Indolo[2,3-b]carbazoles with tunable ground states: How Clar's aromatic sextet determines the singlet biradical character

Ding Luo, Sangsu Lee, Bin Zheng, Zhe Sun, Wangdong Zeng, Kuo Wei Huang, Ko Furukawa, Dongho Kim, Richard D. Webster, Jishan Wu

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

Polycyclic hydrocarbons (PHs) with a singlet biradical ground state have recently attracted extensive interest in physical organic chemistry and materials science. Replacing the carbon radical center in the open-shell PHs with a more electronegative nitrogen atom is expected to result in the more stable aminyl radical. In this work, two kinetically blocked stable/persistent derivatives (1 and 2) of indolo[2,3-b]carbazole, an isoelectronic structure of the known indeno[2,1-b]fluorene, were synthesized and showed different ground states. Based on variable-temperature NMR/ESR measurements and density functional theory calculations, it was found that the indolo[2,3-b]carbazole derivative 1 is a persistent singlet biradical in the ground state with a moderate biradical character (y0 = 0.269) and a small singlet-triplet energy gap (ΔES-T ≅ -1.78 kcal mol-1), while the more extended dibenzo-indolo[2,3-b]carbazole 2 exhibits a quinoidal closed-shell ground state. The difference can be explained by considering the number of aromatic sextet rings gained from the closed-shell to the open-shell biradical resonance form, that is to say, two for compound 1 and one for compound 2, which determines their different biradical characters. The optical and electronic properties of 2 and the corresponding aromatic precursors were investigated by one-photon absorption, transient absorption and two-photon absorption (TPA) spectroscopies and electrochemistry. Amphoteric redox behaviour, a short excited lifetime and a moderate TPA cross section were observed for 2, which can be correlated to its antiaromaticity and small biradical character. Compound 2 showed high reactivity to protic solvents due to its extremely low-lying LUMO energy level. Unusual oxidative dimerization was also observed for the unblocked dihydro-indolo[2,3-b]carbazole precursors 6 and 11. Our studies shed light on the rational design of persistent aminyl biradicals with tunable properties in the future. This journal is

Original languageEnglish
Pages (from-to)4944-4952
Number of pages9
JournalChemical Science
Volume5
Issue number12
DOIs
Publication statusPublished - 2014 Dec 1

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Ground state
Cyclic Hydrocarbons
Photons
Derivatives
Dimerization
Electrochemistry
Materials science
Absorption spectroscopy
Electronic properties
Electron energy levels
Density functional theory
Paramagnetic resonance
Energy gap
Nitrogen
Carbon
Optical properties
Nuclear magnetic resonance
Atoms
indolo(3,2-b)carbazole
Temperature

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Luo, Ding ; Lee, Sangsu ; Zheng, Bin ; Sun, Zhe ; Zeng, Wangdong ; Huang, Kuo Wei ; Furukawa, Ko ; Kim, Dongho ; Webster, Richard D. ; Wu, Jishan. / Indolo[2,3-b]carbazoles with tunable ground states : How Clar's aromatic sextet determines the singlet biradical character. In: Chemical Science. 2014 ; Vol. 5, No. 12. pp. 4944-4952.
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abstract = "Polycyclic hydrocarbons (PHs) with a singlet biradical ground state have recently attracted extensive interest in physical organic chemistry and materials science. Replacing the carbon radical center in the open-shell PHs with a more electronegative nitrogen atom is expected to result in the more stable aminyl radical. In this work, two kinetically blocked stable/persistent derivatives (1 and 2) of indolo[2,3-b]carbazole, an isoelectronic structure of the known indeno[2,1-b]fluorene, were synthesized and showed different ground states. Based on variable-temperature NMR/ESR measurements and density functional theory calculations, it was found that the indolo[2,3-b]carbazole derivative 1 is a persistent singlet biradical in the ground state with a moderate biradical character (y0 = 0.269) and a small singlet-triplet energy gap (ΔES-T ≅ -1.78 kcal mol-1), while the more extended dibenzo-indolo[2,3-b]carbazole 2 exhibits a quinoidal closed-shell ground state. The difference can be explained by considering the number of aromatic sextet rings gained from the closed-shell to the open-shell biradical resonance form, that is to say, two for compound 1 and one for compound 2, which determines their different biradical characters. The optical and electronic properties of 2 and the corresponding aromatic precursors were investigated by one-photon absorption, transient absorption and two-photon absorption (TPA) spectroscopies and electrochemistry. Amphoteric redox behaviour, a short excited lifetime and a moderate TPA cross section were observed for 2, which can be correlated to its antiaromaticity and small biradical character. Compound 2 showed high reactivity to protic solvents due to its extremely low-lying LUMO energy level. Unusual oxidative dimerization was also observed for the unblocked dihydro-indolo[2,3-b]carbazole precursors 6 and 11. Our studies shed light on the rational design of persistent aminyl biradicals with tunable properties in the future. This journal is",
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Luo, D, Lee, S, Zheng, B, Sun, Z, Zeng, W, Huang, KW, Furukawa, K, Kim, D, Webster, RD & Wu, J 2014, 'Indolo[2,3-b]carbazoles with tunable ground states: How Clar's aromatic sextet determines the singlet biradical character', Chemical Science, vol. 5, no. 12, pp. 4944-4952. https://doi.org/10.1039/c4sc01843e

