⋅⋅O, H⋅⋅⋅F, and S⋅⋅⋅F interactions. These studies in the solid and gas phases show the relevance of associating dialkoxyphenylene and fluorinated phenylene fragments with thiophene to lead to oligomers with improved electronic delocalization for electronic or optoelectronic devices.

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“…Moreover, polyether‐based electrolytes show high ionic conductivities . The introduction of highly polar chains in conjugated polythiophene derivatives can effectively enhance the ionic sensitivity . Many attempts have been paid on polythiophene, and 3,4‐alkylenedioxythiophene (XDOT)‐based ECPs .…”

Section: Introductionmentioning

confidence: 99%

“…[23][24][25][26][27] The introduction of highly polar chains in conjugated polythiophene derivatives can effectively enhance the ionic sensitivity. [28][29][30][31][32][33][34][35][36] Many attempts have been paid on polythiophene, [31][32][33][34][35] and 3,4-alkylenedioxythiophene (XDOT)based ECPs. [29,36] For example, Giovannitti et al modified the thiophene backbone with glycolated chains that can facilitate ion penetration in electrolyte-gated transistors.…”

Section: Introductionmentioning

confidence: 99%

The Effect of Oligo(Ethylene Oxide) Side Chains: A Strategy to Improve Contrast and Switching Speed in Electrochromic Polymers

et al. 2020

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Solution‐processable electrochromic polymers (ECPs) with high performance are urgently needed for extensive applications. Nevertheless, they suffer from slow switching speed because of low ionic conductivities. Herein, we present an effective strategy to improve the contrast and switching speed in ECPs via facile side‐chain engineering. A novel electrochromic thieno[3,2‐b]thiophene‐based polymer (PmOTTBTD) is designed and successfully synthesized by introducing oligo(ethylene oxide) side chains with high ionic conductivity. Compared to the counterpart POTTBTD without modification by oligo(ethylene oxide) chains, PmOTTBTD demonstrates nearly double contrast (42 % vs. 24 %) with a fast oxidation switching process that just takes half of the time when detected under 400 nm, as well as much higher coloration efficiencies (e. g. 239.04 cm2 C−1 vs. 226.26 cm2 C−1 @ 400 nm and 314.04 cm2 C−1 vs. 174.00 cm2 C−1 @ 650∼700 nm). Besides, PmOTTBTD exhibits excellent stability with negligible decay after 3000 cycles. Our work suggests a facile strategy that could be adopted to realize high‐performance ECPs via molecular design tuning.

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Synthesis and characterization of thienylene–phenylene copolymers with oligo(ethylene oxide) side chains

Cited by 25 publications

References 50 publications

Absorption and photoluminescence of a new thienylene–phenylene copolymer

Absorption and photoluminescence of a new thienylene–phenylene copolymer

Comprehensive Analysis of Fragment Orbital Interactions to Build Highly π‐Conjugated Thienylene‐Substituted Phenylene Oligomers

The Effect of Oligo(Ethylene Oxide) Side Chains: A Strategy to Improve Contrast and Switching Speed in Electrochromic Polymers

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