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

研究成果: ジャーナルへの寄稿学術誌査読

131 被引用数 (Scopus)

抄録

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.

本文言語英語
ページ(範囲)6363-6371
ページ数9
ジャーナルJournal of the American Chemical Society
135
16
DOI
出版ステータス出版済み - 4月 24 2013
外部発表はい

!!!All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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