The synthesis of π-electron molecular rods with a thiophene or thieno[3,2-b]thiophene core unit and sulfur alligator clips

Seidler, Arnošt; Svoboda, Jiřı́; Dekoj, Václav; Chocholoušová, Jana Vacek; Vacek, Jaroslav; Stará̈, Irena G.; Starý, Ivo

doi:10.1016/j.tetlet.2013.03.084

Cited by 11 publications

(11 citation statements)

References 37 publications

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“…Trimethylsilylacetylene (392 mg, 4.00 mmol) was added to a stirred solution of [45] . 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 25 and purity check with NMR and MS. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 26 KF (188 mg, 3.24 mmol) in 20 mL CH 3 OH and 5 mL THF was heated to reflux under nitrogen atmosphere for 24 h. The crude product was collected by filtration, washed with methanol and hexane.…”

Section: Syntheses Of Bis((trimethylsilyl)ethynyl)thienoacenesmentioning

confidence: 99%

Bonding and Electronic Properties of Linear Diethynyl Oligothienoacene-Bridged Diruthenium Complexes and Their Oxidized Forms

Zhang

et al. 2017

Inorg. Chem.

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A series of five diruthenium diethynyl complexes based on α,β-fused oligothienoacenes in the core of the bridging ligands [{Ru(dppe)Cp*}(μ-C≡C-L-C≡C)] [dppe = 1,2-bis(diphenylphosphino)ethane, Cp* = η-CMe; L = thieno[3,2-b]thiophene (4), thieno[2,3-b]thiophene (5), 3,4-dimethylthieno[2,3-b]thiophene (6), dithieno[3,2-b:2',3'-d]thiophene (7), and thieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene (8)] have been synthesized and fully characterized electrochemically and spectroscopically. Elongation of the redox noninnocent oligothienoacene bridge core causes a smaller potential difference between the initial two anodic steps, not seen for free dialkyl oligothienoacenes, and increased positive charge delocalization over the conjugated bridge backbone. The highest occupied molecular orbital of the parent complexes resides predominantly on the oligothienoacene core, with strong participation of the ethynyl linkers and slightly smaller contribution from the metallic termini. This bonding character makes the initial one-electron oxidation symmetrical, as revealed by combined voltammetric and spectroscopic (IR, UV-vis-near-IR, and electron paramagnetic resonance) methods as well as density functional theory (DFT) and time-dependent DFT calculations of truncated and selected nontruncated models of the studied series. The remarkable gradual appearance of two C≡C stretching absorptions in the IR spectra of the monocationic diethynyl complexes is ascribed to increasing vibronic coupling of the IR-forbidden ν(C≡C) mode of the oxidized -[C≡C-core-C≡C]- bridge with a low-lying π-π*(intrabridge)/metal-to-ligand charge-transfer electronic transition in the near-to-mid-IR spectral region.

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Section: Syntheses Of Bis((trimethylsilyl)ethynyl)thienoacenesmentioning

confidence: 99%

Bonding and Electronic Properties of Linear Diethynyl Oligothienoacene-Bridged Diruthenium Complexes and Their Oxidized Forms

Zhang

et al. 2017

Inorg. Chem.

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“…Monomers, 2,5-diethynyl-3-hexylthiophene (DET) and 2,5-diethynyl-3,6-didodecylthieno[3,2- b ]thiophene (DETT), − were synthesized from commercially available starting materials by adopting the procedures reported in the literature (Schemes S1 and S2 and Figures S1–S11). The monomers were then polymerized by Hay coupling in air-bubbled chloroform using CuCl/ N , N , N ′, N ′-tetramethylethylenediamine (TMEDA) as catalysts .…”

Section: Results and Discussionmentioning

confidence: 99%

“…All reagents and chemicals were purchased from Tokyo Chemical Industry (TCI), Kanto Chemical, Co., Inc., and Sigma-Aldrich, and used as received unless otherwise stated. Polymers pDET and pDETT, monomers DET, and DETT − were synthesized by using the modified procedures reported in the literature.…”

