2024
DOI: 10.1002/chem.202400916
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Thermal Equilibrium Between Quinoid/Biradical Forms Enhancing Electrochemical Amphotericity

Yusuke Ishigaki,
Shin‐ichi Mizuno,
Kazuma Sugawara
et al.

Abstract: Upon dibenzo annulation on Thiele’s hydrocarbon (tetraphenyl‐p‐quinodimethane), the quinoid form and the biradical form adopt quite different geometries, and thus are no longer resonance structures. When these two forms can interconvert rapidly due to the small energy barrier (ΔG‡), the equilibrated mixture contains both forms in a ratio that is determined by the energy difference (ΔGo) between the two forms. For a series of tetrakis[5‐(4‐methoxyphenyl)‐2‐thienyl]‐substituted derivatives, the more stable quino… Show more

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Cited by 4 publications
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“…The removal of an electron from this radical cation is at least as facile, or even more facile, than the initial oxidation and thus occurs immediately, thereby generating rac - 1 2+ (potential compression/inversion, Figure S23). However, alternative mechanisms in which a conformational rearrangement precedes electron transfer , cannot be ruled out, as discussed in detail in the Supporting Information (Figures S24–S26). Regardless of the exact mechanism, oxidation (as well as reduction) proceeds without the buildup of the potentially reactive radical cation intermediate, an important feature of this system that undoubtedly contributes to its high degree of reversibility and stability (vide infra).…”
Section: Resultsmentioning
confidence: 99%
“…The removal of an electron from this radical cation is at least as facile, or even more facile, than the initial oxidation and thus occurs immediately, thereby generating rac - 1 2+ (potential compression/inversion, Figure S23). However, alternative mechanisms in which a conformational rearrangement precedes electron transfer , cannot be ruled out, as discussed in detail in the Supporting Information (Figures S24–S26). Regardless of the exact mechanism, oxidation (as well as reduction) proceeds without the buildup of the potentially reactive radical cation intermediate, an important feature of this system that undoubtedly contributes to its high degree of reversibility and stability (vide infra).…”
Section: Resultsmentioning
confidence: 99%