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<p>Highly conjugated, two-dimensional oligomers (2DOs) are desirable because they are expected to be soluble and processable like small molecules while possessing electronic properties akin to highly conjugated polymers. Here, we report one-pot syntheses of 2DOs prepared from acene-2,3-dicarbaldehydes and either <i>p</i>-xylylenediamine (<b>2DO-1</b>) or 1,2-ethylenediamine (<b>2DO-2</b>). Product structures were characterized using UV–vis, FT-IR and <sup>1</sup>H NMR spectroscopies as well as time-dependent density functional theory (TD-DFT). Surprisingly, 2DOs prepared from <i>o</i>-phthalaldehyde showed broad band UV–vis absorptions from 250 to 650&#xa0;nm with optical HOMO–LUMO gaps of ~ 2.3&#xa0;eV, suggesting partial dehydrogenation under the reaction conditions employed forming localized regions of highly conjugated π-systems. TD-DFT calculations on simplified 2DOs with varying levels of dehydrogenation corroborate the experimental results. Separate TD-DFT calculations demonstrated progressively smaller HOMO–LUMO gaps upon incorporation of progressively larger acene moieties in the 2DOs. Thus, the electronic properties of 2DOs prepared from acene-2,3-dicarbaldehydes are tunable in two distinct manners.</p> Graphical abstract <p></p>

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2D oligomers (2DOs) derived from acene-2,3-dicarbaldehydes

  • 期刊论文

  • 发表日期：

    2025年6月12日

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  • Qian Liu,
  • Glen P. Miller

摘要

Highly conjugated, two-dimensional oligomers (2DOs) are desirable because they are expected to be soluble and processable like small molecules while possessing electronic properties akin to highly conjugated polymers. Here, we report one-pot syntheses of 2DOs prepared from acene-2,3-dicarbaldehydes and either p-xylylenediamine (2DO-1) or 1,2-ethylenediamine (2DO-2). Product structures were characterized using UV–vis, FT-IR and 1H NMR spectroscopies as well as time-dependent density functional theory (TD-DFT). Surprisingly, 2DOs prepared from o-phthalaldehyde showed broad band UV–vis absorptions from 250 to 650 nm with optical HOMO–LUMO gaps of ~ 2.3 eV, suggesting partial dehydrogenation under the reaction conditions employed forming localized regions of highly conjugated π-systems. TD-DFT calculations on simplified 2DOs with varying levels of dehydrogenation corroborate the experimental results. Separate TD-DFT calculations demonstrated progressively smaller HOMO–LUMO gaps upon incorporation of progressively larger acene moieties in the 2DOs. Thus, the electronic properties of 2DOs prepared from acene-2,3-dicarbaldehydes are tunable in two distinct manners.

Graphical abstract