Indolo[2,3-b]carbazoles with tunable ground states : How Clar's aromatic sextet determines the singlet biradical character. / Luo, Ding; Lee, Sangsu; Zheng, Bin; Sun, Zhe; Zeng, Wangdong; Huang, Kuo Wei; Furukawa, Ko; Kim, Dongho; Webster, Richard D.; Wu, Jishan.

In: Chemical Science, Vol. 5, No. 12, 01.12.2014, p. 4944-4952.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Indolo[2,3-b]carbazoles with tunable ground states

T2 - How Clar's aromatic sextet determines the singlet biradical character

AU - Luo, Ding

AU - Lee, Sangsu

AU - Zheng, Bin

AU - Sun, Zhe

AU - Zeng, Wangdong

AU - Huang, Kuo Wei

AU - Furukawa, Ko

AU - Kim, Dongho

AU - Webster, Richard D.

AU - Wu, Jishan

PY - 2014/12/1

Y1 - 2014/12/1

N2 - Polycyclic hydrocarbons (PHs) with a singlet biradical ground state have recently attracted extensive interest in physical organic chemistry and materials science. Replacing the carbon radical center in the open-shell PHs with a more electronegative nitrogen atom is expected to result in the more stable aminyl radical. In this work, two kinetically blocked stable/persistent derivatives (1 and 2) of indolo[2,3-b]carbazole, an isoelectronic structure of the known indeno[2,1-b]fluorene, were synthesized and showed different ground states. Based on variable-temperature NMR/ESR measurements and density functional theory calculations, it was found that the indolo[2,3-b]carbazole derivative 1 is a persistent singlet biradical in the ground state with a moderate biradical character (y0 = 0.269) and a small singlet-triplet energy gap (ΔES-T ≅ -1.78 kcal mol-1), while the more extended dibenzo-indolo[2,3-b]carbazole 2 exhibits a quinoidal closed-shell ground state. The difference can be explained by considering the number of aromatic sextet rings gained from the closed-shell to the open-shell biradical resonance form, that is to say, two for compound 1 and one for compound 2, which determines their different biradical characters. The optical and electronic properties of 2 and the corresponding aromatic precursors were investigated by one-photon absorption, transient absorption and two-photon absorption (TPA) spectroscopies and electrochemistry. Amphoteric redox behaviour, a short excited lifetime and a moderate TPA cross section were observed for 2, which can be correlated to its antiaromaticity and small biradical character. Compound 2 showed high reactivity to protic solvents due to its extremely low-lying LUMO energy level. Unusual oxidative dimerization was also observed for the unblocked dihydro-indolo[2,3-b]carbazole precursors 6 and 11. Our studies shed light on the rational design of persistent aminyl biradicals with tunable properties in the future. This journal is

AB - Polycyclic hydrocarbons (PHs) with a singlet biradical ground state have recently attracted extensive interest in physical organic chemistry and materials science. Replacing the carbon radical center in the open-shell PHs with a more electronegative nitrogen atom is expected to result in the more stable aminyl radical. In this work, two kinetically blocked stable/persistent derivatives (1 and 2) of indolo[2,3-b]carbazole, an isoelectronic structure of the known indeno[2,1-b]fluorene, were synthesized and showed different ground states. Based on variable-temperature NMR/ESR measurements and density functional theory calculations, it was found that the indolo[2,3-b]carbazole derivative 1 is a persistent singlet biradical in the ground state with a moderate biradical character (y0 = 0.269) and a small singlet-triplet energy gap (ΔES-T ≅ -1.78 kcal mol-1), while the more extended dibenzo-indolo[2,3-b]carbazole 2 exhibits a quinoidal closed-shell ground state. The difference can be explained by considering the number of aromatic sextet rings gained from the closed-shell to the open-shell biradical resonance form, that is to say, two for compound 1 and one for compound 2, which determines their different biradical characters. The optical and electronic properties of 2 and the corresponding aromatic precursors were investigated by one-photon absorption, transient absorption and two-photon absorption (TPA) spectroscopies and electrochemistry. Amphoteric redox behaviour, a short excited lifetime and a moderate TPA cross section were observed for 2, which can be correlated to its antiaromaticity and small biradical character. Compound 2 showed high reactivity to protic solvents due to its extremely low-lying LUMO energy level. Unusual oxidative dimerization was also observed for the unblocked dihydro-indolo[2,3-b]carbazole precursors 6 and 11. Our studies shed light on the rational design of persistent aminyl biradicals with tunable properties in the future. This journal is

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