Manipulating the Monolayer: Dynamic Covalent Nanoparticle Building Blocks

Abstract: Virtually every application of monolayer-stabilized nanoparticles requires optimization and interrogation of surface-bound chemical functionality. Yet, robust approaches for nanomaterial surface engineering are critically under-developed.¹

'Dynamic covalent nanoparticle (DCNP) building blocks' combine the error-correcting and stimuli-responsive features of equilibrium processes, with the stability and vast structural diversity of nonbiomolecular covalent chemistry, all within nanoparticle-bound monolayers. This presents a 'best-of-both-worlds' strategy for post-synthetic surface engineering, facilitating reversible modification of nanoparticle-bound functionality using methods that are essentially independent of the underlying nanomaterial.^2–5

Here I will introduce the DCNP concept using the example of hydrazone exchange within gold nanoparticle-bound monolayers; I will discuss the role that monolayer-stabilized nanoparticles can play as 'pseudomolecular' models for surface-confined chemical processes; and I will show how understanding the molecular-level details of surface-bound dynamic covalent processes can be used to achieve rational and predictable control over nanoparticle properties and assembly.

1          W. Edwards and E. R. Kay, ChemNanoMat, 2016, 2, 87–98.

2          F. della Sala and E. R. Kay, Angew. Chem. Int. Ed., 2015, 54, 4187–4191.

3          S. Borsley and E. R. Kay, Chem. Commun., 2016, 52, 9117–9120.

4          E. R. Kay, Chem. Eur. J., 2016, 22, 10706–10716.

5          W. Edwards, N. Marro, G. Turner, E. R. Kay Chem. Sci. 2018, 9, 125–133.