Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids

Zhe Sun; Sangsu Lee; Kyuhyung Park; Xiaojian Zhu; Wenhua Zhang; Bin Zheng; Pan Hu; Zebing Zeng; Soumyajit Das; Yuan Li; Chunyan Chi; Runwei Li; Kuo-Wei Huang; Jun Ding; Dongho Kim; Jishan Wu

doi:10.1021/ja410279j

Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids

Zhe Sun, Sangsu Lee, Kyuhyung Park, Xiaojian Zhu, Wenhua Zhang, Bin Zheng, Pan Hu, Zebing Zeng, Soumyajit Das, Yuan Li, Chunyan Chi, Runwei Li, Kuo-Wei Huang, Jun Ding, Dongho Kim, Jishan Wu

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152 Scopus citations

Abstract

Clar's aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar's aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. © 2013 American Chemical Society.

Original language	English (US)
Pages (from-to)	18229-18236
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	135
Issue number	48
DOIs	https://doi.org/10.1021/ja410279j
State	Published - Nov 20 2013

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: J.W. acknowledges financial support from a MOE Tier 2 grant (MOE2011-T2-2-130) and IMRE Core funding (IMRE/13-1C0205). The work at Yonsei University was supported by the Midcareer Researcher Program (2010-0029668) and the Global Research Laboratory (2013K1A1A2A02050183) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT (Information and Communication Technologies) and Future Planning. K.-W.H. acknowledges financial support from KAUST.

ASJC Scopus subject areas

Biochemistry
Colloid and Surface Chemistry
General Chemistry
Catalysis

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10.1021/ja410279j

Cite this

Sun, Z., Lee, S., Park, K., Zhu, X., Zhang, W., Zheng, B., Hu, P., Zeng, Z., Das, S., Li, Y., Chi, C., Li, R., Huang, K.-W., Ding, J., Kim, D., & Wu, J. (2013). Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids. Journal of the American Chemical Society, 135(48), 18229-18236. https://doi.org/10.1021/ja410279j

@article{9c06b7b308624c45a3a093a972c42505,

title = "Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids",

abstract = "Clar's aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar's aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. {\textcopyright} 2013 American Chemical Society.",

author = "Zhe Sun and Sangsu Lee and Kyuhyung Park and Xiaojian Zhu and Wenhua Zhang and Bin Zheng and Pan Hu and Zebing Zeng and Soumyajit Das and Yuan Li and Chunyan Chi and Runwei Li and Kuo-Wei Huang and Jun Ding and Dongho Kim and Jishan Wu",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: J.W. acknowledges financial support from a MOE Tier 2 grant (MOE2011-T2-2-130) and IMRE Core funding (IMRE/13-1C0205). The work at Yonsei University was supported by the Midcareer Researcher Program (2010-0029668) and the Global Research Laboratory (2013K1A1A2A02050183) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT (Information and Communication Technologies) and Future Planning. K.-W.H. acknowledges financial support from KAUST.",

year = "2013",

month = nov,

day = "20",

doi = "10.1021/ja410279j",

language = "English (US)",

volume = "135",

pages = "18229--18236",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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Sun, Z, Lee, S, Park, K, Zhu, X, Zhang, W, Zheng, B, Hu, P, Zeng, Z, Das, S, Li, Y, Chi, C, Li, R, Huang, K-W, Ding, J, Kim, D & Wu, J 2013, 'Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids', Journal of the American Chemical Society, vol. 135, no. 48, pp. 18229-18236. https://doi.org/10.1021/ja410279j

TY - JOUR

T1 - Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids

AU - Sun, Zhe

AU - Lee, Sangsu

AU - Park, Kyuhyung

AU - Zhu, Xiaojian

AU - Zhang, Wenhua

AU - Zheng, Bin

AU - Hu, Pan

AU - Zeng, Zebing

AU - Das, Soumyajit

AU - Li, Yuan

AU - Chi, Chunyan

AU - Li, Runwei

AU - Huang, Kuo-Wei

AU - Ding, Jun

AU - Kim, Dongho

AU - Wu, Jishan

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: J.W. acknowledges financial support from a MOE Tier 2 grant (MOE2011-T2-2-130) and IMRE Core funding (IMRE/13-1C0205). The work at Yonsei University was supported by the Midcareer Researcher Program (2010-0029668) and the Global Research Laboratory (2013K1A1A2A02050183) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT (Information and Communication Technologies) and Future Planning. K.-W.H. acknowledges financial support from KAUST.

PY - 2013/11/20

Y1 - 2013/11/20

N2 - Clar's aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar's aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. © 2013 American Chemical Society.

AB - Clar's aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar's aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. © 2013 American Chemical Society.

UR - http://hdl.handle.net/10754/563140

UR - https://pubs.acs.org/doi/10.1021/ja410279j

UR - http://www.scopus.com/inward/record.url?scp=84889797865&partnerID=8YFLogxK

U2 - 10.1021/ja410279j

DO - 10.1021/ja410279j

M3 - Article

SN - 0002-7863

VL - 135

SP - 18229

EP - 18236

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 48

ER -

Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids

Abstract

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CCDC 954025: Experimental Crystal Structure Determination : 4,14-Dimesityl-9,19-bis(2-(tri-isopropylsilyl)ethynyl)benzo(a,de,l,op)pentacene

CCDC 954023: Experimental Crystal Structure Determination : 5,15-bis(4-t-Butylphenyl)-9,19-dimesityldinaphtho(3,2,1-de:3',2',1'-op)pentacene chloroform solvate

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Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 954025: Experimental Crystal Structure Determination : 4,14-Dimesityl-9,19-bis(2-(tri-isopropylsilyl)ethynyl)benzo(a,de,l,op)pentacene

CCDC 954023: Experimental Crystal Structure Determination : 5,15-bis(4-t-Butylphenyl)-9,19-dimesityldinaphtho(3,2,1-de:3',2',1'-op)pentacene chloroform solvate

Cite this