Synthese, electrochemical properties and crystal structure of tetracyano-p-quinodimethane (TCNQ) derivatives with π-extended systems containing a sulfur atom

Cruz, Pilar de la; Martín, Nazario; Miguel, Fuencisla; Seoane, Carlos; Albert, Armando; Cano, F. H.; Leverenz, Andreas; Hanack, Michael

doi:10.1016/0379-6779(92)90050-s

Cited by 12 publications

(4 citation statements)

References 19 publications

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“…[15] After the introduction of the dicyanomethylene groups in 8 and 9 a new band, which grows in at approximately 330 nm, alongside a red-shift and an increase in intensity of the longest wavelength band is observed. Such changes are typical for these transformations [18,19,58,59] and can be attributed primarily to the lowering of the LUMO energy, and thereby the optical HOMO-LUMO gap (E g opt ), by the presence of the strongly electron-accepting dicyanomethylene units.…”

Section: Uv/vis Absorbance Spectroscopymentioning

confidence: 99%

“…In the DFT optimised structures of 5 and 8 the thienyl protons are angled ~11°further away than the phenyl protons on the other side of the quinone. While TCAQ and a number of TCAQ analogues based on [b]-thiophene and benzo-[b]thiophene [19,58,59,66,67] fused benzoquinones display potential inversion, the all-thiophene compounds 1-4 do not, [16][17][18] so the presence of a phenyl ring on at least one side of the quinone appears to be a prerequisite for potential inversion in these systems.…”

Section: Cyclic Voltammetrymentioning

confidence: 99%

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Structure‐Property Relationships for Potential Inversion From Electron Acceptors Based on Thiophene‐Fused Triptycene Quinones, 1,4‐Diketones and Their Malononitrile Adducts

Warrington,

Montanaro,

Elsegood

et al. 2024

Chemistry A European J

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The synthesis and properties of a series of 11,11,12,12‐tetracyano‐9,10‐anthraquinodimethane (TCAQ) inspired electron acceptors based on thiophene‐fused quinone and triptycene motifs is presented. This has yielded insights into structure‐property relationships for establishing and modulating simultaneous two electron reduction processes in TCAQ analogues. These new compounds were synthesised using a Friedel‐Crafts acylation between triptycene and thiophene‐3,4‐dicarbonyl chloride. Isomeric para‐quinones featuring a [c]‐fused thiophene on one side and a β,β‐ or α,β‐fused triptycene on the other were isolated alongside a thiophene‐3,4‐diketone which bears two triptycene fragments. Knoevenagel condensation of these products with malononitrile produced a quinoidal bis(dicyanomethylene), an oxo‐dicyanomethylene and an acyclic bis(dicyanomethylene). This series of new electron accepting molecules has been studied using X‐ray crystallography and the implications of their 3D structures on NMR and UV/vis absorbance spectroscopy and cyclic voltammetry results have been ascertained with conclusions underpinned by computational methods.

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Section: Uv/vis Absorbance Spectroscopymentioning

confidence: 99%

Section: Cyclic Voltammetrymentioning

confidence: 99%

Structure‐Property Relationships for Potential Inversion From Electron Acceptors Based on Thiophene‐Fused Triptycene Quinones, 1,4‐Diketones and Their Malononitrile Adducts

Warrington,

Montanaro,

Elsegood

et al. 2024

Chemistry A European J

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“…Naphtho[2,3- b ]thiophene-4,9-dione (NT) derivatives are investigated in medicinal chemistry as bioactive synthetic products possessing anticancer, − antiprotozoal, − and antipsoriatic properties. − In materials chemistry, NTs are promising precursors for the synthesis of electron-deficient compounds − and the preparation of building blocks for air-stable organic semiconductors. − …”

Section: Introductionmentioning

confidence: 99%

One-Pot Synthesis of 2-R-Naphtho[2,3-b]thiophene-4,9-diones via Cyclization of 2-(R-Ethynyl)-1,4-naphthoquinones with Na₂S₂O₃

et al. 2021

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The concise and efficient one-pot synthesis of 2-Rnaphtho [2,3-b]thiophene-4,9-diones from 2-bromo-1,4-naphthoquinone and alkynes has been developed. The reaction proceeds through the formation of 2-(R-ethynyl)-1,4-naphthoquinones, which undergo transformation with Na 2 S 2 O 3 to 2-R-naphtho[2,3b]thiophene-4,9-diones via C−H sulfuration, accompanied by the formation of the aromatic Bunte salt, followed by its air oxidation and 5-endo-dig cyclization. The protocol is characterized by simplicity, good tolerance for functional groups, relatively mild conditions, and commercially available starting compounds.

