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Dynamic control of chirality and self-assembly of double-stranded helicates with light

Abstract

Helicity switching in biological and artificial systems is a fundamental process that allows for the dynamic control of structures and their functions. In contrast to chemical approaches to responsive behaviour in helicates, the use of light as an external stimulus offers unique opportunities to invert the chirality of helical structures in a non-invasive manner with high spatiotemporal precision. Here, we report that unidirectional rotary motors with connecting oligobipyridyl ligands, which can dynamically change their chirality upon irradiation, assemble into metal helicates that are responsive to light. The motor function controls the self-assembly process as well as the helical chirality, allowing switching between oligomers and double-stranded helicates with distinct handedness. The unidirectionality of the light-induced motion governs the sequence of programmable steps, enabling the highly regulated self-assembly of fully responsive helical structures. This discovery paves the way for the future development of new chirality-dependent photoresponsive systems including smart materials, enantioselective catalysts and light-driven molecular machines.

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Figure 1: Schematic representation of the design and concept of the dynamic double-stranded helicates.
Figure 2: 1H NMR spectra of (P,P)-trans-L1, (M,M)-cis-L1, (P,P)-cis-L1 and the corresponding Cu(I) complexes.
Figure 3: 1H NMR spectra of (P,P)-trans-L2, (M,M)-cis-L2, (P,P)-cis-L2 and the corresponding Cu(I) complexes.
Figure 4: Determination of the absolute configuration of L2-Cu2.
Figure 5: Programmed dynamic assembly processes of L1-Cu and L2-Cu2 induced by light and heat.

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Acknowledgements

This work was supported financially by the European Research Council (Advanced Investigator Grant no. 227897 to B.L.F.), the Netherlands Organization for Scientific Research (NWO-CW), the Ministry of Education, Culture and Science (Gravitation Program 024.001.035), the Royal Netherlands Academy of Arts and Sciences (KNAW) and NRSC-Catalysis. The authors thank W.R. Browne for discussions. Dedicated to Jean-Marie Lehn on the occasion of the 50th anniversary of his Laboratory.

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D.Z. and B.L.F. conceived the project. D.Z. designed, synthesized and tested the compounds. T.v.L. synthesized L1. J.C. carried out the DFT modelling. B.L.F. guided the research. B.L.F. and D.Z. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Ben L. Feringa.

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The authors declare no competing financial interests.

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Zhao, D., van Leeuwen, T., Cheng, J. et al. Dynamic control of chirality and self-assembly of double-stranded helicates with light. Nature Chem 9, 250–256 (2017). https://doi.org/10.1038/nchem.2668

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