Double-helical assembly of heterodimeric nanoclusters into supercrystals

DNA has long been used as a template for the construction of helical assemblies of inorganic nanoparticles.sup.1-5. For example, gold nanoparticles decorated with DNA (or with peptides) can create helical assemblies.sup.6-9. But without such biological ligands, helices are difficult to achieve and their mechanism of formation is challenging to understand.sup.10,11. Atomically precise nanoclusters that are protected by ligands such as thiolate.sup.12,13 have demonstrated hierarchical structural complexity in their assembly at the interparticle and intraparticle levels, similar to biomolecules and their assemblies.sup.14. Furthermore, carrier dynamics can be controlled by engineering the structure of the nanoclusters.sup.15. But these nanoclusters usually have isotropic structures.sup.16,17 and often assemble into commonly found supercrystals.sup.18. Here we report the synthesis of homodimeric and heterodimeric gold nanoclusters and their self-assembly into superstructures. While the homodimeric nanoclusters form layer-by-layer superstructures, the heterodimeric nanoclusters self-assemble into double- and quadruple-helical superstructures. These complex arrangements are the result of two different motif pairs, one pair per monomer, where each motif bonds with its paired motif on a neighbouring heterodimer. This motif pairing is reminiscent of the paired interactions of nucleobases in DNA helices. Meanwhile, the surrounding ligands on the clusters show doubly or triply paired steric interactions. The helical assembly is driven by van der Waals interactions through particle rotation and conformational matching. Furthermore, the heterodimeric clusters have a carrier lifetime that is roughly 65 times longer than that of the homodimeric clusters. Our findings suggest new approaches for increasing complexity in the structural design and engineering of precision in supercrystals. Ligand-protected gold nanoclusters are engineered to form complex arrangements of double and quadruple helices, which are based on the pairing of motifs on neighbouring enantiomers, akin to the base pairing seen in DNA double helices.
Author(s): Yingwei Li [sup.1] , Meng Zhou [sup.2] , Yongbo Song [sup.3] , Tatsuya Higaki [sup.1] , He Wang [sup.2] , Rongchao Jin [sup.1] Author Affiliations: (1) Department of Chemistry, [...]