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<p>The structural preferences of molecular assemblies are governed by a delicate balance between strong directional forces and diffuse dispersion contacts. Mixed trimers of pyrrole (Py) and benzene (Bz) provide an ideal benchmark to probe this interplay: the robust N-H⋯<i>π</i> interaction anchoring the Py-Bz dimer competes with the drive toward compact, dispersion-stabilized arrangements in larger clusters. Here, we report the first high-resolution structural characterization of the Py-(Bz)<sub>2</sub> and (Py)<sub>2</sub>-Bz trimers and the (Py)<sub>2</sub>-(Bz)<sub>2</sub> tetramer using chirped-pulse Fourier transform microwave spectroscopy combined with dispersion-corrected DFT calculations and intensity-based cross-correlation analysis. The results show that while N-H⋯<i>π</i> and C-H⋯<i>π</i> interactions serve as primary anchors, the overall geometries are dictated by space-filling principles that maximize dispersion contacts. These findings establish pyrrole-benzene hetero clusters as a rigorous benchmark for theoretical methods and provide fundamental insight into the forces guiding aromatic aggregation and self-assembly in complex molecular systems.</p><p></p>

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Space filling shapes the interaction networks in mixed pyrrole-benzene trimers and tetramers

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年4月17日

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  • Simon Lobsiger,
  • Zbigniew Kisiel,
  • Caroline S. Glick,
  • George C. Shields,
  • Brooks H. Pate,
  • Cristóbal Pérez

摘要

The structural preferences of molecular assemblies are governed by a delicate balance between strong directional forces and diffuse dispersion contacts. Mixed trimers of pyrrole (Py) and benzene (Bz) provide an ideal benchmark to probe this interplay: the robust N-H⋯π interaction anchoring the Py-Bz dimer competes with the drive toward compact, dispersion-stabilized arrangements in larger clusters. Here, we report the first high-resolution structural characterization of the Py-(Bz)2 and (Py)2-Bz trimers and the (Py)2-(Bz)2 tetramer using chirped-pulse Fourier transform microwave spectroscopy combined with dispersion-corrected DFT calculations and intensity-based cross-correlation analysis. The results show that while N-H⋯π and C-H⋯π interactions serve as primary anchors, the overall geometries are dictated by space-filling principles that maximize dispersion contacts. These findings establish pyrrole-benzene hetero clusters as a rigorous benchmark for theoretical methods and provide fundamental insight into the forces guiding aromatic aggregation and self-assembly in complex molecular systems.