Toward Functionalized Conducting Polymers:  Synthesis and Characterization of Novel β-(Styryl)terthiophenes

Collis, Gavin E.; Burrell, Anthony K.; Scott, Sonya M.; Officer, David L.

doi:10.1021/jo034855g

Cited by 68 publications

(56 citation statements)

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“…The synthesis of the indanedionefunctionalized terthiophene (TTh) monomers 2 and 3 required the preparation of the corresponding aldehydes 1a (R = OC 6 H 13 ) or 1b (R = OC 10 H 21 ) (Scheme 1). These were easily prepared by the Suzuki coupling route that we had previously developed for the synthesis of terthiophene-3 0 -aldehyde (1c) 15 and the corresponding 4-alkoxyboronic acids. 14 The indanedione-functionalized TTh monomers 2 and 3 were synthesized in 81% and 62% yield, respectively, from the corresponding aldehydes 1a and 1b via Knoevenagel condensations with 1,3-indanedione (Scheme 1).…”

Section: Methodsmentioning

confidence: 99%

“…The 1 H NMR spectrum of the indanedione-TTh 3 showed a sharp single proton signal at 8.6 ppm (Figure 1a), attributed to the hydrogen of the central thiophene ring, shifted considerably from its expected position at ∼7.5 ppm (shaded box). 15 The shift likely results from the deshielding effect of the neighboring indanedione carbonyl group, suggesting that monomer 3 adopts the conformation shown in Figure 1 (inset), indicative of significant conjugative overlap between the terthiophene moiety and the indanedione substituent. This is supported by the UV-vis spectrum of 3, which exhibits two bands: the first at 353 nm, a typical terthiophene absorption band, and the second smaller absorption band at 471 nm, which we assign to an ICT band (Figure 1c), analogous to that observed previously for terthiophene indanedione, 10 as well as by Roquet et al for a thiophene indanedione derivative.…”

Section: Methodsmentioning

confidence: 99%

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Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

et al. 2010

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Officer, D. L. (2010). Indanedione-substituted poly(terthiophene)s: Processable conducting polymers with intramolecular charge transfer interactions. Macromolecules, 43 (8), 3817-3827. Indanedione-substituted poly(terthiophene)s: Processable conducting polymers with intramolecular charge transfer interactions AbstractThe electrochemical and chemical syntheses of poly(terthiophene)s bearing an indanedione pendant group and displaying intramolecular charge transfer interactions have been achieved. The nature of the charge transfer interaction is characterized through DFT calculations and experimental studies, including resonance Raman spectroscopy and absorption and emission data through a Lippert-Mataga analysis. It is found that the low-energy transition present in the indanedione-bearing monomer species has considerable charge transfer character with a dipole change of II D. Decomposition of the indanedione group occurred during hydrazine reduction after chemical polymerization. A soluble, low molecular weight indanedione-substituted polymer (weight average 4500 Da) was nonetheless obtained following the use of a milder reducing agent, triethanolamine. To the best of our knowledge, this is the first example of the use of triethanolamine for the reduction of an oxidized polythiophene, providing a milder and safer alternative to hydrazine. In an attempt to produce higher molecular weight processable polymers with intramolecular charge transfer interactions, a copolymer of the indanedione-substituted terthiophene and a dihexylterthiophene was synthesized. The electronic conjugation of the produced polymers was characterized by Raman frequency dispersion experiments and show dispersion rate parameters similar to those observed for other substituted polythiophenes. ABSTRACT: The electrochemical and chemical syntheses of poly(terthiophene)s bearing an indanedione pendant group and displaying intramolecular charge transfer interactions have been achieved. The nature of the charge transfer interaction is characterized through DFT calculations and experimental studies, including resonance Raman spectroscopy and absorption and emission data through a Lippert-Mataga analysis. It is found that the low-energy transition present in the indanedione-bearing monomer species has considerable charge transfer character with a dipole change of 11 D. Decomposition of the indanedione group occurred during hydrazine reduction after chemical polymerization. A soluble, low molecular weight indanedionesubstituted polymer (weight average 4500 Da) was nonetheless obtained following the use of a milder reducing agent, triethanolamine. To the best of our knowledge, this is the first example of the use of triethanolamine for the reduction of an oxidized polythiophene, providing a milder and safer alternative to hydrazine. In an attempt to produce higher molecular weight processable polymers with intramolecular charge transfer interactions, a copolymer of the indanedione-substituted terthiophene and a dihexylterthiophene was synthesized. The ...

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

et al. 2010

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“…3 0 -Formyl-2:2 0 ,5 0 :2 00 -terthiophene (1) 3 0 -Formyl-2:2 0 ,5 0 :2 00 -terthiophene was synthesized according to Ref. [23]. 1 …”

Section: Monomer Synthesismentioning

confidence: 99%

Synthesis of a functionalized polythiophene as an active substrate for a label-free electrochemical genosensor

Peng

Zhang

Spires

et al. 2007

Polymer

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“…[51] Unsubstituted terthiophene was purchased from Aldrich and used without further purification. The synthesis and purification of DM-pe3T via its aldehyde precursor 5,5''-dimethyl-3'-formyl-2:2',5':2''-terthiophene is detailed below.…”

Section: Methodsmentioning

confidence: 99%

Raman Spectroscopy of Short‐Lived Terthiophene Radical Cations Generated by Photochemical and Chemical Oxidation

et al. 2006

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The Raman spectra of various terthiophene radical cations are investigated; namely those of unsubstituted terthiophene and two styryl-substituted terthiophenes. Transient pump-probe resonance Raman spectroscopy is used to measure the short-lived radical cation spectra of non-end-capped 2,2':5',2''-terthiophene (3T) and 3'-[(E)-2-(4-nitrophenyl)ethenyl]-2,2':5',2''-terthiophene (NO2-pe3T). For these two compounds, the radical cations are generated via either direct photogeneration or photochemically using the electron acceptor tetracyanoethylene. The radical cation of 5,5''-dimethyl-3'-[(E)-2-phenylethenyl]-2,2':5',2''-terthiophene (DM-pe3T) is stable for up to five minutes as a result of the two alpha end caps and continuous-wave resonance Raman spectroscopy and chemical oxidation is used to obtain the spectrum of this radical cation. The resonance Raman spectra of all three terthiophene radical cations are dominated by a group of very intense bands in the low-frequency region. These bands have been assigned, by density functional theory methods, to C-S stretching modes coupled to thiophene ring deformations. These modes are significantly less intense in the sigma-dimer of NO2-pe3T [i.e. the corresponding styryl sexithiophene (NO2-pe3T)2]. This observation is attributed to a smaller change in the C--S bond order in the sexithiophene compared to the analogous terthiophene. This bond order difference may be rationalised by consideration of the singly occupied molecular orbital and lowest unoccupied molecular orbital, which are involved in the electronic transition probed by the laser excitation wavelength.

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Toward Functionalized Conducting Polymers: Synthesis and Characterization of Novel β-(Styryl)terthiophenes

Cited by 68 publications

References 61 publications

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

Synthesis of a functionalized polythiophene as an active substrate for a label-free electrochemical genosensor

Raman Spectroscopy of Short‐Lived Terthiophene Radical Cations Generated by Photochemical and Chemical Oxidation

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