Synthesis of New Types of Ferrocene Dimers Bridged by a Fused Oligothiophene Spacer and Study of Their Electrochemical Oxidation Process via a Mixed‐Valence State

Muraoka, Hiroyuki; Watanabe, Yudai; Takahashi, Aki; Kamoto, Hironobu; Ogawa, Satoshi

doi:10.1002/hc.21156

Cited by 10 publications

(8 citation statements)

References 34 publications

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“…This prevalence stems from their well-defined structure, high chemical stability, together with outstanding electronic properties. Mixed-valence systems containing monomeric thiophene, 2,5-divinylthiophene, or 2,5-diethynylthiophene, received considerable attention with ferrocene, − M(dppe)Cp*, or M(dppe)Cp (M = Ru or Fe) as the capping units. Recently, the mixed valence systems were used to quantitatively discuss the distance dependence of charge-transfer processes with oligomers of various lengths.…”

Section: Introductionmentioning

confidence: 99%

Delocalization-to-Localization Charge Transition in Divinylthiophene-Bridged Biruthenium Complexes as a Function of Length of the Bridging Chain by Both IR Spectroscopy and Theoretical Investigations

Qian

et al. 2019

J. Phys. Chem. C

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A series of biruthenium complexes linked by oligothiophene bridges of variable lengths (4a–4d) have been prepared to probe intramolecular electronic delocalization as a function of the chain length of the bridging ligand. In going from monothiophene to quaterthiophene-bridged biruthenium-vinyl complex radical cations (4a +–4d +), the transition from a positive charge delocalized state to a localized state is clearly displayed by IR spectroscopy and density functional theory calculations and the bridge contributing to the charge and the unpaired spin density exhibits good linear correlation with the length of the bridging chain. The shortest member 4a + displays a charge delocalized mixed-valence property as a result of the strong electronic coupling between two ruthenium termini. In the longest member 4d + , the charge is nearly fully localized at the bridge and the mixed-valence property disappears. Therefore, for even longer systems, the charge should be exclusively localized on the bridge.

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Section: Introductionmentioning

confidence: 99%

Delocalization-to-Localization Charge Transition in Divinylthiophene-Bridged Biruthenium Complexes as a Function of Length of the Bridging Chain by Both IR Spectroscopy and Theoretical Investigations

Qian

et al. 2019

J. Phys. Chem. C

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“…Examples of bimetallic BDT are rather rare . The bis(ferrocenyl) derivative, 2,6-bis(ferrocenyl)benzo[1,2- b :4,5- b ″]dithiophene ( 1 ), was previously synthesized by Negishi ferrocenylation of the appropriate bromo-substituted derivative of BDT .…”

Section: Introductionmentioning

confidence: 99%

“…Actually, the formation of mixed-valence species is often accountable for the aforementioned performances. The factors affecting the formation, stability, and nature of mixed-valence states in multi(ferrocenyl) derivatives were methodically examined. ,, In particular, it was found that the electron transfer mechanism in mixed-valence intermediates is mostly based on the Marcus–Hush theory …”

Section: Introductionmentioning

confidence: 99%

Testing the Conjugative Properties of Benzodithiophene and Benzotrithiophene in Charge Transfer Multi(ferrocenyl) Systems

et al. 2018

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The charge transfer properties of the mono-, di-, and tricationic derivatives of bis(ferrocenyl)benzodithiophene and tris(ferrocenyl)benzotrithiophene were investigated. The cations were generated by chemical oxidation using ferrocenium(BF4) and acetylferrocenium(BF4) as the oxidative agents, and monitored in the visible and NIR regions. By changing the supporting electrolyte from [nBu4N][PF6] to [nBu4][B(C6F5)4] we were able to selectively generate the monocationic species of bis and triferrocenyl complexes. The redox and optical properties of the cationic derivatives were rationalized by an in-depth electrochemical and optical study. The comparison with the results previously obtained for the structurally related bis(ferrocenyl)-s-indacene and tris(ferrocenyl)-trindene allowed for the evaluation of the huge influence of thiolation on the metal-metal electronic coupling. RESULTS AND DISCUSSION Electrochemistry. Oxidative cyclic voltammetry (CV) of 1 and 2 recorded under argon in CH2Cl2/0.1 M nBu4NB(C6F5)4, (Figures 1a,c). Large waves with oxidation potential maximum at 0.27 (1) and 0.24 V (2) are present.

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“…The multi‐step oxidation process derived from the multi‐ferrocene system can be controlled by the π‐conjugated spacer connecting ferrocene fragments due to the fact that the strength of the electronic communication between the mixed‐valent metal centers strongly depends on the electronic nature and length of the linking π‐conjugated spacer. Thus, there have been investigations of multi‐ferrocene derivatives bridged by a wide variety of π‐conjugated spacers such as aromatics (eg, benzene), heteroaromatics (eg, pyrrole, phosphole, furan, thiophene), and their oligomers (eg, oligopyrrole:, oligofuran, oligothiophene).…”

Section: Introductionmentioning

confidence: 99%

Electrochemical studies of the multi‐step multi‐electron redox process of tetraferrocenyloligothiophenes with electron donor and acceptor abilities

Muraoka

Ozawa

Ogawa

2018

Heteroatom Chemistry

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We have designed and synthesized tetraferrocenyloligothiophenes, namely, 4,4′5,5′‐tetraferrocenyl‐2,2′‐bithiophene (TFBT) and 4,4″,5,5″‐tetraferrocenyl‐2,2′:5′,2″‐terthiophene (TFTT). By using an electrochemical technique, we revealed that tetraferrocenyloligothiophenes show multi‐redox reactions derived from four ferrocene fragments and one α‐oligothiophene spacer, and a number of the thiophene rings in the α‐oligothiophene spacer can be attuned to the redox potentials and the multiple electron transfer process. Consequently, we have succeeded in the construction of different types of multi‐step multi‐electron redox systems by constructing four organometallic redox‐active ferrocenes and one organic redox‐active α‐oligothiophene differing in the number of thiophene rings.

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Synthesis of New Types of Ferrocene Dimers Bridged by a Fused Oligothiophene Spacer and Study of Their Electrochemical Oxidation Process via a Mixed‐Valence State

Cited by 10 publications

References 34 publications

Delocalization-to-Localization Charge Transition in Divinylthiophene-Bridged Biruthenium Complexes as a Function of Length of the Bridging Chain by Both IR Spectroscopy and Theoretical Investigations

Delocalization-to-Localization Charge Transition in Divinylthiophene-Bridged Biruthenium Complexes as a Function of Length of the Bridging Chain by Both IR Spectroscopy and Theoretical Investigations

Testing the Conjugative Properties of Benzodithiophene and Benzotrithiophene in Charge Transfer Multi(ferrocenyl) Systems

Electrochemical studies of the multi‐step multi‐electron redox process of tetraferrocenyloligothiophenes with electron donor and acceptor abilities

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