Article Structural flexibility and mobility of coordination polymers on Cu(111)

Waka Nakanishi SAMURAI ORCID ; Masayuki Takeuchi SAMURAI ORCID ; Keisuke Sagisaka SAMURAI ORCID

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Waka Nakanishi, Masayuki Takeuchi, Keisuke Sagisaka. Structural flexibility and mobility of coordination polymers on Cu(111). Chemical Science. 2025, 16 (21), 9156-9162.

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(abstract)

Coordination polymers on surfaces have been investigated at the atomic level via scanning tunneling microscopy (STM), revealing a variety of structures and electronic states. However, analysis of their dynamic behaviours at low temperatures has been hampered due to the strong adsorption of organic ligands on metal surfaces. In this study, we designed 2,7-dicyano-9,9-dimethyl-9H-fluorene (DCF) as a ligand for coordination polymer in order to reveal its mobility at low temperatures. The dimethyl group attached to the ligand reduces the interaction with the metal surface and serves as an indicator of the ligand orientation. This enables individual tracking of DCF in DCF-Cu polymer on Cu(111) after their coordination with copper adatoms. Upon heating from 4 K to 78 K, branched structures were less mobile, while linear structures and short polymers with free ends exhibited higher mobility. Partial cleavage, recombination, and insertion of the polymer chains were observed in some sections of the polymer chains. Density functional theory (DFT) calculations suggest that the flexibility of the coordination angle (180° ± 20°) facilitates such transformations. This study provided a direct observation of the motion differences attributed to polymer chain structures as proposed in real materials.

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Keyword: coordination polymer, STM, dynamic behaviour, on-surface, flexibility, single molecule, motion

Date published: 2025-04-28

Publisher: Royal Society of Chemistry (RSC)

Journal:

  • Chemical Science (ISSN: 20416520) vol. 16 issue. 21 p. 9156-9162

Funding:

  • National Institute for Materials Science JPMXP1224NM5109
  • Japan Society for the Promotion of Science 22K04860
  • Japan Society for the Promotion of Science 22K05088
  • Ministry of Education, Culture, Sports, Science and Technology

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

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First published URL: https://doi.org/10.1039/d5sc01949d

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Updated at: 2025-06-03 16:16:22 +0900

Published on MDR: 2025-06-04 08:20:16 +0900

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