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A flow-system array for the discovery and scale up of inorganic clusters

Nature Chemistry volume 4, pages 1037–1043 (2012)Cite this article

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Abstract

The batch synthesis of inorganic clusters can be both time consuming and limited by a lack of reproducibility. Flow-system approaches, now common in organic synthesis, have not been utilized widely for the synthesis of clusters. Herein we combine an automated flow process with multiple batch crystallizations for the screening and scale up of syntheses of polyoxometalates and manganese-based single-molecule magnets. Scale up of the synthesis of these architectures was achieved by programming a multiple-pump reactor system to vary reaction conditions sequentially, and thus explore a larger parameter space in a shorter time than conventionally possible. Also, the potential for using the array as a discovery tool is demonstrated. Successful conditions for product isolation were identified easily from the array of reactions, and a direct route to ‘scale up’ was then immediately available simply by continuous application of these flow conditions. In all cases, large quantities of phase-pure material were obtained and the time taken for the discovery, repetition and scale up decreased.

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Figure 1: Reaction input parameters were altered to generate reaction arrays to be screened for the crystallization of polyoxomolybdate targets.
Figure 2: Arbitrary ratios of reagent flow rates used to create the 5 × 10 reaction arrays for screening of the syntheses of {Mo36} (1) and {Mo154} (2).
Figure 3: Charts of pH measurements for the 5 × 10 screening arrays.
Figure 4: Plot of ultraviolet–visible absorbance for diluted fractions of an {Mo154} reaction array that shows a similar periodic trend to the pH.
Figure 5: The reagent inputs to the flow-system array were switched to those relevant for the syntheses of manganese-based SMMs.
Figure 6: Percentage yield as a function of manganese concentration [Mn] and ligand concentration [L] (mol l−1) in the synthesis of compound 7.

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Acknowledgements

This work was supported by the Engineering and Physical Sciences Research Council, WestCHEM, The Leverhulme Trust and the University of Glasgow. L.C. thanks the Royal Society/Wolfson Foundation for a merit award. H.N.M. thanks the Royal Society of Edinburgh and Marie Curie Actions for financial support. We also thank J. McIver for technical assistance in assembling the electronics and flow kit.

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Authors and Affiliations

  1. WestCHEM, School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK

    Craig J. Richmond, Haralampos N. Miras, Andreu Ruiz de la Oliva, Hongying Zang, Victor Sans, De-Liang Long & Leroy Cronin

  2. School of Engineering and Design, Brunel University, Uxbridge, UB8 3PH, Middlesex, UK

    Leonid Paramonov & Charalampos Makatsoris

  3. School of Chemistry, University of Edinburgh, Kings Buildings, Edinburgh, EH9 3JJ, UK

    Ross Inglis & Euan K. Brechin

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Contributions

L.C. conceived the overall idea and designed the flow system, including the control concept. L.C. and C.J.R. designed experiments, analysed data, prepared the figures and co-wrote the manuscript. H.N.M. helped with some of the flow-system design, provided advice and assisted with crystallography. A.R. applied and corroborated the syntheses and compound analysis. D.L. solved and checked the crystallographic data. C.J.R. and L.P. co-wrote the software interface used for the programmed pump control and C.M. helped in the verification of the interface. E.K.B and R.I. provided help with the synthesis of the Mn-based complexes. V.S. provided help with chemical engineering aspects and H.Z. helped with the synthesis of compound 6.

Corresponding author

Correspondence to Leroy Cronin.

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Supplementary information

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Supplementary information (PDF 1113 kb)

Supplementary information

Crystallographic data for compound 4 (CIF 32 kb)

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Crystallographic data for compound 6 (CIF 102 kb)

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Crystallographic data for compound 9 (CIF 54 kb)

Supplementary information

Script for pumping sequences (TXT 37 kb)

Supplementary information

Script for pumping sequence for Mo96 cluster (TXT 8 kb)

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Richmond, C., Miras, H., de la Oliva, A. et al. A flow-system array for the discovery and scale up of inorganic clusters. Nature Chem 4, 1037–1043 (2012). https://doi.org/10.1038/nchem.1489

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