Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity

The Role of the Bridge Structure

Pan Hu, Sangsu Lee, Kyu Hyung Park, Soumyajit Das, Tun Seng Herng, Théo P. Gonçalves, Kuo Wei Huang, Jun Ding, Dongho Kim, Jishan Wu

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl-or pentafluorophenyl-substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability in an ambient environment, while OZI-M has high reactivity and can be easily oxidized to a dioxo product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F, and 15.

Original languageEnglish
Pages (from-to)2911-2919
Number of pages9
JournalJournal of Organic Chemistry
Volume81
Issue number7
DOIs
Publication statusPublished - 2016 Apr 15

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Chemical reactivity
Isomers
Bearings (structural)
Shells (structures)
Alkylation
Dehydrogenation
Ground state
Physical properties
Derivatives
octazethrene

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Hu, Pan ; Lee, Sangsu ; Park, Kyu Hyung ; Das, Soumyajit ; Herng, Tun Seng ; Gonçalves, Théo P. ; Huang, Kuo Wei ; Ding, Jun ; Kim, Dongho ; Wu, Jishan. / Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity : The Role of the Bridge Structure. In: Journal of Organic Chemistry. 2016 ; Vol. 81, No. 7. pp. 2911-2919.
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Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity : The Role of the Bridge Structure. / Hu, Pan; Lee, Sangsu; Park, Kyu Hyung; Das, Soumyajit; Herng, Tun Seng; Gonçalves, Théo P.; Huang, Kuo Wei; Ding, Jun; Kim, Dongho; Wu, Jishan.

In: Journal of Organic Chemistry, Vol. 81, No. 7, 15.04.2016, p. 2911-2919.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity

T2 - The Role of the Bridge Structure

AU - Hu, Pan

AU - Lee, Sangsu

AU - Park, Kyu Hyung

AU - Das, Soumyajit

AU - Herng, Tun Seng

AU - Gonçalves, Théo P.

AU - Huang, Kuo Wei

AU - Ding, Jun

AU - Kim, Dongho

AU - Wu, Jishan

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N2 - The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl-or pentafluorophenyl-substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability in an ambient environment, while OZI-M has high reactivity and can be easily oxidized to a dioxo product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F, and 15.

AB - The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl-or pentafluorophenyl-substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability in an ambient environment, while OZI-M has high reactivity and can be easily oxidized to a dioxo product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F, and 15.

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