Reactions between 1‐Ethynylazulenes and 7,7,8,8‐Tetracyanoquinodimethane (TCNQ): Preparation, Properties, and Redox Behavior of Novel Azulene‐Substituted Redox‐Active Chromophores

Shoji, Taku; Ito, Shunji; Toyota, Kozo; Iwamoto, Takeaki; Yasunami, Michio; Morita, Noboru

doi:10.1002/ejoc.200900539

Cited by 66 publications

(26 citation statements)

References 20 publications

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“…2). 11 Since the values are consistent with those of 16, 2H-cyclohepta [b]furan-2-one substituent contributes less effectively for electrochemical reduction compared with 1-azulenyl moiety as shown in Scheme 7. Thus, the first reduction potential of these compounds might 55 depend on the 1-azulenyl substituent.…”

Section: Electrochemistrysupporting

confidence: 69%

“…13 To the synthesis of the novel 15 DCNQ derivatives, the [2+2] cycloaddition-cycloreversion sequence was applied to the acetylene derivatives 1-9 with TCNQ under the conditions described in the literature. 6,11 Thus, the reaction of 1 with TCNQ in refluxing ethyl acetate afforded 10 in 91% yield as a sole product (Scheme 1). Proposed reaction 20 sequence is also shown in Scheme 1.…”

Section: Synthesismentioning

confidence: 99%

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Synthesis of donor–acceptor chromophores by the [2 + 2] cycloaddition of arylethynyl-2H-cyclohepta[b]furan-2-ones with 7,7,8,8-tetracyanoquinodimethane

et al. 2012

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Arylethynyl-2H-cyclohepta [b]furan-2-ones reacted with 7,7,8, in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed cyclobutene derivatives, to afford the corresponding dicyanoquinodimethane (DCNQ) chromophores in excellent yields. The intramolecular charge-transfer (ICT) interactions between the 2H-cyclohepta[b]furan-2-one 10 ring and DCNQ acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties depended on the number of DCNQ units in the molecule. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions. 15

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Section: Electrochemistrysupporting

confidence: 69%

Section: Synthesismentioning

confidence: 99%

Synthesis of donor–acceptor chromophores by the [2 + 2] cycloaddition of arylethynyl-2H-cyclohepta[b]furan-2-ones with 7,7,8,8-tetracyanoquinodimethane

et al. 2012

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“…[32] We also described the [2+ +2] CA-RE reaction of 1-ethynylazulenes with TCNQ to give the corresponding 1-AzDCNQs. [33] The formation of 1-AzTCBDs and 1-AzDCNQs indicates that the reactivity of the alkyne moietyi nt he [2+ +2] CA-RE reaction is significantly enhanced by the 1-azulenyl group, due to its stronge lectrondonating abilities.…”

Section: -Azulenyl Tcbds With Aryl Substituentsmentioning

confidence: 99%

Azulene‐Based Donor–Acceptor Systems: Synthesis, Optical, and Electrochemical Properties

Shoji

Ito

2017

Chemistry A European J

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We describe the synthesis and properties of azulene‐substituted 1,1,4,4‐tetracyanobutadienes (AzTCBDs) and heteroazulenyl TCBDs. TCBD derivatives were prepared in good to excellent yields through reaction of the corresponding 1‐ethynylazulenes with tetracyanoethylene (TCNE). In contrast, the reaction between propargyl alcohols and the 1‐azulenyl group in TCNE generated 2‐aminofuran derivatives, which were transformed into 6‐aminofulvenes with a 1‐azulenyl substituent upon treatment with several amines. The optical and electrochemical properties of the AzTCBDs were clarified by UV/Vis and voltammetry. The AzTCBD derivatives exhibited electrochromism, showing a multi‐step color change under electrochemical redox conditions. The multistage redox properties of AzTCBDs could be useful for the development of novel organic electronic materials.

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“…This compound was designed for organic transistor applications but its electron-rich nature is perfectly suited to electron-poor adducts such as nitriles and formed the basis for the work on the novel panchromatic chromophore investigated in this study. Following the extensive work by Diederich (Michinobu et al, 2006) and Shoji (Shoji et al, 2008;Shoji et al, 2009;Shoji et al, 2011) on single and double alkyne cycloadditions with nitrile adducts via a ring-opening of tetracyanocyclobutene intermediates, 7,7,8,8-tetracyanoquinodimethane (TCNQ) was added in a similar fashion to the electron-rich molecular rod and afford the target material in moderate yield (45 %). The synthetic route was designed to include hexyl chains to ensure solubility of all intermediates in common organic solvents and processability of the final target LB154.…”

Section: Resultsmentioning

confidence: 99%

A bifunctional smart material: the synthesis of a metal-free black pigment for optoelectronic applications from an organic semiconducting molecular rod

Jones

Luo

Kazlauciunas

et al. 2018

PRT

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A bifunctional smart material: the synthesis of a metal-free black pigment for optoelectronic applications from an organic semiconducting molecular rod. Pigment and Resin Technology, 47 (1). AbstractPurpose -To synthesise and evaluate the properties of a novel smart material consisting of a metal-free organic black pigment with a unique chromophore for bifunctional applications in optoelectronics.Design/methodology/approach -A robust and highly efficient organic reaction, namely, a double [2 + 2] cycloaddition, was deployed to transform a rod-like structure for chargetransfer applications to a strongly-conjugated light-absorbing molecule for both optical and electronic applications.Findings -The synthesis and characterisation of an air-stable metal-free black pigment is reported which contains an unconventional donor-acceptor panchromatic chromophore with an absorption window spanning 600 nm; the compound was synthetically converted from an organic semiconducting molecular rod and retains strong charge-transfer properties. The chromophore is comprised of tetracyanoquinodimethane (TCNQ) adduct either side of a dithienothiophenyl (DTT) core, capped with hexyl thiophenes that ensures solubility in common organic solvents. Its propensity to form excellent thin-films on different substrates such as glass and paper, with a total opacity in organic solvent, gives it the potential for wideranging applications in organic optoelectronics. Research limitations/implications -The synthetic chemistry and fundamental propertiesare investigated in the present study, with more detailed treatments and analysis to be soon developed. One leading smart material is presented, with further derivatives under investigation.Practical implications -The work presented shows the possibility of converting structures from one application to another with relative ease, but retain properties for both, using wellknown and facile conditions. Originality / value -The structures are novel, and an enhanced air-stable organic panchromatic chromophore is reported for processing in common organic solvents.

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Reactions between 1‐Ethynylazulenes and 7,7,8,8‐Tetracyanoquinodimethane (TCNQ): Preparation, Properties, and Redox Behavior of Novel Azulene‐Substituted Redox‐Active Chromophores

Cited by 66 publications

References 20 publications

Synthesis of donor–acceptor chromophores by the [2 + 2] cycloaddition of arylethynyl-2H-cyclohepta[b]furan-2-ones with 7,7,8,8-tetracyanoquinodimethane

Synthesis of donor–acceptor chromophores by the [2 + 2] cycloaddition of arylethynyl-2H-cyclohepta[b]furan-2-ones with 7,7,8,8-tetracyanoquinodimethane

Azulene‐Based Donor–Acceptor Systems: Synthesis, Optical, and Electrochemical Properties

A bifunctional smart material: the synthesis of a metal-free black pigment for optoelectronic applications from an organic semiconducting molecular rod

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