Figure 3. UV/Vis spectra of all three Au 32 clusters 1 Et (blue), 1 Pr (orange), and 1 Bu (green) in dichloromethane. The spectra show one clear band at 480 nm, three weak bands at 600, 662, and 727 nm, and five shoulders at 395, 448, 510, 538, and 565 nm. Angewandte ChemieCommunications 5904 www.angewandte.org

The collective properties of self-assembled nanoparticles with long-range order bear immense potential for customized electronic materials by design. However, to mitigate the shortcoming of the finite-size distribution of nanoparticles and thus, the inherent energetic disorder within assemblies, atomically precise nanoclusters are the most promising building blocks. We report an easy and broadly applicable method for the controlled self-assembly of atomically precise Au32(nBu3P)12Cl8 nanoclusters into micro-crystals. This enables the determination of emergent optoelectronic properties which resulted from long-range order in such assemblies. Compared to the same nanoclusters in glassy, polycrystalline ensembles, we find a 100-fold increase in the electric conductivity and charge carrier mobility as well as additional optical transitions. We show that these effects are due to a vanishing energetic disorder and a drastically reduced activation energy to charge transport in the highly ordered assemblies. This first correlation of structure and electronic properties by comparing glassy and crystalline self-assembled superstructures of atomically precise gold nanoclusters paves the way towards functional materials with novel collective optoelectronic properties.

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