Emergence of conformational diversity and complexity of supramolecular structure by the interaction of a simple molecule with a uniform surface
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 quasidegeneracy of molecular configurations in supramolecular self-assembly, and the adsorbate-adsorbent interface as the driver for this system to behave counterintuitively to equilibrium thermodynamics.
Authors
- Jonathan P. Hill (ORCID: https://orcid.org/0000-0002-4229-5842)
- Yoshitaka Matsushita (ORCID: https://orcid.org/0000-0002-4968-8905)
- Cristian Morari (ORCID: https://orcid.org/0000-0003-1989-3278)
- Luiza Buimagă-Iarinca (ORCID: https://orcid.org/0000-0002-4600-0765)
- Aisha Ahsan (ORCID: https://orcid.org/0000-0003-3358-202X)
- Katsuhiko Ariga (ORCID: https://orcid.org/0000-0002-2445-2955)
- Yutaka Wakayama (ORCID: https://orcid.org/0000-0002-0801-8884)
- Yusuke Yamauchi (ORCID: https://orcid.org/0000-0001-7854-927X)
- Seyedeh Fatemeh Mousavi (ORCID: https://orcid.org/0000-0003-1455-4437)
- Thomas A. Jung (ORCID: https://orcid.org/0000-0003-0717-9886)
- Waka Nakanishi (ORCID: https://orcid.org/0000-0001-6801-1839)
- N. Saradha Devi
- Aaron H. Oechsle
Institutions
- The University of Queensland (AU)
- University of Basel (CH)
- Yonsei University (KR)
- National Institute for Materials Science (JP)
- Paul Scherrer Institute (CH)
- Innovative Research (United States) (US)
- National Institute for Research and Development of Isotopic and Molecular Technologies (RO)
- Nagoya University (JP)
- The University of Tokyo (JP)
Publication Details
- Journal
- Communications Chemistry
- Published
- 2025-07-24
- DOI
- https://doi.org/10.1038/s42004-025-01607-x
- Citations
- 1
- Primary Topic
- Surface Chemistry and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.67
Funders
- National Science Foundation
- Australian National Fabrication Facility
- Universität Basel
- Ministry of Education, Culture, Sports, Science and Technology
- Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
- Kommission für Technologie und Innovation
- Paul Scherrer Institut
- Swiss Nanoscience Institute
- National Institute for Materials Science
- Exploratory Research for Advanced Technology