Assembly of an Axially Chiral Dynamic Redox System with a Perfluorobiphenyl Skeleton into Dumbbell‐ or Tripod‐type Electron Donors

Tamaoki, Hitomi; Katoono, Ryo; Fujiwara, Kenshu; Suzuki, Takanori

doi:10.1002/anie.201510935

Cited by 14 publications

(6 citation statements)

References 45 publications

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“…We continued our synthesis by taking advantage of the S N Ar‐reactivity of perfluorobiphenyls that proceeds selectively at the 4,4′‐positions, which is desirable for extending the π‐conjugation along the long‐axis of the biphenyl skeleton. As shown in Scheme , the reaction of 2 with ethynyltriisopropylsilane (1.2 equiv.)…”

Section: Resultsmentioning

confidence: 99%

Molecular Wires with Controllable π‐Delocalization Incorporating Redox‐Triggered π‐Conjugated Switching Units

et al. 2018

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A perfluorobiphenyl‐2,2′‐diyl dication and its corresponding dihydrophenanthrene‐type electron donor are interconvertible upon two‐electron transfer. Redox‐triggered C−C bond‐formation/cleavage caused a drastic change in the torsion angle of the biphenyl unit. Thus, π‐delocalization ON/OFF switching was observed as a change in the UV absorption upon electrolysis of the linearly extended analogue with two phenylethynyl groups. A further extended π‐system with a molecular length of ca. 3.5 nm, which has two switching units, was synthesized. Spectroelectrograms as well as voltammetric analyses showed that the two units act nearly simultaneously because of the very small inter‐unit electrostatic repulsion in the tetracationic state. Thus, the present pair is a promising candidate as a switching unit for “molecular wires” with controllable π‐delocalization, in which a higher ON/OFF ratio of delocalization could be realized by incorporating multiple switching units.

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Section: Resultsmentioning

confidence: 99%

Molecular Wires with Controllable π‐Delocalization Incorporating Redox‐Triggered π‐Conjugated Switching Units

et al. 2018

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“…In addition to MIMs, dynamic redox (dyrex) systems have been shown to exhibit electrochemical bistability as well as facile two‐electron (2 e) transfer at nearly the same potential, which results from drastic structural changes as well as formation/cleavage of a covalent bond upon redox reactions. Thus, dyrex systems with a functional group for binding to a surface (e.g., disulfide on Au) are promising candidates for the formation of molecular layers as a prototype of unimolecular memory …”

Section: Methodsmentioning

confidence: 99%

Organic Molecular Layer with High Electrochemical Bistability: Synthesis, Structure, and Properties of a Dynamic Redox System with Lipoate Units for Binding to Au(111)

