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On-surface generation and imaging of arynes by atomic force microscopy

Nature Chemistry volume 7, pages 623–628 (2015)Cite this article

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Abstract

Reactive intermediates are involved in many chemical transformations. However, their characterization is a great challenge because of their short lifetimes and high reactivities. Arynes, formally derived from arenes by the removal of two hydrogen atoms from adjacent carbon atoms, are prominent reactive intermediates that have been hypothesized for more than a century. Their rich chemistry enables a widespread use in synthetic chemistry, as they are advantageous building blocks for the construction of polycyclic compounds that contain aromatic rings. Here, we demonstrate the generation and characterization of individual polycyclic aryne molecules on an ultrathin insulating film by means of low-temperature scanning tunnelling microscopy and atomic force microscopy. Bond-order analysis suggests that a cumulene resonance structure is the dominant one, and the aryne reactivity is preserved at cryogenic temperatures. Our results provide important insights into the chemistry of these elusive intermediates and their potential application in the field of on-surface synthesis.

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Figure 1: Chemical transformation studied on a surface.
Figure 2: STM imaging and the on-surface generation of arynes on NaCl(2Ml)/Cu(111).
Figure 3: High-resolution AFM imaging of the reaction compounds.
Figure 4: Structure and bond-length evaluation of aryne and NP molecules.
Figure 5: On-surface chemistry of an aryne.

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Acknowledgements

We thank R. Allenspach for valuable comments on the manuscript. The research leading to these results received funding from the European Union projects PAMS (agreement no. 610446), the ITN QTea (317485), the European Research Council Advanced Grant CEMAS (291194), the Spanish Ministry of Science and Competitiveness (MINECO, MAT2013-46593-C6-6-P, CTQ2013-44142-P) and FEDER.

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Authors and Affiliations

  1. IBM Research–Zurich, Rüschlikon, 8803, Switzerland

    Niko Pavliček, Bruno Schuler, Nikolaj Moll, Gerhard Meyer & Leo Gross

  2. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, 15782, Spain

    Sara Collazos, Dolores Pérez, Enrique Guitián & Diego Peña

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  1. Niko Pavliček
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Contributions

N.P., B.S., G.M. and L.G. performed the STM/AFM experiments. S.C., Do.P., E.G. and Di.P. synthesized the molecules. N.M. performed the DFT calculations. All the authors discussed the results and contributed to the manuscript.

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Correspondence to Niko Pavliček or Diego Peña.

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Pavliček, N., Schuler, B., Collazos, S. et al. On-surface generation and imaging of arynes by atomic force microscopy. Nature Chem 7, 623–628 (2015). https://doi.org/10.1038/nchem.2300

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