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Real-time monitoring of reaction stereochemistry through single-molecule observations of chirality-induced spin selectivity

Nature Chemistry volume 15, pages 972–979 (2023)Cite this article

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Abstract

Stereochemistry has an essential role in organic synthesis, biological catalysis and physical processes. In situ chirality identification and asymmetric synthesis are non-trivial tasks, especially for single-molecule systems. However, going beyond the chiral characterization of a large number of molecules (which inevitably leads to ensemble averaging) is crucial for elucidating the different properties induced by the chiral nature of the molecules. Here we report direct monitoring of chirality variations during a Michael addition followed by proton transfer and keto–enol tautomerism in a single molecule. Taking advantage of the chirality-induced spin selectivity effect, continuous current measurements through a single-molecule junction revealed in situ chirality variations during the reaction. Chirality identification at a high sensitivity level provides a promising tool for the study of symmetry-breaking reactions and sheds light on the origin of the chirality-induced spin selectivity effect itself.

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Fig. 1: Monitoring of the Michael reaction in a molecular junction setup.
Fig. 2: Complete description of the Michael addition on a routine Au/Cr/graphene/single molecule/graphene/Cr/Au device.
Fig. 3: Single-molecule spin filtering and the CISS effect.
Fig. 4: Real-time monitoring of chirality variations during the reaction.

Data availability

Additional discussions and data supporting this article are available in the Supplementary Information. 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, 2017YFA0204901 and 2021YFA1200101), National Natural Science Foundation of China (22150013, 22173050, 21727806 and 21933001), Tencent Foundation (through the Xplorer Prize), Natural Science Foundation of Beijing (2222009) and Frontiers Science Center for New Organic Matter at Nankai University (63181206). Y.D. acknowledges support from the Israel Science Foundation (1360/17). S.Z. and Z.L. appreciate support from the High-Performance Computing Platform of the Center for Life Science (Peking University) and High-Performance Computing Platform of Peking University.

Author information

Author notes

  1. These authors contributed equally: Chen Yang, Yanwei Li.

Authors and Affiliations

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

    Chen Yang, Shuyao Zhou, Yilin Guo, Zhirong Liu & Xuefeng Guo

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

    Yanwei Li

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

    Yanwei Li & Kendall N. Houk

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

    Chuancheng Jia & Xuefeng Guo

  5. Department of Chemistry, Ben-Gurion University of the Negev, Be’er-Sheva, Israel

    Yonatan Dubi

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  1. Chen Yang
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Contributions

X.G., Y.D. and K.N.H. conceived of and designed the experiments. C.Y., Y.G. and C.J. fabricated the devices and performed the device measurements. Y.D., Y.L., S.Z. and Z.L. built and analysed the theoretical model and performed the quantum transport calculation. X.G., Y.D., K.N.H. and C.Y. analysed the data and wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Kendall N. Houk, Yonatan Dubi or Xuefeng Guo.

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The authors declare no competing interests.

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Nature Chemistry thanks Ismael Diez Perez, Kun Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary methods and Figs. 1–49.

Source data

Source Data Fig. 2

I−t curves, corresponding histogram and potential energy surface and statistical source data.

Source Data Fig. 3

Experimental and simulated I–V curves and CISS polarization.

Source Data Fig. 4

I–t curves, corresponding histogram and potential energy surface.

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Yang, C., Li, Y., Zhou, S. et al. Real-time monitoring of reaction stereochemistry through single-molecule observations of chirality-induced spin selectivity. Nat. Chem. 15, 972–979 (2023). https://doi.org/10.1038/s41557-023-01212-2

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