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On-surface cyclization of vinyl groups on poly-para-phenylene involving an unusual pentagon to hexagon transformation

Marco Di Giovannantonio1,2*, Zijie Qiu3,4*, Carlo A. Pignedoli1*, Sobi Asako5,6*, Pascal Ruffieux1*, Klaus Müllen3,7*, Akimitsu Narita3,6*, Roman Fasel1,8*

1 Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600 Dübendorf, Switzerland

2 Istituto di Struttura della Materia – CNR (ISM-CNR), 00133 Roma, Italy

3 Max Planck Institute for Polymer Research, 55128 Mainz, Germany

4 School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, Shenzhen, Guangdong 518172, China

5 RIKEN Center for Sustainable Resource Science, Wako, Saitama 351-0198, Japan

6 Organic and Carbon Nanomaterials Unit, Okinawa Institute of Science and Technology Graduate University, Okinawa 904-0495, Japan

7 Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany

8 Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, 3012 Bern, Switzerland

* Corresponding authors emails: marco.digiovannantonio@ism.cnr.it, zijieqiu@cuhk.edu.cn, carlo.pignedoli@empa.ch, sobi.asako@riken.jp, pascal.ruffieux@empa.ch, muellen@mpip-mainz.mpg.de, akimitsu.narita@oist.jp, roman.fasel@empa.ch
DOI10.24435/materialscloud:6f-kw [version v1]

Publication date: Feb 15, 2024

How to cite this record

Marco Di Giovannantonio, Zijie Qiu, Carlo A. Pignedoli, Sobi Asako, Pascal Ruffieux, Klaus Müllen, Akimitsu Narita, Roman Fasel, On-surface cyclization of vinyl groups on poly-para-phenylene involving an unusual pentagon to hexagon transformation, Materials Cloud Archive 2024.31 (2024), https://doi.org/10.24435/materialscloud:6f-kw


On-surface synthesis relies on carefully designed molecular precursors that are thermally activated to afford desired, covalently coupled architectures. In a recent publication, we studied the reactions of vinyl groups on poly-para-phenylene and provided a comprehensive description of all the reaction steps taking place on the Au(111) surface under ultrahigh vacuum conditions. We find that vinyl groups successfully cyclize with the phenylene rings in the ortho positions, forming a dimethyl-dihydroindenofluorene as the repeating unit, which can be further dehydrogenated to a dimethylene-dihydroindenofluorene structure. Interestingly, the obtained polymer can be transformed cleanly into thermodynamically stable polybenzo[k]tetraphene at higher temperature, involving a previously elusive pentagon-to-hexagon transformation via ring opening and rearrangement on a metal surface. Our insights into the reaction cascade unveil fundamental chemical processes involving vinyl groups on surfaces. Because the formation of specific products is highly temperature-dependent, this innovative approach offers a valuable tool for fabricating complex, low-dimensional nanostructures with high precision and yield. This record contains the data that support the scientific results in the publication.

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External references

Journal reference (Manuscript where the scientific results are discussed)
M. Di Giovannantonio, Z. Qiu, C. A. Pignedoli, S. Asako, P. Ruffieux, K. Müllen, A. Narita, R. Fasel, Nat. Commun. (2024) doi:10.1038/s41467-024-46173-3


MARVEL/P4 CSCS On-surface synthesis SPM DFT Vinyl cyclization

Version history:

2024.31 (version v1) [This version] Feb 15, 2024 DOI10.24435/materialscloud:6f-kw