Pushing extended p-quinodimethanes to the limit: Stable tetracyano-oligo(N-annulated perylene)quinodimethanes with tunable ground states

Zebing Zeng, Masatoshi Ishida, José L. Zafra, Xiaojian Zhu, Young Mo Sung, Nina Bao, Richard D. Webster, Byung Sun Lee, Run Wei Li, Wangdong Zeng, Yuan Li, Chunyan Chi, Juan T.López Navarrete, Jun Ding, Juan Casado, Dongho Kim, Jishan Wu

Research output: Contribution to journalArticle

107 Citations (Scopus)

Abstract

p-Quinodimethane (p-QDM) is a fundamental building block for the design of π-conjugated systems with low band gap and open-shell biradical character. However, synthesis of extended p-QDMs has usually suffered from their intrinsic high reactivity and poor solubility. In this work, benzannulation together with terminal cyano-substitution was demonstrated to be an efficient approach for the synthesis of a series of soluble and stable tetracyano-oligo(N-annulated perylene)quinodimethanes nPer-CN (n = 1-6), with the longest molecule having 12 para-linked benzenoid rings! The geometry and electronic structures of these oligomers were investigated by steady-state and transient absorption spectroscopy, nuclear magnetic resonance, electron spin resonance, superconducting quantum interference device, and FT Raman spectroscopy assisted by density functional theory calculations. They showed tunable ground states, varying from a closed-shell quinoidal structure for monomer, to a singlet biradical for dimer, trimer, and tetramer, and to a triplet biradical for pentamer and hexamer. Large two-photon absorption cross-section values were observed in the near-infrared range, which also exhibited a clear chain-length dependence.

Original languageEnglish
Pages (from-to)6363-6371
Number of pages9
JournalJournal of the American Chemical Society
Volume135
Issue number16
DOIs
Publication statusPublished - 2013 Apr 24

Fingerprint

Perylene
Ground state
Raman Spectrum Analysis
SQUIDs
Electron Spin Resonance Spectroscopy
Absorption spectroscopy
Chain length
Photons
Oligomers
Dimers
Solubility
Electronic structure
Density functional theory
Paramagnetic resonance
Raman spectroscopy
Energy gap
Substitution reactions
Magnetic Resonance Spectroscopy
Monomers
Nuclear magnetic resonance

All Science Journal Classification (ASJC) codes

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

Cite this

Zeng, Zebing ; Ishida, Masatoshi ; Zafra, José L. ; Zhu, Xiaojian ; Sung, Young Mo ; Bao, Nina ; Webster, Richard D. ; Lee, Byung Sun ; Li, Run Wei ; Zeng, Wangdong ; Li, Yuan ; Chi, Chunyan ; Navarrete, Juan T.López ; Ding, Jun ; Casado, Juan ; Kim, Dongho ; Wu, Jishan. / Pushing extended p-quinodimethanes to the limit : Stable tetracyano-oligo(N-annulated perylene)quinodimethanes with tunable ground states. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 16. pp. 6363-6371.
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abstract = "p-Quinodimethane (p-QDM) is a fundamental building block for the design of π-conjugated systems with low band gap and open-shell biradical character. However, synthesis of extended p-QDMs has usually suffered from their intrinsic high reactivity and poor solubility. In this work, benzannulation together with terminal cyano-substitution was demonstrated to be an efficient approach for the synthesis of a series of soluble and stable tetracyano-oligo(N-annulated perylene)quinodimethanes nPer-CN (n = 1-6), with the longest molecule having 12 para-linked benzenoid rings! The geometry and electronic structures of these oligomers were investigated by steady-state and transient absorption spectroscopy, nuclear magnetic resonance, electron spin resonance, superconducting quantum interference device, and FT Raman spectroscopy assisted by density functional theory calculations. They showed tunable ground states, varying from a closed-shell quinoidal structure for monomer, to a singlet biradical for dimer, trimer, and tetramer, and to a triplet biradical for pentamer and hexamer. Large two-photon absorption cross-section values were observed in the near-infrared range, which also exhibited a clear chain-length dependence.",
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Zeng, Z, Ishida, M, Zafra, JL, Zhu, X, Sung, YM, Bao, N, Webster, RD, Lee, BS, Li, RW, Zeng, W, Li, Y, Chi, C, Navarrete, JTL, Ding, J, Casado, J, Kim, D & Wu, J 2013, 'Pushing extended p-quinodimethanes to the limit: Stable tetracyano-oligo(N-annulated perylene)quinodimethanes with tunable ground states', Journal of the American Chemical Society, vol. 135, no. 16, pp. 6363-6371. https://doi.org/10.1021/ja402467y

Pushing extended p-quinodimethanes to the limit : Stable tetracyano-oligo(N-annulated perylene)quinodimethanes with tunable ground states. / Zeng, Zebing; Ishida, Masatoshi; Zafra, José L.; Zhu, Xiaojian; Sung, Young Mo; Bao, Nina; Webster, Richard D.; Lee, Byung Sun; Li, Run Wei; Zeng, Wangdong; Li, Yuan; Chi, Chunyan; Navarrete, Juan T.López; Ding, Jun; Casado, Juan; Kim, Dongho; Wu, Jishan.

In: Journal of the American Chemical Society, Vol. 135, No. 16, 24.04.2013, p. 6363-6371.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Pushing extended p-quinodimethanes to the limit

T2 - Stable tetracyano-oligo(N-annulated perylene)quinodimethanes with tunable ground states

AU - Zeng, Zebing

AU - Ishida, Masatoshi

AU - Zafra, José L.

AU - Zhu, Xiaojian

AU - Sung, Young Mo

AU - Bao, Nina

AU - Webster, Richard D.

AU - Lee, Byung Sun

AU - Li, Run Wei

AU - Zeng, Wangdong

AU - Li, Yuan

AU - Chi, Chunyan

AU - Navarrete, Juan T.López

AU - Ding, Jun

AU - Casado, Juan

AU - Kim, Dongho

AU - Wu, Jishan

PY - 2013/4/24

Y1 - 2013/4/24

N2 - p-Quinodimethane (p-QDM) is a fundamental building block for the design of π-conjugated systems with low band gap and open-shell biradical character. However, synthesis of extended p-QDMs has usually suffered from their intrinsic high reactivity and poor solubility. In this work, benzannulation together with terminal cyano-substitution was demonstrated to be an efficient approach for the synthesis of a series of soluble and stable tetracyano-oligo(N-annulated perylene)quinodimethanes nPer-CN (n = 1-6), with the longest molecule having 12 para-linked benzenoid rings! The geometry and electronic structures of these oligomers were investigated by steady-state and transient absorption spectroscopy, nuclear magnetic resonance, electron spin resonance, superconducting quantum interference device, and FT Raman spectroscopy assisted by density functional theory calculations. They showed tunable ground states, varying from a closed-shell quinoidal structure for monomer, to a singlet biradical for dimer, trimer, and tetramer, and to a triplet biradical for pentamer and hexamer. Large two-photon absorption cross-section values were observed in the near-infrared range, which also exhibited a clear chain-length dependence.

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