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Full on-device manipulation of olefin metathesis for precise manufacturing

Nature Nanotechnology volume 20, pages 246–254 (2025)Cite this article

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Abstract

Olefin metathesis, as a powerful metal-catalysed carbon–carbon bond-forming method, has achieved considerable progress in recent years. However, the complexity originating from multicomponent interactions has long impeded a complete mechanistic understanding of olefin metathesis, which hampers further optimization of the reaction. Here, we clarify both productive and hidden degenerate pathways of ring-closing metathesis by focusing on one individual catalyst, using a sensitive single-molecule electrical detection platform. In addition to visualizing the full pathway, we found that the conventionally unwanted degenerate pathways have an unexpected constructive coupling effect on the productive pathway, and both types of pathway can be regulated by an external electric field. We then pushed forward this ability to ring-opening metathesis polymerization involving more interactive components. With single-monomer-insertion-event resolution, precise on-device synthesis of a single polymer was achieved by online manipulation of monomer insertion dynamics, intramolecular chain transfer, stereoregularity, degree of polymerization and block copolymerization. These results offer a comprehensive mechanistic understanding of olefin metathesis, exemplifying infinite opportunities for practical precise manufacturing.

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Fig. 1: Schematic of a single-catalyst junction focusing on RCM and ROMP.
Fig. 2: Electrical characterization and signal assignment for RCM at single-catalyst junctions.
Fig. 3: Manipulation of backbiting in ROMP.
Fig. 4: Stereo control of ROMP.
Fig. 5: Precise synthesis of block copolymers.

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Data availability

The data supporting the findings of this study are available within the paper and Supplementary Information. The datasets used in Supplementary Information are available online from the Zenodo repository at https://doi.org/10.5281/zenodo.13777604. Source data are provided with this paper.

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Acknowledgements

We acknowledge primary financial support from the National Key R&D Program of China (2022YFE0128700 (to X.G.) and 2021YFA1200101 (to X.G.)), the National Natural Science Foundation of China (22150013 (to X.G.) and 21933001 (to X.G.)), the New Cornerstone Science Foundation through the XPLORER PRIZE (to X.G.), Beijing National Laboratory for Molecular Sciences (BNLMS-CXXM-202407 (to X.G.)), the Natural Science Foundation of Beijing (2222009 (to X.G.)), ‘Frontiers Science Centre for New Organic Matter’ at Nankai University (63181206 (to X.G.)), the Taishan Scholars Program of Shandong Province (tsqn202211012 (to Y.L.)), the China National Postdoctoral Program for Innovative Talents (BX20220014 (to C.Y.)), the National Natural Science Foundation of China (22303003 (to C.Y.)), the General Project of China Postdoctoral Science Foundation (2023M730049 (to C.Y.)), the China National Postdoctoral Program for Innovative Talents (BX20230024 (to Y.G.)) and the General Project of China Postdoctoral Science Foundation (2023M740065 (to Y.G.)).

Author information

Author notes

  1. These authors contributed equally: Yilin Guo, Chen Yang, Lei Zhang.

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, National Biomedical Imaging Centre, College of Chemistry and Molecular Engineering, Peking University, Beijing, People’s Republic of China

    Yilin Guo, Chen Yang, Lei Zhang, Yan Xu & Xuefeng Guo

  2. Department of Chemical Physics, University of Science and Technology of China, Hefei, People’s Republic of China

    Yujie Hu & Xingxing Li

  3. Centre of Single-Molecule Sciences, Institute of Modern Optics, Frontiers Science Centre for New Organic Matter, College of Electronic Information and Optical Engineering, Nankai University, Tianjin, People’s Republic of China

    Jie Hao, Chuancheng Jia & Xuefeng Guo

  4. Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA, USA

    Yang Yang

  5. School of Materials Science and Engineering, Peking University, Beijing, People’s Republic of China

    Fanyang Mo

  6. Environment Research Institute, Shandong University, Qingdao, People’s Republic of China

    Yanwei Li

  7. Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, USA

    Kendall N. Houk

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Contributions

X.G., Y.G. and C.Y. conceived and designed the experiments. Y.G. and C.Y. fabricated the devices and performed the device measurements. L.Z. and F.M. carried out the molecular synthesis. Y.L., Y.H., X.L. and J.H. built and analysed the computational model and performed the quantum transport calculation. X.G., F.M., Y.G., C.Y., Y.Y., K.N.H., Y.X. and C.J. analysed the data and wrote the paper. All the authors discussed the results and commented on the paper.

