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Plasmonic visible–near infrared photothermal activation of olefin metathesis enabling photoresponsive materials

Nature Chemistry volume 15, pages 475–482 (2023)Cite this article

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Abstract

Light-induced catalysis and thermoplasmonics are promising fields creating many opportunities for innovative research. Recent advances in light-induced olefin metathesis have led to new applications in polymer and material science, but further improvements to reaction scope and efficiency are desired. Herein, we present the activation of latent ruthenium-based olefin metathesis catalysts via the photothermal response of plasmonic gold nanobipyramids. Simple synthetic control over gold nanobipyramid size results in tunable localized surface plasmon resonance bands enabling catalyst initiation with low-energy visible and infrared light. This approach was applied to the ROMP of dicyclopentadiene, affording plasmonic polymer composites with exceptional photoresponsive and mechanical properties. Moreover, this method of catalyst activation was proven to be remarkably more efficient than activation through conventional heating in all the metathesis processes tested. This study paves the way for providing a wide range of photoinduced olefin metathesis processes in particular and photoinduced latent organic reactions in general by direct photothermal activation of thermally latent catalysts.

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Fig. 1: Plasmon-induced DCPD polymerization.
Fig. 2: Moulding and printing of PPCs.
Fig. 3: Photoresponsive reaction vials.
Fig. 4: Mechanical characterization of AuBP–pDCPD composite.

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All data supporting this study can be found within the paper and the Supplementary Information and Videos. Source data are provided with this paper.

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Acknowledgements

We thank T. Lemcoff for editing all Supplementary Videos. We thank E. Nativ-Roth for taking all SEM images. We thank R. Schneck and Y. Unigovski for carrying out the tensile strength measurements. This work was supported by the Zuckerman STEM Leadership Program and the Israel Science Foundation (ISF) grant no. 2491/20 to Y.W., and ISF grant no. 506/18 to N.G.L. The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript.

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Authors and Affiliations

  1. Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva, Israel

    Nir Lemcoff, Noy B. Nechmad, Or Eivgi, Elad Yehezkel, Ofir Shelonchik, Ravindra S. Phatake, Doron Yesodi, Anna Vaisman, Aritra Biswas, N. Gabriel Lemcoff & Yossi Weizmann

  2. Ilse Katz Institute for Nanotechnology Science, Ben-Gurion University of the Negev, Beer-Sheva, Israel

    N. Gabriel Lemcoff & Yossi Weizmann

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  1. Nir Lemcoff
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Contributions

Y.W. and N.G.L. supervised the project. N.L., N.B.N. and O.E. conducted all experiments. E.Y., N.L. and O.S. set up the LED temperature regulation system. N.L., O.S., A.B. and D.Y. synthesized the nanoparticles. N.L., N.B.N., A.V. and O.E. synthesized all catalysts. R.S.P. and N.B.N. conducted the mechanical analysis experiments. N.L., O.E., N.G.L. and Y.W. wrote the manuscript.

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Correspondence to Yossi Weizmann.

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Nature Chemistry thanks Jianfang 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 Figs. 1–81 and Tables 1–7.

Supplementary Video 1

Side-by-side videos of a PPC850 film (20 OD) being irradiated with an 850 nm LED (100 W). On the left is the normal recording. On the right is the thermal camera (Flir One) recording, including its temperature reading.

Supplementary Video 2

Preparation process of photoresponsive PPC660 (20 OD) coil. Initially, the ‘soft’ polymer was shaped. After the shaping was complete, photothermal curing was achieved by irradiating with a 660 nm LED (200 W). Finally, the coil’s toughness was demonstrated.

Supplementary Video 3

Preparation process of photoresponsive PPC850 (20 OD) knot. Initially, the ‘soft’ polymer was shaped into a knot. It was then irradiated with an 850 nm LED (100 W) until photothermal curing was complete. Finally, the knot’s toughness was demonstrated; one can clearly see that cured sections are rigid, and non-cured sections are flexible.

Supplementary Video 4

Side-by-side video of a funnel blocked by the photoresponsive jojoba-derived wax (embedded with AuBP850 at 10 OD). The funnel was filled with water and then irradiated with an 850 nm LED (100 W). The wax’s photothermal response caused its melting, and the water was spilled. This simple demonstration hints at potential applications for materials of this type.

Source data

Source Data Fig. 1

Underlying raw data of Fig. 1b,c.

Source Data Fig. 3

Underlying raw data of Fig. 3c,d.

Source Data Fig. 4

Underlying raw data of Fig. 4a,b.

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Lemcoff, N., Nechmad, N.B., Eivgi, O. et al. Plasmonic visible–near infrared photothermal activation of olefin metathesis enabling photoresponsive materials. Nat. Chem. 15, 475–482 (2023). https://doi.org/10.1038/s41557-022-01124-7

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