Approaching Materials with Atomic Precision Using Supramolecular Cluster Assemblies

Supramolecular chemistry is a major area of chemistry that utilizes weaker non-covalent interactions between molecules, including hydrogen bonding, van der Waals, electrostatic, π···π, and C–H···π interactions. Such forces have been the basis of several molecular self-assemblies and host–guest complexes in organic, inorganic, and biological systems. Atomically precise nanoclusters (NCs) are materials of growing interest that display interesting structure–property correlations. The evolving science of such systems reaffirms their molecular behavior. This gives a possibility of exploring their supramolecular chemistry, leading to assemblies with similar or dissimilar cluster molecules. Such assemblies with compositional, structural, and conformational precision may ultimately result in cluster-assembled hybrid materials. In this Account, we present recent advancements on different possibilities of supramolecular interactions in atomically precise cluster systems that can occur at different length scales. We first present a brief discussion of the aspicule model of clusters, considering Au25(SR)18 as an example, that can explain various aspects of its atomic precision and distinguish the similar or dissimilar interacting sites in their structures. The supramolecular interaction of 4-tert-butylbenzyl mercaptan (BBSH)-protected [Au25(SBB)18]？ NCs with cyclodextrins (CD) to form Au25SBB18∩CDn (n = 1–4) and that of [Ag29(BDT)12]3– with fullerenes to form [Ag29(BDT)12(C60)n]3– (n = 1–9) (BDT = 1,3-benzenedithiolate) are discussed subsequently. The formation of these adducts was studied by electrospray ionization mass spectrometry (ESI MS), optical absorption and NMR spectroscopy. In the subsequent sections, we discuss how variation in intercluster interactions can lead to polymorphic crystals, which are observable in single-crystal X-ray diffraction. Taking [Ag29(BDT)12(TPP)4]3– (TPP = triphenylphosphine) clusters as an example, we discuss how the different patterns of C–H···π and π···π interactions between the secondary ligands can alter the packing of the NCs into cubic and trigonal lattices. Finally, we discuss how the supramolecular interactions of atomically precise clusters can result in their hybrid assemblies with plasmonic nanostructures. The interaction of p-mercaptobenzoic acid (p-MBA)-protected Ag44(p-MBA)30 NCs with tellurium nanowires (Te NWs) can form crossed-bilayer precision assemblies with a woven-fabric-like structure with an angle of 81° between the layers. Similar crossed-bilayer assemblies show an angle of 77° when Au102(p-MBA)44 clusters