et al. 2017

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Biphenyl-2,2'-diylbis(10-methyl-9-methyleneacridan)-type electron donor 1,w hich has two tethered cyclic disulfideu nits at the 6,6'-positions, was designeda nd synthesized as the first member of ad ynamic redox (dyrex) system that can form molecular layerso naA u(111)e lectrode. Upon the two-electron (2 e) oxidation of 1,t he persistentd icationic dye 2 2 + was generated with the formationofanew CÀCbond, whichisr eversibly cleaved upon 2e reduction to regenerate 1 (dyrex behavior). Similar dyrex interconversion occurs in the molecular layer of 1 on gold. The chemical identities of 1/Au and electrochemically generated 2 2 + /Au wereu nambiguously determined by in situ IR spectroscopy in the attenuated totalr eflection mode. In situ scanning tunneling microscopy (STM) was conducted under electrochemical conditions to examine the surfaces tructure of 1 adsorbed on aA u(111)e lectrode. Although no longrange-ordered morphology was found in the STM image of 1, an in situ STM study of the potential-induced dyrex reaction of 1 to 2 2 + showed that the grained spots in the image became slightly brighter.There has been growing interesti nt he use of molecular layers (e.g.,s elf-assembled monolayers)o na ne lectrode surface with respectt ot heir potential application in molecular devices such as switches, data storage devices, and sensors. [2] An electrochemically bistable redox speciesb ound to as urface would be advantageous for the realization of am olecular-based data storagee lement( unimolecular memory), [2] since mutuale lectron exchange between neighboring molecules with different redox states would be suppressed. Unfortunately,t his situation is difficult to attain based on conventional organic redox systems, because the redox potential in the neutral state is identical to that in the reverse process for the corresponding ionic state.Some mechanicallyi nterlocked molecules (MIMs) exhibit bistability through rearrangement of the subunits depending on the redox state. [3] In addition to MIMs, dynamic redox (dyrex) systems [2a, 4] have been shown to exhibit electrochemical bistability as well as facile two-electron( 2e)t ransfer at nearly the same potential, whichr esults from drastic structural changes as well as formation/cleavage of ac ovalentb ond upon redox reactions. Thus, dyrex systems with af unctional group for binding to as urface( e.g.,d isulfide on Au) are promising candidates for the formation of molecular layersa saprototypeo fu nimolecular memory. [2a, 5] The 1,2-dithiolane ring of a-lipoic acid is often used as as urface-modifying pendant, as demonstrated by severalM IM derivatives containing at etrathiafulvalene unit. [6] Therefore, we designed ad yrex donor to which wasa ttached two units of lipoate at the 2,2'-positions of ab iphenyl (BP) framework that can be converted into ad ihydrophenanthrene (DHP) derivative through CÀCb ond formationu pon2et ransfer.B P-DHP-based dyrex systems can be categorized into two types: [4c] an exotype pair (EX-EX 2 + )a nd an endo-type pair (EN-EN 2 + ) (Sch...

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“…[27][28][29] The research of EC materials grafting chiral groups is becoming a rising hotspot. [30][31][32] For instance, a multiple chiral switching device with rich optical properties inheriting from base-responsive dyes has been fabricated based on proton-coupled electron transfer (PCET) mechanism. [30] In addition, some chiroptical molecular switches have been realized by the combination of chiral chromophores with electrochemically active viologen derivatives [33] or some conducting polymers.…”

Section: Introductionmentioning

confidence: 99%

A Flexible Circularly Polarized Luminescence Switching Device Based on Proton‐Coupled Electron Transfer

et al. 2022

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Flexible circularly polarized luminescence (CPL) switching devices have been long‐awaited due to their promising potential application in wearable optoelectronic devices. However, on account of the few materials and complicated design of manufacturing systems, how to fabricate a flexible electric‐field‐driven CPL‐switching device is still a serious challenge. Herein, a flexible device with multiple optical switching properties (CPL, circular dichroism (CD), fluorescence, color) is designed and prepared efficiently based on proton‐coupled electron transfer (PCET) mechanism by optimizing the chiral structure of switching molecule. More importantly, this device can maintain the switching performance even after 300 bending‐unbending cycles. It has a remarkable comprehensive performance containing bistable property, low open voltage, and good cycling stability. Then, prototype devices with designed patterns have been fabricated, which opens a new application pattern of CPL‐switching materials.

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Assembly of an Axially Chiral Dynamic Redox System with a Perfluorobiphenyl Skeleton into Dumbbell‐ or Tripod‐type Electron Donors

Cited by 14 publications

References 45 publications

Molecular Wires with Controllable π‐Delocalization Incorporating Redox‐Triggered π‐Conjugated Switching Units

Molecular Wires with Controllable π‐Delocalization Incorporating Redox‐Triggered π‐Conjugated Switching Units

Organic Molecular Layer with High Electrochemical Bistability: Synthesis, Structure, and Properties of a Dynamic Redox System with Lipoate Units for Binding to Au(111)

A Flexible Circularly Polarized Luminescence Switching Device Based on Proton‐Coupled Electron Transfer

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