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On-surface synthesis of ballbot-type N-heterocyclic carbene polymers

Nature Chemistry volume 15, pages 1737–1744 (2023)Cite this article

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Abstract

N-Heterocyclic carbenes (NHCs) are established ligands for metal complexes and surfaces. Here we go beyond monomeric NHCs and report on the synthesis of NHC polymers on gold surfaces, consisting of ballbot-type repeating units bound to single Au adatoms. We designed, synthesized and deposited precursors containing different halogens on gold surfaces under ultrahigh vacuum. Conformational, electronic and charge transport properties were assessed by combining low-temperature scanning tunneling microscopy, non-contact atomic force microscopy, X-ray photoelectron spectroscopy, first-principles calculations and reactive force field simulations. The confirmed ballbot-type nature of the NHCs explains the high surface mobility of the incommensurate NHC polymers, which is prerequisite for their desired spatial alignment. The delicate balance between mobility and polymerization rate allows essential parameters for controlling polymer directionality to be derived. These polymers open up new opportunities in the fields of nanoelectronics, surface functionalization and catalysis.

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Fig. 1: General aspects of NHCs on surfaces.
Fig. 2: Self-assembly of IPrI2 on Au(111).
Fig. 3: Polymerization of IPrI2 on Au(111).
Fig. 4: Polymers acquired from IPrI2 molecules and their mobility and orientation on Au(100).
Fig. 5: Selective formation of ordered NHC polymers on Au(100).

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Data supporting the findings of this work are available within this paper or its Supplementary Information.

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Acknowledgements

F.G. and N.L.D. acknowledge financial support from the Deutsche Forschungsgemeinschaft (SFB 858 and SFB 1459), as do H.F. (SFB 858, FU 299/18-1) and H.M. (MO 2345/4-1, 519972808). Q.D. acknowledges financial support from the National Natural Science Foundation of China (U2032206) and the Strategic Priority Research Program of Chinese Academy of Sciences (XDB36000000). H.-J.G. acknowledges financial support from the National Natural Science Foundation of China (61888102) and the National Key Research and Development Program of China (2019YFA0308500). L.H. acknowledges financial support from the National Key Research and Development Program of China (2018YFA0305800). Computations were carried out using the PALMA II HPC cluster provided by the University of Münster.

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Authors and Affiliations

  1. CAS Key Laboratory of Nanophotonic Materials and Devices, CAS Key Laboratory of Standardization and Measurement for Nanotechnology, National Center for Nanoscience and Technology, Beijing, PR China

    Jindong Ren & Qing Dai

  2. Physikalisches Institut, Westfälische Wilhelms-Universität, Münster, Germany

    Jindong Ren, Bertram Schulze Lammers, Harry Mönig & Harald Fuchs

  3. Center for Nanotechnology, Münster, Germany

    Jindong Ren, Bertram Schulze Lammers, Harry Mönig & Harald Fuchs

  4. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Münster, Germany

    Maximilian Koy, Christian Gutheil, Arne Nalop & Frank Glorius

  5. Institute for Solid State Theory and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität, Münster, Germany

    Helena Osthues, Marvin Nyenhuis & Nikos L. Doltsinis

  6. Beijing National Center for Condensed Matter Physics and Institute of Physics, Chinese Academy of Sciences, Beijing, PR China

    Qi Zheng, Yao Xiao, Li Huang & Hong-Jun Gao

  7. University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, PR China

    Qi Zheng, Yao Xiao, Li Huang & Hong-Jun Gao

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  1. Jindong Ren
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Contributions

F.G. and H.F. initiated the project. F.G., H.F., H.M., M.K. and J.R. designed the experiments and coordinated the study. M.K., A.N. and C.G. designed and synthesized the molecules. J.R. and B.S.L. performed the STM measurements and analysed them with H.M. and Q.D.; H.O., M.N. and N.L.D. performed DFT and ReaxFF calculations. B.S.L., H.M. and J.R. did the nc-AFM(CuOx- tips)/XPS experiments and interpreted the data. Q.Z., L.H., Y.X., J.R. and H.-J.G. did the nc-AFM experiment using CO-functionalized tips. J.R. wrote the manuscript together with M.K., H.O., Q.D., H.M., N.L.D., H.F. and F.G. All the authors read and commented on the manuscript.

Corresponding authors

Correspondence to Hong-Jun Gao, Harry Mönig, Nikos L. Doltsinis, Harald Fuchs or Frank Glorius.

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Ren, J., Koy, M., Osthues, H. et al. On-surface synthesis of ballbot-type N-heterocyclic carbene polymers. Nat. Chem. 15, 1737–1744 (2023). https://doi.org/10.1038/s41557-023-01310-1

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