Synthesis of functionalizable derivatives of 3,4‐ethylenedioxythiophene and their solid‐state polymerizations

Gulprasertrat, Narut; Chapromma, Jirasak; Aree, Thammarat; Sritana-anant, Yongsak

doi:10.1002/app.42233

Cited by 6 publications

(7 citation statements)

References 25 publications

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“…The idea of SSP of a suitable monomer in a well-ordered crystalline state was already realized in the 1960s and 1970s with polydiacetylenes and (SN)x, but SSP of a thiophene derivative was serendipitously discovered and reported by Wudl and Perepichka, who observed that prolonged storage (about two years) of 2,5-dibromo-3,4-ethylenedioxythiophene(DBEDOT) at room temperature gave a bluish conjugated polymer [ 116 ]. Over time, other scientists confirmed and employed this C-Br/C-Br polycondensation method [ 115 , 117 , 118 , 119 ].…”

Section: Resultsmentioning

confidence: 99%

Thiophene α-Chain-End-Functionalized Oligo(2-methyl-2-oxazoline) as Precursor Amphiphilic Macromonomer for Grafted Conjugated Oligomers/Polymers and as a Multifunctional Material with Relevant Properties for Biomedical Applications

Bendrea¹,

Cianga²,

Ailiesei³

et al. 2022

IJMS

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Because the combination of π-conjugated polymers with biocompatible synthetic counterparts leads to the development of bio-relevant functional materials, this paper reports a new oligo(2-methyl-2-oxazoline) (OMeOx)-containing thiophene macromonomer, denoted Th-OMeOx. It can be used as a reactive precursor for synthesis of a polymerizable 2,2’-3-OMeOx-substituted bithiophene by Suzuki coupling. Also a grafted polythiophene amphiphile with OMeOx side chains was synthesized by its self-acid-assisted polymerization (SAAP) in bulk. The results showed that Th-OMeOx is not only a reactive intermediate but also a versatile functional material in itself. This is due to the presence of 2-bromo-substituted thiophene and ω-hydroxyl functional end-groups, and due to the multiple functionalities encoded in its structure (photosensitivity, water self-dispersibility, self-assembling capacity). Thus, analysis of its behavior in solvents of different selectivities revealed that Th-OMeOx forms self-assembled structures (micelles or vesicles) by “direct dissolution”.Unexpectedly, by exciting the Th-OMeOx micelles formed in water with λabs of the OMeOx repeating units, the intensity of fluorescence emission varied in a concentration-dependent manner.These self-assembled structures showed excitation-dependent luminescence as well. Attributed to the clusteroluminescence phenomenon due to the aggregation and through space interactions of electron-rich groups in non-conjugated, non-aromatic OMeOx, this behavior certifies that polypeptides mimic the character of Th-OMeOx as a non-conventional intrinsic luminescent material.

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Section: Resultsmentioning

confidence: 99%

Thiophene α-Chain-End-Functionalized Oligo(2-methyl-2-oxazoline) as Precursor Amphiphilic Macromonomer for Grafted Conjugated Oligomers/Polymers and as a Multifunctional Material with Relevant Properties for Biomedical Applications

Bendrea¹,

Cianga²,

Ailiesei³

et al. 2022

IJMS

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“…In all reports focused on the XRD structures of 2,5-dibromothiophenes in relation to the effect of XB on the SSP, ,,, only the distances between Br atoms in the neighboring molecules were analyzed, while the angle C–Br···Br–C was only considered in one paper . The distance approach is certainly insufficient to attribute bromine···bromine contacts to Type I (packing effect) or Type II (real XB) according to the IUPAC classification .…”

Section: Resultsmentioning

confidence: 99%

“…According to another hypothesis, the polymerization is promoted by the anti-orientation of thiophene rings in one-dimensional XB linked chains . In a subsequent report, it was observed that large Br···Br separations do not prevent SSP but reduce its rate at a qualitative level. The effect of a decrease in the SSP rate along with an increase in the X···X distance was demonstrated for the polymerization of some diiodothiophene derivatives …”