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“…Anthra [2,3-d]thiazole-5,10-dione [3] itself and the majority of its derivatives have been patented as vat dyes, but latterly derivatives have found use as dichroic dyes for liquid crystals [4,5] and its photochromic derivatives have been patented as active media for CD discs [6]. Anthra[2,3-b]thiophene-5,10-dione (of which seven derivatives [7][8][9] have been reported) and anthra [2,3-d]isothiazole-5,10-dione [10] have been studied less. The synthesis and study of the spectroscopic properties of derivatives of this series can have _______ * For Communication 5 see [1].…”

mentioning

confidence: 99%

Heterocyclic analogs of 5,12-naphthacenequinone 6. Synthesis of 4,11-dimethoxy derivatives of anthra-[2,3-b]thiophene-5,10-dione and anthra[2,3-d]isothiazole-5,10-dione

Shchekotikhin

Lusikov

Buyanov

et al. 2007

Chem Heterocycl Compd

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Annelation of a heterocyclic fragment with the anthraquinone chromophore significantly affects the photochemical properties of a compound hence the synthesis of heterocyclic analogs of naphthacenequinone and a study of the relationship between chemical structure and spectroscopic properties allows us to direct the synthesis of a compound with targeted spectroscopic and photochemical characteristics. It was found that derivatives of the heterocyclic analogs of naphthacenequinone containing α-alkoxy groups (e.g. 4,11-dimethoxy derivatives of naphtho[2,3-f]indazole-5,10-diones [2]) show fluorescence with large Stokes shift values. Continuing a systematic study of heterocyclic analogs of naphthacenequinone analogs we have prepared and studied the spectroscopic properties of the methoxy derivatives of several thio analogs of 5,12-naphthacenequinone.Analysis of the literature data has shown that the most studied class of thio analogs of 5,12-naphthacenequinone are anthra[2,3-d]thiazole-5,10-diones amongst which series about 40 derivatives have been obtained up to this time. Anthra[2,3-d]thiazole-5,10-dione [3] itself and the majority of its derivatives have been patented as vat dyes, but latterly derivatives have found use as dichroic dyes for liquid crystals [4,5] and its photochromic derivatives have been patented as active media for CD discs [6]. Anthra[2,3-b]thiophene-5,10-dione (of which seven derivatives [7-9] have been reported) and anthra[2,3-d]isothiazole-5,10-dione [10] have been studied less. The synthesis and study of the spectroscopic properties of derivatives of this series can have _______ * For Communication 5 see [1].

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Synthese, electrochemical properties and crystal structure of tetracyano-p-quinodimethane (TCNQ) derivatives with π-extended systems containing a sulfur atom

Cited by 12 publications

References 19 publications

Structure‐Property Relationships for Potential Inversion From Electron Acceptors Based on Thiophene‐Fused Triptycene Quinones, 1,4‐Diketones and Their Malononitrile Adducts

Structure‐Property Relationships for Potential Inversion From Electron Acceptors Based on Thiophene‐Fused Triptycene Quinones, 1,4‐Diketones and Their Malononitrile Adducts

One-Pot Synthesis of 2-R-Naphtho[2,3-b]thiophene-4,9-diones via Cyclization of 2-(R-Ethynyl)-1,4-naphthoquinones with Na₂S₂O₃

Heterocyclic analogs of 5,12-naphthacenequinone 6. Synthesis of 4,11-dimethoxy derivatives of anthra-[2,3-b]thiophene-5,10-dione and anthra[2,3-d]isothiazole-5,10-dione

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Synthese, electrochemical properties and crystal structure of tetracyano-p-quinodimethane (TCNQ) derivatives with π-extended systems containing a sulfur atom

Cited by 12 publications

References 19 publications

Structure‐Property Relationships for Potential Inversion From Electron Acceptors Based on Thiophene‐Fused Triptycene Quinones, 1,4‐Diketones and Their Malononitrile Adducts

Structure‐Property Relationships for Potential Inversion From Electron Acceptors Based on Thiophene‐Fused Triptycene Quinones, 1,4‐Diketones and Their Malononitrile Adducts

One-Pot Synthesis of 2-R-Naphtho[2,3-b]thiophene-4,9-diones via Cyclization of 2-(R-Ethynyl)-1,4-naphthoquinones with Na2S2O3

Heterocyclic analogs of 5,12-naphthacenequinone 6. Synthesis of 4,11-dimethoxy derivatives of anthra-[2,3-b]thiophene-5,10-dione and anthra[2,3-d]isothiazole-5,10-dione

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One-Pot Synthesis of 2-R-Naphtho[2,3-b]thiophene-4,9-diones via Cyclization of 2-(R-Ethynyl)-1,4-naphthoquinones with Na₂S₂O₃