Anisotropic Assembly of Nanocrystal/Molecular Hierarchical Superlattices Decoding from Tris-Amide Triarylamines Supramolecular Networks.

Directed assembly of nanocrystals from conventional templates suffers from poor control over the periodicity of the nanocrystal assembly, which is largely due to the fact that the template exists prior to the assembly and is not generally adaptive. Herein, small organic molecules (tris-amide triarylamines, TATA) are demonstrated as conceptual templates from self-assembly through noncovalent interactions. The as-formed supramolecular structures with terminated alkyl chains, resembling the structure of as-synthesized nanocrystals capped with alkyl chains, are able to interact with nanocrystals through van der Waals attractive forces, thereby enabling directed assembly of nanocrystals into ordered superlattices. Specifically, it is found that, as determined by the substituted alkyl chains of TATA, either H or J-aggregates of TATA can be achieved, which eventually produce several distinct supramolecular structures, from rods to spindles, to rings, and to spheres, serving as on-pathway intermediate that directs the assembly of nanocrystals into diverse nanocrystal superlattices. The approach described can be applicable to produce ordered nanocrystal assemblies of a wide range of nanocrystals, independent of size and shape and without ligand exchange process. Strikingly, a helical TATA stacking can direct assembly of binary nanocrystal mixtures into NaZn13 binary superhelix.