Section: Introductionmentioning

confidence: 96%

2,5-Dibromothiophenes: Halogen Bond Involving Packing Patterns and Their Relevance to Solid-State Polymerization

Baykov

Presnukhina

Novikov

et al. 2021

Crystal Growth & Design

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A series of 2,5-dibromo-3-R-thiophenes (R = COONa 1, CN 2, CONH2 3, CON(H)Me 4, CON(H)Bn 5, CON(CH2CH2)2O 6, CON(H)NH2 7, CON(H)OH 8) were prepared and studied via high-resolution ESI-MS, 1H and 13C{H} NMR, IR, and X-ray diffraction. The analysis of the X-ray structures revealed Br···Br halogen bonds (XBs) as structure-directing interactions. A search of the Cambridge Structural Database showed an additional 12 structures of 2,5-dibromothiophenes whose structures featured Br···Br XBs. The crystal packing patterns for all these 2,5-dibromothiophenes were classified, and three general types were identified: (i) chains held by XBs, where each Br acts either as an XB donor or as an XB acceptor; (ii) zigzag arrays, where each Br functions simultaneously as an XB donor and acceptor; and (iii) rhombic assemblies with Br atoms at each vertex. DFT calculations, followed by topological analyses of the electron density distribution (QTAIM analysis) at the M06-2X/DZP-DKH level of theory, were performed to evaluate the strength of these XBs. The established energies were in the range from 0.5 to 2.2 kcal/mol, regardless of the packing type.

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“…The polymer films, modified with bioactive macromolecules, show enhanced biological activity. Finally, functionalizable derivatives of EDOT were polymerized in the solid state, and active PEDOT-based chains were produced [ 195 ]. However, to the best of our knowledge, the polymers were not used for postmodification.…”

Section: Covalent Functionalization Of Conductive Polymersmentioning

confidence: 99%

Functionalization of Conductive Polymers through Covalent Postmodification

et al. 2022

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Organic chemical reactions have been used to functionalize preformed conducting polymers (CPs). The extensive work performed on polyaniline (PANI), polypyrrole (PPy), and polythiophene (PT) is described together with the more limited work on other CPs. Two approaches have been taken for the functionalization: (i) direct reactions on the CP chains and (ii) reaction with substituted CPs bearing reactive groups (e.g., ester). Electrophilic aromatic substitution, SEAr, is directly made on the non-conductive (reduced form) of the CPs. In PANI and PPy, the N-H can be electrophilically substituted. The nitrogen nucleophile could produce nucleophilic substitutions (SN) on alkyl or acyl groups. Another direct reaction is the nucleophilic conjugate addition on the oxidized form of the polymer (PANI, PPy or PT). In the case of PT, the main functionalization method was indirect, and the linking of functional groups via attachment to reactive groups was already present in the monomer. The same is the case for most other conducting polymers, such as poly(fluorene). The target properties which are improved by the functionalization of the different polymers is also discussed.

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Synthesis of functionalizable derivatives of 3,4‐ethylenedioxythiophene and their solid‐state polymerizations

Cited by 6 publications

References 25 publications

Thiophene α-Chain-End-Functionalized Oligo(2-methyl-2-oxazoline) as Precursor Amphiphilic Macromonomer for Grafted Conjugated Oligomers/Polymers and as a Multifunctional Material with Relevant Properties for Biomedical Applications

Thiophene α-Chain-End-Functionalized Oligo(2-methyl-2-oxazoline) as Precursor Amphiphilic Macromonomer for Grafted Conjugated Oligomers/Polymers and as a Multifunctional Material with Relevant Properties for Biomedical Applications

2,5-Dibromothiophenes: Halogen Bond Involving Packing Patterns and Their Relevance to Solid-State Polymerization

Functionalization of Conductive Polymers through Covalent Postmodification

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