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<p>Organic donor-acceptor cocrystals of <i>π</i>-conjugated molecues have shown diverse applications in materials science. However, most cocrystals exist in neutral forms dominated by <i>π</i>-<i>π</i> interactions, while the ionic congeners and corresponding properties are rarely studied due to difficulties in harnessing the degree of charge transfer. Herein, we report cocrystals of axially N-embedded quasi-carbon nanohoops (<b>DPP-D</b> and <b>DPP-T</b>) with electron deficient guests. By modulating the electron affinity of the acceptor guests, the electronic structures of the complexes can be tuned from neutral to ionic states. Specifically, <b>DPP-D</b> interacts with TCNB molecules to form neutral superstructures via intermolecular <i>π</i>-<i>π</i> interactions, giving rise to a deep-red emission in the solid state. In contrast, an ionic complex showing near-infrared region absorptions and paramagnetic character on account of strong charge-transfer interactions is generated when DDQ molecules are involved. Their unique properties can be explained by different degrees of charge transfer and assembly modes, which have clearly been manifested by crystal structures and theoretical calculations. Our studies provide rare examples of <i>π</i>-conjugated macrocycle-based donor-acceptor cocrystals in both neutral and ionic forms, and give insight to the design of multicomponent carbon nanomaterials.</p>

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Cocrystals of axially N-embedded quasi-carbon nanohoops via modulating the electron affinity of guest acceptors

  • 期刊论文

  • 发表日期：

    2025年1月16日

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  • Li Zhang,
  • Shuhai Qiu,
  • Shunlong Hu,
  • Hanren Xu,
  • Xuwen Sun,
  • Wei Jiang,
  • Da-Hui Qu,
  • Zhaohui Wang

摘要

Organic donor-acceptor cocrystals of π-conjugated molecues have shown diverse applications in materials science. However, most cocrystals exist in neutral forms dominated by π-π interactions, while the ionic congeners and corresponding properties are rarely studied due to difficulties in harnessing the degree of charge transfer. Herein, we report cocrystals of axially N-embedded quasi-carbon nanohoops (DPP-D and DPP-T) with electron deficient guests. By modulating the electron affinity of the acceptor guests, the electronic structures of the complexes can be tuned from neutral to ionic states. Specifically, DPP-D interacts with TCNB molecules to form neutral superstructures via intermolecular π-π interactions, giving rise to a deep-red emission in the solid state. In contrast, an ionic complex showing near-infrared region absorptions and paramagnetic character on account of strong charge-transfer interactions is generated when DDQ molecules are involved. Their unique properties can be explained by different degrees of charge transfer and assembly modes, which have clearly been manifested by crystal structures and theoretical calculations. Our studies provide rare examples of π-conjugated macrocycle-based donor-acceptor cocrystals in both neutral and ionic forms, and give insight to the design of multicomponent carbon nanomaterials.