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Dramatic acceleration of the Hopf cyclization on gold(111): from enediynes to unusual graphene nanoribbons

Chenxiao Zhao1*, Carlo A. Pignedoli1*, Dayanni D. Bhagwandin2, Wangwei Xu1, Pascal Rufieux1, Roman Fasel1,3, Yves Rubin2

1 Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland

2 Department of Chemistry and Biochemistry, University of California, Los Angeles

3 University of Bern, Bern, Switzerland

* Corresponding authors emails: chenxiao.zhao@emap.ch, carlo.pignedoli@empa.ch
DOI10.24435/materialscloud:62-ew [version v1]

Publication date: May 21, 2024

How to cite this record

Chenxiao Zhao, Carlo A. Pignedoli, Dayanni D. Bhagwandin, Wangwei Xu, Pascal Rufieux, Roman Fasel, Yves Rubin, Dramatic acceleration of the Hopf cyclization on gold(111): from enediynes to unusual graphene nanoribbons, Materials Cloud Archive 2024.75 (2024), https://doi.org/10.24435/materialscloud:62-ew


Hopf et al. first reported the high-temperature 6π-electrocyclization of cis-hexa-1,3-diene-5-yne to benzene in 1969. Subsequent studies using this cyclization have been limited by its very high reaction barrier. Here, we show that the reaction barrier for two model systems, (E)-1,3,4,6-tetraphenyl-3-hexen-1,5-diyne (1a) and (E)-3,4-bis(4-iodophenyl)-1,6-diphenyl-3-hexen-1,5-diyne 1b, is decreased by nearly half on a Au(111) surface. In recent work, we have used scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM) to monitor the Hopf cyclization of enediynes 1a,b on Au(111). Enediyne 1a undergoes two sequential, quantitative Hopf cyclizations, first to naphthalene derivative 2, and finally to chrysene 3. Density functional theory (DFT) calculations reveal that a gold atom from the Au(111) surface is involved in all steps of this reaction, and that it is crucial to lowering the reaction barrier. Our findings have important implications for the synthesis of novel graphene nanoribbons. Ullman coupling of enediyne 1b at 20 ˚C on Au(111), followed by a series of Hopf cyclizations and aromatization reactions at higher temperatures, produces nanoribbons 12, and eventually 13 upon further heating. These results show for the first time that graphene nanoribbons can be synthesized on-surface using the Hopf cyclization mechanism. This record contains all simulation data that support our scientific work.

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External references

Journal reference (Manuscript where the results are discussed)
C. Zhao, D. D. Bhagwandin, W. Xu, P. Rufieux, C. A. Pignedoli, R. Fasel. and Y. Rubin, J. Am. Chem. Soc. 2024, 146, 4, 2474–2483 doi:10.1021/jacs.3c10144


MARVEL/P4 SNSF CSCS DFT STM nc-AFM on surface synthesis

Version history:

2024.75 (version v1) [This version] May 21, 2024 DOI10.24435/materialscloud:62-ew