7,7,8,8‐Tetraaryl‐<i>o</i>‐quinodimethane Stabilized by Dibenzo Annulation: A Helical π‐Electron System That Exhibits Electrochromic and Unique Chiroptical Properties

Suzuki, Takanori; Sakano, Yuto; Iwai, Tomohiro; Iwashita, Shinichi; Miura, Yusho; Katoono, Ryo; Kawai, Hidetoshi; Fujiwara, Kenshu; Tsuji, Yasushi; Fukushima, Takanori

doi:10.1002/chem.201203092

Cited by 25 publications

(5 citation statements)

References 45 publications

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“…Namely, it was shown that covalent assemblies properly incorporating couples of redox-active units can give rise to the formation of a (C sp3 –C sp3 ) carbon–carbon bond that bridges electrochemically active components following a reductive or an oxidative process. For example, typically integrated redox-active chromophoric units are trityliums, ,, heterotricyclic hydrocarbons, , thiophenes, or octamethoxytetraphenylene . Of particular interest is the case of bis-acridinium assemblies (e.g., Chart S1a) that are more or less tightly preorganized with various semirigid to rigid scaffolds, i.e.…”

Section: Resultsmentioning

confidence: 99%

Electron Storage System Based on a Two-Way Inversion of Redox Potentials

et al. 2020

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Molecular-level multielectron handling toward electrical storage is a worthwhile approach to solar energy harvesting. Here, a strategy which uses chemical bonds as electron reservoirs is introduced to demonstrate the new concept of “structronics” (a neologism derived from “structure” and “electronics”). Through this concept, we establish, synthesize, and thoroughly study two multicomponent “super-electrophores”: 1,8-dipyridyliumnaphthalene, 2, and its N,N-bridged cyclophane-like analogue, 3. Within both of them, a covalent bond can be formed and subsequently broken electrochemically. These superelectrophores are based on two electrophoric (pyridinium) units that are, on purpose, spatially arranged by a naphthalene scaffold. A key characteristic of 2 and 3 is that they possess a LUMO that develops through space as the result of the interaction between the closely positioned electrophoric units. In the context of electron storage, this “super-LUMO” serves as an empty reservoir, which can be filled by a two-electron reduction, giving rise to an elongated C–C bond or “super-HOMO”. Because of its weakened nature, this bond can undergo an electrochemically driven cleavage at a significantly more anodicyet accessiblepotential, thereby restoring the availability of the electron pair (reservoir emptying). In the representative case study of 2, an inversion of potential in both of the two-electron processes of bond formation and bond-cleavage is demonstrated. Overall, the structronic function is characterized by an electrochemical hysteresis and a chemical reversibility. This structronic superelectrophore can be viewed as the three-dimensional counterpart of benchmark methyl viologen (MV).

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Section: Resultsmentioning

confidence: 99%

Electron Storage System Based on a Two-Way Inversion of Redox Potentials

et al. 2020

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“…This result is explained by assuming that the conformational change in dichloromethane is faster than that in benzonitrile. The observed results suggest that 2 could be classified as a dynamic redox system [28–30] . This dynamic redox behavior of 2 could be attributed to the intrinsic electron‐donor ability of TTF inserted in the diphenoquinone moiety.…”

Section: Resultsmentioning

confidence: 86%

Tetrathiafulvalene‐Inserted Diphenoquinone: Synthesis, Structure, and Dynamic Redox Property

Mitsuoka

Sakamaki

Fujiwara

2020

Chemistry A European J

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A new tetrathiafulvalene (TTF) derivative is synthesized, which is substituted with two phenoxy radicals on one 1,3‐dithiole ring, and may have either open‐shell diradical or closed‐shell extended‐quinoidal ground states. X‐ray single crystal analysis and NMR measurements prove that this molecule has a closed‐shell extended quinoidal structure both in the solid state and in solution. DFT calculations show the donor–acceptor electronic properties of this molecule with a well‐separated HOMO–LUMO distribution and a small HOMO–LUMO energy gap. Because of this donor–acceptor character, this molecule gives both the dication and the dianion species by electrochemical oxidation and reduction. Furthermore, during the redox process between the neutral and dication states, this molecule exhibits unique changes in the cyclic voltammogram upon repeating the cycles or varying the scan rate. The observed electrochemical behavior is explained by the conformational changes in the electrochemically generated species, thus indicating that this molecule is classified as a dynamic redox system.

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“…An interesting method for coupling molecular motions with physical responses in solution is a dynamic redox system . Conformational changes of the π-electronic core due to redox processes affect the electronic nature of the molecule, which results in electrochromic behavior with electrochemical bistability. , For instance, the butterfly-shaped molecular conformation of 11,11,12,12-tetracyanoanthra-9,10-quinodimethane (TCNAQ) in a neutral state was transformed to a planar structure in a dianionic state through two-electron reduction. The CC double-bond character of dicyanomethylene CC(CN) 2 groups in neutral TCNAQ was transformed to C–C single bonds by reduction, which relaxed the steric hindrance between CC(CN) 2 groups and hydrogen atoms of neighboring benzene rings in the dianion state.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Behavior, Electrochromism, and Two-Photon Absorption of Dicyanomethylenated Quinacridone

et al. 2014

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Molecular structures of dicyanomethylenated quinacridone (1) as a solid and in solution were examined on the basis of single-crystal X-ray structural analysis, temperature-dependent (1)H NMR in CD2Cl2, and theoretical calculations. Crystal 1 had a curved, butterfly-shaped molecular structure. Thermally activated flipping between the curved, butterfly-shaped structure and an armchair structure occurred in solution. Electrochemical reduction triggered a dynamic change from the curved, butterfly-shaped conformation in the neutral state to a planar conformation in the dianion state, which represented electrochromic behavior with electrochemical bistability. A large two-photon absorption cross section of compound 1 was observed in the resonance-enhancement region of 423 GM (1 GM = 1 × 10(-50) cm(4) s photon(-1) molecule(-1)) at 710 nm. Multiple donor-acceptor charge-transfer pathways of molecule 1 enhanced two-photon absorption.

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7,7,8,8‐Tetraaryl‐o‐quinodimethane Stabilized by Dibenzo Annulation: A Helical π‐Electron System That Exhibits Electrochromic and Unique Chiroptical Properties

Cited by 25 publications

References 45 publications

Electron Storage System Based on a Two-Way Inversion of Redox Potentials

Electron Storage System Based on a Two-Way Inversion of Redox Potentials

Tetrathiafulvalene‐Inserted Diphenoquinone: Synthesis, Structure, and Dynamic Redox Property

Dynamic Behavior, Electrochromism, and Two-Photon Absorption of Dicyanomethylenated Quinacridone

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