A Doubly Nitrogen-Bridged Chiral Spirobifluorene Dimeric Macrocycle: Synthesis, Properties, and Thermally Activated Electron Exchange in the Oxidized State

Abstract A doubly nitrogen-bridged chiral spirobifluorene dimer with a rigid double-helical structure was synthesized, and its one-electron oxidized species was investigated as a mixed-valence system. Variable-temperature ESR measurements revealed thermally activated intramolecular electron exchange with a very small activation enthalpy (ΔH‡ = 1.25 kcal mol–1), despite limited electronic communication across the doubly spiro-linked redox units.

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Publication Details

Journal
Organic Letters
Published
2026-09-10
DOI
https://doi.org/10.1021/acs.orglett.6c02599
Primary Topic
Synthesis and Properties of Aromatic Compounds
Type
article
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A Doubly Nitrogen-Bridged Chiral Spirobifluorene Dimeric Macrocycle: Synthesis, Properties, and Thermally Activated Electron Exchange in the Oxidized State

Shinobu Aoyagi, Tomoya Imai, Toru Amaya, Daisuke Sakamaki et al.
Organic Letters
Synthesis and Properties of Aromatic Compounds
article

A Doubly Nitrogen-Bridged Chiral Spirobifluorene Dimeric Macrocycle: Synthesis, Properties, and Thermally Activated Electron Exchange in the Oxidized State

Shinobu Aoyagi, Tomoya Imai, Toru Amaya, Daisuke Sakamaki, Takuya Kodama, Rina Nakazono, Haruka Mizukawa
article en

Abstract

Abstract A doubly nitrogen-bridged chiral spirobifluorene dimer with a rigid double-helical structure was synthesized, and its one-electron oxidized species was investigated as a mixed-valence system. Variable-temperature ESR measurements revealed thermally activated intramolecular electron exchange with a very small activation enthalpy (ΔH‡ = 1.25 kcal mol–1), despite limited electronic communication across the doubly spiro-linked redox units.

Organic Letters
Osaka University of Economics (JP), Nagoya City University (JP), Metropolitan University (RS), Nagoya City University Hospital (JP), Metropolitan University (VE), Tokyo Metropolitan University (JP), The University of Osaka (JP)
Life in Land
Openalex Percentile: Top 20%
Synthesis and Properties of Aromatic Compounds
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A Doubly Nitrogen-Bridged Chiral Spirobifluorene Dimeric Macrocycle: Synthesis, Properties, and Thermally Activated Electron Exchange in the Oxidized State — Shinobu Aoyagi, Tomoya Imai, et al. · Organic Letters (2026) | TGRS Research Map | TGRS