Scientists during the past few decades have been trying to understand and control molecular self-assembly. The aim of effectively controlling the formation of building blocks at small scales lies at very foundations of any future nanotechnology utilizing inorganic systems and is vital if we are to access the room available at the bottom. Molecular metal oxides, or polyoxometalates (POMs) offer a route to achieve this control at a molecular level. In fact, POMs are an archetypal family of self-assembled molecular clusters that display a vast range of physical properties, structural features and sizes. Over the last twenty years the polyoxometalate community has developed synthetic methodologies, theoretical approaches and analytical techniques allowing to understand their complex self-assembly mechanisms and reactions. In this contribution I will describe the latest advances, building on the basic principles that rule POM self-assembly, towards the understanding of their complex chemical transformations, leading to the design of reactivity by structural control. I will focus on developments in spectroscopy and also the immense challenge of monitoring and controlling the kinetics of cluster assembly as well as how smart automation may help us with the digital design of experiments, see Figure.

Exploring the self-assembly of molecular metal oxide nanoclusters

256th National Meeting (2018)

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