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Main-chain metallopolymers at the static–dynamic boundary based on nickelocene

Nature Chemistry volume 9, pages 743–750 (2017)Cite this article

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Abstract

Interactions between metal ions and ligands in metal-containing polymers involve two bonding extremes: persistent covalent bonding, in which the polymers are essentially static in nature, or labile coordination bonding, which leads to dynamic supramolecular materials. Main-chain polymetallocenes based on ferrocene and cobaltocene fall into the former category because of the presence of strong metal–cyclopentadienyl bonds. Herein, we describe a main-chain polynickelocene—formed by ring-opening polymerization of a moderately strained [3]nickelocenophane monomer—that can be switched between static and dynamic states because of the relatively weak nickel–cyclopentadienyl ligand interactions. This is illustrated by the observation that, at a low concentration or at an elevated temperature in a coordinating or polar solvent, depolymerization of the polynickelocene occurs. A study of this dynamic polymer–monomer equilibrium by 1H NMR spectroscopy allowed the determination of the associated thermodynamic parameters. Microrheology data, however, indicated that under similar conditions the polynickelocene is considered to be static on the shorter rheological timescale.

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Figure 1: Summary of monomer [n]metallocenophanes and polymetallocenes.
Figure 2: The stacked 1H NMR spectra (500 MHz, d5-pyridine, 25 °C) show the effect of the initial monomer concentration on the conversion of tricarba[3]nickelocenophane monomer 5 into polynickelocene 7.
Figure 3: Example 1H NMR spectra that show the presence of cyclic oligomers 6x in equilibrium mixtures of monomer 5 and polymer 7.
Figure 4: Stacked 1H NMR spectra (500 MHz, d5-pyridine) that show the effect of temperature on the reversible conversion of monomer 5 into polymer 7.
Figure 5: Thermodynamic ROP parameters and influence of metallocene ring tilt in [n]metallocenophanes.

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Acknowledgements

R.A.M., A.D.R., G.R.W. and I.M. thank the Engineering and Physical Sciences Research Council (EPSRC) for funding. D.W.H. is supported by a EPSRC doctoral training centre grant [EP/G036780/1]. The authors thank B. MacCreath for assistance in performing the DLS microrheology measurements.

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Authors and Affiliations

  1. School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK

    Rebecca A. Musgrave, Andrew D. Russell, Dominic W. Hayward, George R. Whittell, Paul G. Lawrence, Paul J. Gates & Ian Manners

  2. Department of Chemistry, University of Oxford, Chemical Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK

    Jennifer C. Green

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Contributions

R.A.M., A.D.R. and I.M. devised the project. R.A.M. carried out the experiments with assistance from A.D.R. The SAXS data were collected and analysed by D.W.H. Microrheology experiments were performed by R.A.M. and G.R.W. Paramagnetic NMR experiments were designed with assistance from P.G.L., mass spectrometry was performed by P.J.G. and computational chemistry was performed by J.C.G. The manuscript was written by R.A.M. with input from A.D.R., G.R.W. and I.M. The project was supervised by I.M. with input from G.R.W.

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Correspondence to Ian Manners.

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Musgrave, R., Russell, A., Hayward, D. et al. Main-chain metallopolymers at the static–dynamic boundary based on nickelocene. Nature Chem 9, 743–750 (2017). https://doi.org/10.1038/nchem.2743

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