Section: Methodsmentioning

confidence: 99%

Cross-Linking of Poly(arylenebutadiynylene)s and Its Effect on Charge Carrier Mobilities in Thin-Film Transistors

et al. 2021

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Thermal or photochemical 1,4-coupling reactions of butadiyne units can be employed to cross-link polymers. Poly(arylenebutadiynylene)s are solution-processable organic semiconducting polymers which are used in organic electronic devices. However, effects of the topochemical cross-linking reactions of the main chain backbone on the electronic device performances have not been reported before. Intermolecular π–π stacking of the main chain backbones was expected to assist the alignment of the butadiyne units, and this would omit the necessity of introducing conventional aligning groups such as hydrogen-bonding amide units. Two different poly(arylenebutadiynylene)s, namely, crystalline poly(thieno[3,2-b]thiophen-2,5-diylbutadiynelene) (pDETT) and rather amorphous poly(thiophen-2,5-diylbutadiynelene) (pDET), were prepared, and their topochemical cross-linking was comprehensively studied. Grazing-incident wide-angle X-ray scattering (GIWAXS) measurements and density functional theory calculations of pDETT demonstrated the required butadiyne alignment suitable for the thermal topochemical reaction. As the newly formed covalent bonds were almost perpendicular to the polymer backbone plane, the resulting twist of the polymer backbone disrupted the extent of π-conjugation, which should have negatively affected the charge transport properties. However, the very tight molecular packings of pDETT inhibited the formation of excess cross-links. Consequently, the partially cross-linked pDETT film showed an improved charge carrier mobility in organic field-effect transistors as compared to the precursor polymer film. On the other hand, amorphous pDET produced cross-links at the randomly π–π stacked regions by both thermal and UV-induced topochemical reactions, and the resulting films were completely deficient of charge transport.

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“…Naturally, the monothiophenyl molecular rods have been extensively explored in the literature, from alkyl and silyl, groups through aromatic,,, heteroatomic aromatic substituents such as pirydyl , anisyl and methoxy, to bulky aromatic pyrene units. Due to the challenging multi‐step synthesis of the next fused‐ring homologue, thienothiophene (TT), a limited number of structures are reported and include tertiary‐butyl, trimethylsilane,, phenyl and phenylthioacetate . Following this trend, the next homologue in the series is dithienothiophene (DTT), which has yet to be fully explored in the literature and is the focus of the present study.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterisation of Fused Heterocyclic Molecular Rods: A Combined Experimental and Theoretical Study on Diethynyl Dithienothiophenyl Derivatives

et al. 2017

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A structural and electronic diversity of symmetric diethynyl dithienothiophenyl (DTT) molecular rods were synthesised and their properties fully characterised using optical and thermal analysis and complemented with density functional theory (DFT) calculations. It was found that some structures are stable up to 381 °C. Due to the nature of both the derivative and the substituent, physical properties such as electron donating ability and thermal stability can be fine‐tuned to generate rationally designed materials, all of which have excellent solubility in common organic solvents. The single‐crystal x‐ray structures revealed that both bulky silyl and linear alkyl derivatives generate regular lateral close packing between the adjacent molecules, suitable for charge‐transfer in organic thin‐film transistors (OTFTs), whereas the same ethynyl derivative without an alkyl chain gives a non‐planar interlinking structure and thus unsuitable for OTFTs. These air‐stable electron rich DTT‐based molecular rods have strong potential as organic semiconductors for organic electronic applications.

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The synthesis of π-electron molecular rods with a thiophene or thieno[3,2-b]thiophene core unit and sulfur alligator clips

Cited by 11 publications

References 37 publications

Bonding and Electronic Properties of Linear Diethynyl Oligothienoacene-Bridged Diruthenium Complexes and Their Oxidized Forms

Bonding and Electronic Properties of Linear Diethynyl Oligothienoacene-Bridged Diruthenium Complexes and Their Oxidized Forms

Cross-Linking of Poly(arylenebutadiynylene)s and Its Effect on Charge Carrier Mobilities in Thin-Film Transistors

Synthesis and Characterisation of Fused Heterocyclic Molecular Rods: A Combined Experimental and Theoretical Study on Diethynyl Dithienothiophenyl Derivatives

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