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Enantioselective photoinduced cyclodimerization of a prochiral anthracene derivative adsorbed on helical metal nanostructures

Nature Chemistry volume 12, pages 551–559 (2020)Cite this article

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Abstract

The generation of molecular chirality in the absence of any molecular chiral inductor is challenging and of fundamental interest for developing a better understanding of homochirality. Here, we show the manipulation of molecular chirality through control of the handedness of helical metal nanostructures (referred to as nanohelices) that are produced by glancing angle deposition onto a substrate that rotates in either a clockwise or counterclockwise direction. A prochiral molecule, 2-anthracenecarboxylic acid, is stereoselectively adsorbed on the metal nanohelices as enantiomorphous anti-head-to-head dimers. The dimers show either Si–Si or Re–Re facial stacking depending on the handedness of the nanohelices, which results in a specific enantiopreference during their photoinduced cyclodimerization: a left-handed nanohelix leads to the formation of (+)-cyclodimers, whereas a right-handed one gives (–)-cyclodimers. Density functional theory calculations, in good agreement with the experimental results, point to the enantioselectivity mainly arising from the selective spatial matching of either Si–Si or Re–Re facial stacking at the helical surface; it may also be influenced by chiroplasmonic effects.

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Fig. 1: Schematic illustration of the photocyclodimerization of AC mediated by metal NHs.
Fig. 2: Enantioselective photocyclodimerization of AC molecules on one-pitch AgNHs having a P of ~150 nm under irradiation of 365-nm NPL.
Fig. 3: Enantioselective photocyclodimerization of AC molecules on one-pitch CuNHs having a P of ~130 nm under irradiation of 365-nm NPL.
Fig. 4: DFT calculation of the helicity-dependent photochirogenic cyclodimerization of AC.
Fig. 5: DFT calculation of charge transfer between the RH wavelike chiral Ag lattices and the adsorbed complexes.
Fig. 6: Simulation of the optical chirality at the LH-AgNH surface.

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Data availability

Data supporting the findings of this study are available within this paper and its Supplementary Information, and are available from the corresponding author upon reasonable request.

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Acknowledgements

The authors thank U. Mirsaidov and P. Nandi for technical support with HRTEM (National University of Singapore), G. Fu (Xiamen University, China) and Y. Yang (Soochow University, China) for discussions, H. Zhang (Chinese University of Hong Kong) for technical support with TEM, W. Wu (IAM, HKBU) for technical support with XRD and XPS, and financial support from NSFC/91856127/21871194/21971169/21473149/21572142/21372165, the National Key Research and Development Program of China (No. 2017YFA0505903), GRF/12200118, FRG2/17-18/058 (HKBU), FRG2/16-17/013 (HKBU) and HKBU8/CRF/11E (GLAD). G.J.X. and Y.G.W. acknowledge financial support from SUSTech and computational resource support from the Center for Computational Science and Engineering (SUSTech). C.Y. thanks the Comprehensive Training Platform of the Specialized Laboratory, College of Chemistry for financial support and P. Wu of the Analytical & Testing Center, Sichuan University, for analytical support.

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Author notes

  1. These authors contributed equally: Xueqin Wei, Junjun Liu, Guang-Jie Xia.

Authors and Affiliations

  1. Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, State Key Laboratory of Biotherapy, and Healthy Food Evaluation Research Center, Sichuan University, Chengdu, China

    Xueqin Wei, Jason J. Chruma, Wanhua Wu & Cheng Yang

  2. School of Pharmacy, Guangxi Medical University, Nanning, China

    Xueqin Wei

  3. Department of Physics, Institute of Advanced Materials, State Key Laboratory of Environmental and Biological Analysis, Golden Meditech Centre for NeuroRegeneration Sciences, Hong Kong Baptist University (HKBU), Hong Kong SAR, China

    Junjun Liu, Peng Sun & Zhifeng Huang

  4. HKBU Institute of Research and Continuing Education, Shenzhen, China

    Junjun Liu & Zhifeng Huang

  5. Department of Chemistry and Guandong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, China

    Guang-Jie Xia & Yang-Gang Wang

  6. Department of Materials Science and Engineering, SUSTech, Shenzhen, China

    Junhong Deng & Peng Sun

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Contributions

Z.F.H. and C.Y. conceived and designed the study; J.J.L. performed GLAD and material characterization; X.Q.W. and W.H.W performed photocyclodimerization and product analysis; G.J.X. and Y.G.W. performed theoretical simulations of AC photocyclodimerization; J.H.D. and P.S. performed the numerical simulation of optical chirality; Z.F.H., C.Y., Y.G.W. and J.J.C. composed the manuscript. All the authors reviewed and approved the manuscript.

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Correspondence to Cheng Yang, Yang-Gang Wang or Zhifeng Huang.

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Characterization data, computational data, Supplementary Tables 1–3, Figs. 1–23 and refs. 1–9.

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Wei, X., Liu, J., Xia, GJ. et al. Enantioselective photoinduced cyclodimerization of a prochiral anthracene derivative adsorbed on helical metal nanostructures. Nat. Chem. 12, 551–559 (2020). https://doi.org/10.1038/s41557-020-0453-0

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