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On-surface polyarylene synthesis by cycloaromatization of isopropyl substituents

Nature Synthesis volume 1, pages 289–296 (2022)Cite this article

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Abstract

Immobilization of organic molecules on metal surfaces and their coupling via thermally induced C–C bond formation is an important technique in organic and polymer synthesis. Using this approach, insoluble and reactive carbon nanostructures can be synthesized and the reactions monitored in situ using scanning probe microscopy methods. The diversity of conceivable products, however, is limited by the number and variety of known on-surface reactions. Here, we introduce the on-surface synthesis of polyarylenes by intermolecular oxidative coupling of isopropyl substituents of arenes. This [3+3] dimerization reaction forms a new phenylene ring and can be regarded as a formal cycloaromatization. The synthetic value of this reaction is proved by the synthesis of polyarylenes and co-polyarylenes, which we demonstrate by synthesizing poly(2,7-pyrenylene-1,4-phenylene). Scanning tunnelling microscopy and non-contact atomic force microscopy studies, complemented by density functional theory calculations, offer mechanistic insight into the on-surface cycloaromatization reaction.

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Fig. 1: On-surface polyarylene synthesis.
Fig. 2: Formation of new phenylene rings by the homocoupling of diisopropyl-substituted terphenyl on Au(111) and Au(110) surfaces.
Fig. 3: Confirmation of chemical structures of 1–4.
Fig. 4: Theoretical investigation of the reaction mechanism.
Fig. 5: Formation of pyrenylene–phenylene copolymers.
Fig. 6: Design constraints on the [3+3] cycloaromatization reaction.

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Data availability

All the STM, nc-AFM and computational datasets shown in the paper and Supplementary Information are available from Materials Cloud at https://doi.org/10.24435/materialscloud:yy-sc (ref. 58).

Code availability

The CP2K software package is available at https://www.cp2k.org/ and the AiiDAlab software package can be downloaded at https://www.materialscloud.org/work/aiidalab.

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Acknowledgements

This work was supported by the Swiss National Science Foundation (grant no. 200020_182015), the NCCR MARVEL funded by the Swiss National Science Foundation (grant no. 51NF40-182892), the Johannes Gutenberg-Universität Mainz (JGU) through Gutenberg Forschungskolleg Fellowship (GFK) and the Max Planck Society. J.I.U. acknowledges the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie (grant agreement no. 886314). E.J., Y.G. and Z.Q. would like to acknowledge support from the Alexander von Humboldt Foundation. K.M. thanks the Gutenberg Research College for a scholarship. Computational support from the Swiss Supercomputing Center (CSCS) under project ID s904 is gratefully acknowledged. A.K., M.D.G., J.I.U., P.R. and R.F. thank L. Rotach (Empa, Dübendorf) for technical support.

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Author notes

  1. Marco Di Giovannantonio

    Present address: Istituto di Struttura della Materia-CNR (ISM-CNR), Rome, Italy

  2. José I. Urgel

    Present address: IMDEA Nanoscience, Madrid, Spain

  3. Akimitsu Narita

    Present address: Organic and Carbon Nanomaterials Unit, Okinawa Institute of Science and Technology Graduate University, Okinawa, Japan

  4. Xiao-Ye Wang

    Present address: State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, China

  5. These authors contributed equally: Amogh Kinikar, Marco Di Giovannantonio.

Authors and Affiliations

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

    Amogh Kinikar, Marco Di Giovannantonio, José I. Urgel, Kristjan Eimre, Pascal Ruffieux, Carlo A. Pignedoli & Roman Fasel

  2. Max Planck Institute for Polymer Research, Mainz, Germany

    Zijie Qiu, Yanwei Gu, Enquan Jin, Akimitsu Narita, Xiao-Ye Wang & Klaus Müllen

  3. Institute of Physical Chemistry, Johannes Gutenberg-Universität Mainz, Mainz, Germany

    Klaus Müllen

  4. Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, Bern, Switzerland

    Roman Fasel

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Contributions

A.K., K.M., P.R. and R.F. conceived the project. Z.Q., Y.G., E.J. and X.-Y.W. synthesized and characterized the precursor molecules under the supervision of A.N. and K.M. The on-surface synthesis and the STM/nc-AFM measurements were performed by A.K., M.D.G. and J.I.U. under the supervision of P.R. and R.F. The DFT nc-AFM simulations were carried out by K.E., and C.P. did the DFT constrained geometry replica chain and NEB calculations. A.K. and K.M. wrote the manuscript with input from all authors.

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Correspondence to Klaus Müllen, Carlo A. Pignedoli or Roman Fasel.

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Nature Synthesis thanks Leonhard Grill, Leo Gross and Sabine Maier for their contribution to the peer review of this work. Peter Seavill was the primary editor on this article and managed its editorial process and peer review in collaboration with the rest of the editorial team.

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Kinikar, A., Di Giovannantonio, M., Urgel, J.I. et al. On-surface polyarylene synthesis by cycloaromatization of isopropyl substituents. Nat. Synth 1, 289–296 (2022). https://doi.org/10.1038/s44160-022-00032-5

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