Corresponding authors

Correspondence to Fanyang Mo, Yanwei Li, Kendall N. Houk or Xuefeng Guo.

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Nature Nanotechnology thanks Nadim Darwish and Bingqian Xu for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Simulated potential energy profiles of different pathways in RCM.

Gibbs free energies (kcal/mol) and intermediate structures are given in the figure. Computational studies were performed with B3LYP-D3/def2TZVPP//B3LYP/ def2SVP(Ru) 6-31G(d,p)(C H O N Cl). Solvent = toluene; T = 298 K. a. Potential energy profile of the productive pathway. b. Potential energy profile of the degenerate pathway (a). c. Potential energy profile of the degenerate pathway (b). d. Potential energy profile of the degenerate pathway (c). Abbreviations: RS, reactant state; TS, transition state; IM, intermediate; PS, productive state; D, degenerate; a, metathesis pathway (a); b, metathesis pathway (b); c, metathesis pathway (c); t, trans; c, cis. RS = complex 1 + substrate; IM1 = complex 2; IM2 = complex 3; IM3 = complex 4; PS = complex 1 + product; D-a-IM = complex 5; D-b-IM-t = complex 6; D-b-IM-c = complex 7; PS-t = complex 1 + trans-product; PS-c = complex 1 + cis-product.

Extended Data Fig. 2 Statistical dynamic information of ROMP.

a. Dwell time of Ru-based alkylidene (solid line) and metallacyclobutane (dash line) in bias voltage-dependent measurements of ROMP using COE (blue line) and NBE (green line). Abbreviations: alk = alkylidene; mcb = metallacyclobutane. The error scales were derived from the statistics of three different devices (n = 3). Data are presented as mean ± s.d. τmcb was longer than τalk in the polymerization of COE (for example, at VSD = 0.1 V and COE concentration = \(1\times {10}^{-4}\) mol L−1, τmcb = 3202.6 ± 182.5 ms, τalk = 906.5 ± 10.4 ms), indicating that the ring-opening process of metallacyclobutane is the rate-determining step (RDS). As for NBE, the RDS is the formation of metallacyclobutane (for example, at VSD = 0.1 V and NBE concentration = \(1\times {10}^{-4}\) mol L−1, τmcb = 146.8 ± 3.8 ms, τalk = 468.0 ± 5.2 ms), which is consistent with the high ring strain energy of NBE. b. Polymerization rates in bias voltage-dependent measurements of ROMP using COE (blue bar) and NBE (green bar), demonstrating the high activity of NBE as the monomer in ROMP. The error scales were derived from the statistics of three different devices (n = 3). Data are presented as mean ± s.d.

Source data

Extended Data Fig. 3 Statistics of recorded photons of the polymer chain with different numbers of f-COE.

a. Schematic of the polymer chain with the segment sequence of COE(n = 20) → f-COE(n = 1) → COE(n = 20) → f-COE(n = 1) → …. b. For 20 different devices, recorded photon numbers of the polymer chain with different numbers of f-COE (1−4). For each device, the error scales were derived from the statistics of 3 independent tests (n = 3). Data are presented as mean ± s.d.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–49, Discussion, Schemes 1 and 2 and Table 1.

Supplementary Video 1

Real-time optical monitoring of the trajectory of the polymer chain terminus (that is, the fluorescent polystyrene bead) in the polymerization process. A 405 nm, 5 mW laser was focused on the graphene device through a ×100 oil lens and 5,000 photos taken with an exposure time of 50 ms. The bright pixels refer to the real-time location of the fluorescent polystyrene bead.

Source data

Source Data Fig. 2

Statistical source data for Fig. 2.

Source Data Fig. 3

Statistical source data for Fig. 3.

Source Data Fig. 4

Statistical source data for Fig. 4.

Source Data Fig. 5

Statistical source data for Fig. 5.

Source Data Extended Data Fig. 2

Statistical source data for Extended Data Fig. 2.

Source Data Extended Data Fig. 3

Statistical source data for Extended Data Fig. 3.

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Guo, Y., Yang, C., Zhang, L. et al. Full on-device manipulation of olefin metathesis for precise manufacturing. Nat. Nanotechnol. 20, 246–254 (2025). https://doi.org/10.1038/s41565-024-01814-y

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