Designing Libraries of First Generation AB3 and AB2 Self-Assembling Dendrons via the Primary Structure Generated from Combinations of (AB) y −AB3 and (AB) y −AB2 Building Blocks

Structural analysis of three libraries of up to five generations of self-assembling dendrons based on AB3, AB2, and combinations of AB3 with AB2 building blocks (Percec et al. J. Am. Chem. Soc. 2001, 123, 1302) facilitated the discovery of several nanoscale lattices previously unknown for organic compounds (3-D Pm3̄n cubic, 3-D P42/mnm tetragonal, and a crystallographically forbidden 12-fold symmetry liquid quasicrystal) and provided fundamental correlations between the molecular structure of the dendron and the shape and the diameter of the supramolecular dendrimers which, in these experiments, were limited to less than 75 Å. That study concluded that alternative design principles should be elaborated for the assembly of supramolecular dendrimers of larger dimensions. Here we report design principles, synthesis and analysis of first and higher generations AB3 and AB2 self-assembling dendrons, based on various primary structures, and combinations of (AB) y −AB3 and (AB) y −AB2 (i.e., from nondendritic AB where y = 1 to 11 and dendritic AB3 and AB2) building blocks that produced the largest structural (including six new lattices) and dimensional (100 to 217 Å diameter) diversity of supramolecular dendrimers.