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We report an easy and broadly applicable method for the controlledself-assembly of atomically precise Au32(nBu3P)12Cl8 nanoclusters intomicro-crystals. This enables the determination of emergent optoelectronicproperties resulting from long-range order in such assemblies. Compared to thesame nanoclusters in glassy, polycrystalline ensembles, we find a 100-foldincrease in the electric conductivity and charge carrier mobility as well asadditional optical transitions. We show that these effects are due to avanishing energetic disorder and a drastically reduced activation energy tocharge transport in the highly ordered assemblies. This firststructure-transport correlation on self-assembled superstructures of atomicallyprecise gold nanoclusters paves the way towards functional materials with novelcollective optoelectronic properties.

Structural order matters: Enhanced electronic coupling in self assembled micro-crystals of Au-nanoclusters