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A bioinspired approach for controlling accessibility in calix[4]arene-bound metal cluster catalysts

Nature Chemistry volume 2, pages 1062–1068 (2010)Cite this article

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Abstract

In enzymes, the electronic and steric environments of active centres, and therefore their activity in biological processes, are controlled by the surrounding amino acids. In a similar manner, organic ligands have been used for the ‘passivation’ of metal clusters, that is, inhibition of their aggregation and control of their environment. However, the ability of enzymes to maintain large degrees of accessibility has remained difficult to mimic in synthetic systems in which little room, if any, is typically left to bind to other species. Here, using calix[4]arene macrocycles bearing phosphines as crude mimics of the rigid backbones of proteins, we demonstrate the synthesis of gold clusters and the control of their accessibility through an interplay between the sizes of the calixarene ligands and metal cores. For 0.9-nm cores, 25% of all the gold atoms within the cluster bind to the chemisorption probe 2-naphthalenethiol. This accessibility dramatically decreases with 1.1-nm and 4-nm gold cores.

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Figure 1: Illustration of comparative synthetic approach adopted to control the accessibility of gold clusters through bulky calix[4]arene ligands.
Figure 2: Structure of molecular precursors, and images and particle size distributions of gold clusters.
Figure 3: Determination of gold cluster accessibility through the steady-state fluorescence of the 2NT probe molecule.

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Acknowledgements

The authors are grateful to Chevron Corporation for financial support of this research. The authors acknowledge the technical assistance of R. Nichiporuk in the Mass Spectrometry Facility and National Institutes of Health grant no. 10RR022393-01 for the acquisition of the Q-Tof mass spectrometer. The authors also thank F.J. Hollander and A. Dipasquale for assistance with the characterization of 1a, 1b and 1c by means of single-crystal X-ray diffraction. The authors acknowledge the support of the National Center for Electron Microscopy, Lawrence Berkeley Lab, supported by the U.S. Department of Energy under contract no. DE-AC02-05CH11231.

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Author notes

  1. Namal de Silva & Jeong-Myeong Ha

    Present address: Present address: DuPont Central Research and Development, Experimental Station, Route 141 and Henry Clay, Wilmington, Delaware 19880, USA (N.deS.); Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea (J.-M.H.),

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, 94720-1462, California, USA

    Namal de Silva, Jeong-Myeong Ha, Andrew Solovyov, Michael M. Nigra, Isao Ogino & Alexander Katz

  2. Chevron Technology Research Center, 100 Chevron Way, Richmond, 94802, California, USA

    Sheila W. Yeh

  3. College of Chemistry, University of California, Berkeley, 94720-1460, California, USA

    Kathleen A. Durkin

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Contributions

A.S. designed and synthesized all organic ligands. N.d.S. designed and performed the experiments related to the synthesis of gold complexes, crystals for X-ray diffraction and gold clusters. J.-M.H. designed and performed steady-state fluorescence experiments, HAADF-STEM characterization and NMR experiments with labelled complexes and clusters. M.M.N. and I.O. synthesized labelled gold complexes and clusters. S.W.Y. provided XPS characterization of the gold clusters. K.A.D. contributed computational modelling of the gold complexes and clusters. N.d.S., J.-M.H., A.S. and A.K. conceived the experiments and co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Alexander Katz.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 4212 kb)

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Crystallographic data for compound 1a (CIF 20 kb)

Supplementary information

Crystallographic data for compound 1b (CIF 34 kb)

Supplementary information

Crystallographic data for compound 1c (CIF 31 kb)

Supplementary information

Crystallographic data for compound 2b (CIF 48 kb)

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de Silva, N., Ha, JM., Solovyov, A. et al. A bioinspired approach for controlling accessibility in calix[4]arene-bound metal cluster catalysts. Nature Chem 2, 1062–1068 (2010). https://doi.org/10.1038/nchem.860

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