Toward Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

Pan Hu, Sangsu Lee, Tun Seng Herng, Naoki Aratani, Théo P. Gonçalves, Qingbiao Qi, Xueliang Shi, Hiroko Yamada, Kuo Wei Huang, Jun Ding, Dongho Kim, Jishan Wu

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

Open-shell singlet diradicaloids display unique electronic, nonlinear optical, and magnetic activity and could become novel molecular materials for organic electronics, photonics, and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this Article, we report our efforts toward a tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties, and chemical reactivity were systematically investigated by various experimental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device, and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introduction of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/antiaromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.

Original languageEnglish
Pages (from-to)1065-1077
Number of pages13
JournalJournal of the American Chemical Society
Volume138
Issue number3
DOIs
Publication statusPublished - 2016 Jan 27

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Chemical reactivity
Cyclic Hydrocarbons
Fusion reactions
Optics and Photonics
Electrochemistry
Optical Rotation
Magnetoelectronics
SQUIDs
Electron Spin Resonance Spectroscopy
X ray absorption
Naphthalene
Benzene
Photons
Photonics
Ground state
Density functional theory
Paramagnetic resonance
Charge transfer
Electronic equipment
Physical properties

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hu, Pan ; Lee, Sangsu ; Herng, Tun Seng ; Aratani, Naoki ; Gonçalves, Théo P. ; Qi, Qingbiao ; Shi, Xueliang ; Yamada, Hiroko ; Huang, Kuo Wei ; Ding, Jun ; Kim, Dongho ; Wu, Jishan. / Toward Tetraradicaloid : The Effect of Fusion Mode on Radical Character and Chemical Reactivity. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 3. pp. 1065-1077.
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Hu, P, Lee, S, Herng, TS, Aratani, N, Gonçalves, TP, Qi, Q, Shi, X, Yamada, H, Huang, KW, Ding, J, Kim, D & Wu, J 2016, 'Toward Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity', Journal of the American Chemical Society, vol. 138, no. 3, pp. 1065-1077. https://doi.org/10.1021/jacs.5b12532

Toward Tetraradicaloid : The Effect of Fusion Mode on Radical Character and Chemical Reactivity. / Hu, Pan; Lee, Sangsu; Herng, Tun Seng; Aratani, Naoki; Gonçalves, Théo P.; Qi, Qingbiao; Shi, Xueliang; Yamada, Hiroko; Huang, Kuo Wei; Ding, Jun; Kim, Dongho; Wu, Jishan.

In: Journal of the American Chemical Society, Vol. 138, No. 3, 27.01.2016, p. 1065-1077.

Research output: Contribution to journalArticle

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T2 - The Effect of Fusion Mode on Radical Character and Chemical Reactivity

AU - Hu, Pan

AU - Lee, Sangsu

AU - Herng, Tun Seng

AU - Aratani, Naoki

AU - Gonçalves, Théo P.

AU - Qi, Qingbiao

AU - Shi, Xueliang

AU - Yamada, Hiroko

AU - Huang, Kuo Wei

AU - Ding, Jun

AU - Kim, Dongho

AU - Wu, Jishan

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