Oxidative Protonolysis of the Expanded Central C–C Bond in a Di(spiroacridan)-type Hexaphenylethane Derivative Accompanied by UV–vis, FL, and CD Spectral Changes

Suzuki, Takanori; Kuroda, Yusuke; Wada, Kodai; Sakano, Yuto; Katoono, Ryo; Fujiwara, Kenshu; Kakiuchi, Fumitoshi; Fukushima, Takanori

doi:10.1246/cl.140192

Cited by 15 publications

(4 citation statements)

References 26 publications

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“…On the other hand, electrochemical interconversion of dimethyl derivative ( M )‐ 5a /( R ax )‐ 6a 2+ induced changes in the UV–vis, CD, and FL spectra (see TOC figure) . This example demonstrates a three‐way‐output response[17,18c,d,22] to the electrochemical input for a di(acridinium)‐based dyrex pair.…”

Section: Acridinium‐based Dyrex Systems Exhibiting Multi‐output Electmentioning

confidence: 89%

“…In contrast to the planar anti form of bipyridine‐based diacridinium 4 2+ , biphenyl‐based dications prefer the helical syn form with the two 10‐methylacridiniums partly overlapped in a face‐to‐face manner, as can be seen in the X‐ray structure of 6 2+ . Thus, the chiral sense of easily interconvertible ( R ax )‐ and ( S ax )‐ 2 2+ is expected to be biased when a proper chiral auxiliary is attached at the 10‐position of acridinium.…”

Section: Acridinium‐based Dyrex Systems Exhibiting Multi‐output Electmentioning

confidence: 99%

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Bis(10‐methylacridinium)s as a Versatile Platform for Redox‐Active Functionalized Dyes and Novel Structures

Suzuki

Takeda

Ohta

et al. 2014

The Chemical Record

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10-Methylacridinium is a stable aromatic cation exhibiting yellow-orange color and strong green fluorescence (FL), and can be used as a versatile building block in constructing a wide variety of novel π-electron systems. The dications with the two chromophores connected by a proper π spacer undergo reversible "dyrex" (dynamic redox) behavior, and C-C bond formation/cleavage is accompanied by their redox reactions. The prototype is biphenyl-2,2'-diylbis(10-methylacridinium), which exhibits electrochromic response with ON/OFF switching of FL during the reversible interconversion with the di(spiroacridan)-type electron donor. Slight structural alteration under the concept of "MFMS" (maximum function on the minimum skeleton) endowed the dyrex system with metal-binding or chiroptical properties, which could be modified by the redox reactions. Some of the di(spiroacridan) derivatives generated from bis(10-methylacridinium)s have extreme structural parameters, such as the greatest C-C bond length ever reported.

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Section: Acridinium‐based Dyrex Systems Exhibiting Multi‐output Electmentioning

confidence: 89%

Section: Acridinium‐based Dyrex Systems Exhibiting Multi‐output Electmentioning

confidence: 99%

Bis(10‐methylacridinium)s as a Versatile Platform for Redox‐Active Functionalized Dyes and Novel Structures

Suzuki

Takeda

Ohta

et al. 2014

The Chemical Record

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“…Of note, in the case of dicationic 2,2'-substituted 1,1'biphenyl scaffold with 9-acridinium [24] as dibenzoannulated pyridinium electron-acceptor subunit, single-crystal X-ray crystallography establishes a similar proximal layout of the electrophoric units (here referred to as a cis conformation) with a distance separating carbenium atoms smaller than the sum of their van der Waals radii (3.40 Å)…”

Section: Crystal (Solid) State Studymentioning

confidence: 99%

On the Supra‐LUMO Interaction: Case Study of a Sudden Change of Electronic Structure as a Functional Emergence

Gosset

Lachmanová

Cherraben

et al. 2021

Chemistry A European J

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The synergistic functioning of redox-active components that emerges from prototypical 2,2'-di(N-methylpyrid-4ylium)-1,1'-biphenyl is described. Interestingly, even if a trans conformation of the native assembly is expected, due to electrostatic repulsion between cationic pyridinium units, we demonstrate that cis conformation is equally energy-stabilized on account of a peculiar LUMO (SupLUMO) that develops through space, encompassing the two pyridiniums in a single, made-in-one-piece, electronic entity (superelectrophoric behavior). This SupLUMO emergence, with the cis species as superelectrophore embodiment, originates in a sudden change of electronic structure. This finding is substantiated by insights from solid state (single-crystal X-ray diffraction) and solution (NOE NMR and UV-vis-NIR spectroelectrochemistry) studies, combined with electronic structure computations. Electrochemistry shows that electron transfers are so strongly correlated that two-electron reduction mani-fests itself as a single-step process with a large potential inversion consistent with inner creation of a carbon-carbon bond (digital simulation). Besides, absence of reductive formation of dimers is a further indication of a preferential intramolecular reactivity determined by the SupLUMO interaction (cis isomer pre-organization). The redox-gated covalent bond, serving as electron reservoir, was studied via atropisomerism of the reduction product (VT NMR study). The overall picture derived from this in-depth study of 2,2'-di(N-methylpyrid-4-ylium)-1,1'-biphenyl proves that trans and cis species are worth considered as intrinsically sharply different, that is, as doubly-electrophoric and singly-superelectrophoric switchable assemblies, beyond conformational isomerism. Most importantly, the through-space-mediated SupLUMO may come in complement of other weak interactions encountered in Supramolecular Chemistry as a tool for the design of electroactive architectures.

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“…13). It was also shown that the chirality of the molecule can be preserved upon bond cleavage and formation [49]. This would allow bond formation to be observed using circular dichroism (CD) as well as fluorescence and ultraviolet-visible spectroscopy.…”

Section: Other Organic Electroactive Groupsmentioning

confidence: 99%

Electrofluorochromic systems: Molecules and materials exhibiting redox-switchable fluorescence

Al-Kutubi

Zafarani

Rassaei

et al. 2016

European Polymer Journal

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Oxidative Protonolysis of the Expanded Central C–C Bond in a Di(spiroacridan)-type Hexaphenylethane Derivative Accompanied by UV–vis, FL, and CD Spectral Changes

Cited by 15 publications

References 26 publications

Bis(10‐methylacridinium)s as a Versatile Platform for Redox‐Active Functionalized Dyes and Novel Structures

Bis(10‐methylacridinium)s as a Versatile Platform for Redox‐Active Functionalized Dyes and Novel Structures

On the Supra‐LUMO Interaction: Case Study of a Sudden Change of Electronic Structure as a Functional Emergence

Electrofluorochromic systems: Molecules and materials exhibiting redox-switchable fluorescence

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