Article Emergence of conformational diversity and complexity of supramolecular structure by the interaction of a simple molecule with a uniform surface

S. Fatemeh Mousavi ; Aisha Ahsan ; Aaron Oechsle ; Narmadha Devi ; Yoshitaka Matsushita SAMURAI ORCID (National Institute for Materials Science) ; Luiza Buimaga-Iarinca ; Cristian Morari ; Waka Nakanishi SAMURAI ORCID (National Institute for Materials Science) ; Katsuhiko Ariga SAMURAI ORCID (National Institute for Materials Science) ; Yutaka Wakayama SAMURAI ORCID (National Institute for Materials Science) ; Yusuke Yamauchi ; Thomas A. Jung ; Jonathan P. Hill SAMURAI ORCID (National Institute for Materials Science)

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S. Fatemeh Mousavi, Aisha Ahsan, Aaron Oechsle, Narmadha Devi, Yoshitaka Matsushita, Luiza Buimaga-Iarinca, Cristian Morari, Waka Nakanishi, Katsuhiko Ariga, Yutaka Wakayama, Yusuke Yamauchi, Thomas A. Jung, Jonathan P. Hill. Emergence of conformational diversity and complexity of supramolecular structure by the interaction of a simple molecule with a uniform surface. Communications Chemistry. 2025, 8 (1), 214. https://doi.org/10.1038/s42004-025-01607-x

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(abstract)

The emergence of complexity during self-assembly of simple molecular building blocks is an important aspect in the synthesis of nanoarchitectures from supramolecular functional units. In particular, two-dimensional nanostructures are important from the point-of-view of technological applications. Here, a remarkably complex on surface network is observed to form spontaneously from a single molecular module (porphyrin) having multiple site-specific conformations. The interplay of different physicochemical interactions at the surface contributes to the site-specific symmetry breaking of the porphyrin conformation, and was investigated at different substrates. Molecular conformational flexure, relocation in the corrugated surface potential, interactions with surface state electrons, and last but not least mutual intermolecular binding by hydrogen bonding at different elevations above the substrate are critical elements. We discuss the possibility of surfaces and interfaces causing quasi-degeneracy of molecular configurations in supramolecular self-assembly, and the adsorbate-adsorbent interface as the driver for this system to behave counterintuitively to equilibrium thermodynamics.

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Keyword: Porphyrin, Self-assembly, scanning tunneling microscopy, kagome lattice, hydrogen bonding

Date published: 2025-07-24

Publisher: Springer Science and Business Media LLC

Journal:

  • Communications Chemistry (ISSN: 23993669) vol. 8 issue. 1 214

Funding:

  • Japan Science and Technology Agency JPMJER2003 (Yamauchi Space Tectonics Project)
  • Swiss National Science Foundation 200020_162512

Manuscript type: Publisher's version (Version of record)

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First published URL: https://doi.org/10.1038/s42004-025-01607-x

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Updated at: 2025-10-30 16:30:11 +0900

Published on MDR: 2025-10-30 16:23:29 +0900

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