Synthesis and Functionalization of 3,3′-Bis(spirodienone)-Bridged 2,2′-Bithiophene: A New Building Block for Redox-Active Molecular Switching Materials

Kurata, Hiroyuki; Kim, Sang; Fujimoto, Tomoyuki; Matsumoto, Kouzou; Kawase, Takeshi; Kubo, Takashi

doi:10.1021/ol8015379

Cited by 12 publications

(4 citation statements)

References 40 publications

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“…Thiophene-containing organic compounds such as oligothiophenes, polythiophenes, and fused thiophenes have emerged as useful building blocks for electronic, optoelectronic, sensing, and molecular switching materials. − Synthesis and functionalization of oligothiophenes have been extensively investigated because of the utilization of the π-conjugated systems. − Extension of the π conjugation and modification of the thiophene ring are important issues in the area of thiophene-based materials. On the other hand, alkynes are useful starting materials for the preparation of π-conjugated organic compounds. , Late-transition-metal complexes catalyze addition reactions of thioesters and sulfides to alkynes via C–S bond cleavage. , However, only a few studies have been reported on metal-catalyzed reactions of thiophenes with alkynes. , …”

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confidence: 99%

Skeletal Modification of Benzothiophene Mediated by Iron Carbonyls: Insertion of Terminal Alkynes with Migration of Amino and Alkoxy Groups

2013

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A thiolate-bridged diiron carbonyl complex derived from benzothiophene, [Fe2(μ-SC6H4CHCH)(CO)6], reacted with terminal alkynes HCCR (R = SiMe3, Ph, isobutyl) under photoirradiation conditions to afford diiron complexes with a 2,4-pentadienoyl moiety, [Fe2{μ-SC6H4(CH)3C(R)CO}(CO)5], via alkyne and CO insertion. In a similar reaction with N,N-dimethylpropargylamine, a diiron complex with a pentadienyl moiety, [Fe2{μ-SC6H4(CH)3C(NMe2)CH2}(CO)5], was obtained as an alkyne insertion product without CO insertion. This reaction involves 1,2-migration of a dimethylamino group. The corresponding reactions with alkyl propargyl ethers also produced diiron complexes containing pentadienyl moieties with an alkoxycarbonyl group via alkoxy migration with CO insertion. The migration process via C–N or C–O bond cleavage could be related to the coordination ability of N or O in the propargyl compounds.

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Skeletal Modification of Benzothiophene Mediated by Iron Carbonyls: Insertion of Terminal Alkynes with Migration of Amino and Alkoxy Groups

2013

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“…1,2‐Dispirodienones 64 derived from bithiophenes have been shown by electrochemistry to ring‐open (to form 65 ) and ring‐close ( 65 → 64 ) under redox conditions [Scheme , Equation (1)]. Consequently, these molecules could serve as molecular switching materials 7b,7c. To investigate the redox properties of the 1,2‐dispirodienone 10 , we performed electrochemical experiments to determine if bond breaking and bond formation can occur under redox conditions [Scheme , Equation (2)].…”

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confidence: 99%

“…The tert ‐butyl groups are crucial for the stability of these compounds. Interestingly, studies of the redox properties of these molecules have shown that they could be used as molecular switches 7b,7c…”

Section: Introductionmentioning

confidence: 99%

Hypervalent‐Iodine‐Mediated Synthesis of 1,2‐Dispirodienones: Experimental and Theoretical Investigations

et al. 2015

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The oxidation of phenol acetanilides mediated by hypervalent iodine is described. The transformation proceeds through the formation of a carbocationic species that evolves either into a [6,5,6]‐tricyclic compound (1,2‐dispirodienone) or a [6,6,6]‐tricyclic compound (aryl spirodienone). In most examples, the 1,2‐dispirodienones are obtained in good yields. In some cases, depending on the substitution pattern of the phenol acetanilides and the reaction conditions, aryl spirodienones are formed. We performed electrochemical experiments on a 1,2‐dispirodienone to study its redox properties. These data provide evidence that the 1,2‐dispirodienone can ring‐open and ring‐close under redox conditions. The hypervalent‐iodine‐mediated oxidation of phenol acetanilides to 1,2‐dispirodienones was rationalized on the basis of density functional theory (DFT) calculations. In addition, these DFT computations suggest that the formation of the aryl spirodienones occurs by a stepwise reaction pathway, which first involves an ipso attack to yield a [6,5,6]‐tricyclic carbocationic intermediate and then a 1,2‐sigmatropic shift of the bond that connects the two six‐membered rings.

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“…Following this second route, an enhancement of the yield was obtained, going from 33% to 67%. These syntheses were preferred to the Suzuki-Miyaura coupling recently reported [26] because of the difficulty to obtain 3,5-di-tert-butyl-4-hydroxyphenylboronic acid as a pure product in high yields.…”

Section: Synthesismentioning

confidence: 99%

Raman spectroscopic characterization of a thiophene‐based active material for resistive organic nonvolatile memories

Fazzi

Canesi

Bertarelli

et al. 2009

J Raman Spectroscopy

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A combined theoretical and experimental Raman study is presented on a diphenyl bithiophene molecule known as a good candidate for the development of organic nonvolatile memory devices. Spectroscopic markers suitable to distinguish the different stable conformers of the molecule have been predicted and detected. The combined analysis of theoretical and experimental Raman spectra recorded in solution indicates that at room temperature a dynamical equilibrium, characterized by interconversion between the two more stable conformers (namely trans and cis), takes place and that the more populated species is the cis form. Referring to the solid phase instead, Raman spectra of single-crystal samples show the presence of the only trans conformer, as confirmed by X-ray measurements. Finally, Raman spectra of thin films, as those used for the memory device, were collected; samples just deposited from solution and after few hours from the deposition were analyzed. Following the evolution of selective spectroscopic Raman markers, an isomerization process from the abundant cis (as-deposited) to the totally trans (after few hours) conformer in the solid phase was detected. These results open the way to the identification of the molecular isomers present in the thin film of the memory cell and finally of the active molecular species involved in the switching mechanism of the operating device.

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Synthesis and Functionalization of 3,3′-Bis(spirodienone)-Bridged 2,2′-Bithiophene: A New Building Block for Redox-Active Molecular Switching Materials

Cited by 12 publications

References 40 publications

Skeletal Modification of Benzothiophene Mediated by Iron Carbonyls: Insertion of Terminal Alkynes with Migration of Amino and Alkoxy Groups

Skeletal Modification of Benzothiophene Mediated by Iron Carbonyls: Insertion of Terminal Alkynes with Migration of Amino and Alkoxy Groups

Hypervalent‐Iodine‐Mediated Synthesis of 1,2‐Dispirodienones: Experimental and Theoretical Investigations

Raman spectroscopic characterization of a thiophene‐based active material for resistive organic nonvolatile memories

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