A Long Pathway to the Quantitative Assembly of Metallodendrimers

This overview describes our research progression from the study of heterocycle synthesis to dendritic architecture to simple metallomacrocycles, and finally to complex, fractal-based, suprametallomolecular materials. Construction of the first terpyridine-modified dendritic scaffold was followed by the construction and self-assembly of polyterpyridine monomers. Preparation of tristerpyridine building blocks used in concert with bisterpyridine analogs facilitated access to a SierpiAski gasket, as verified by direct visual observation with UHV-STEM, as well as other techniques. Numerous examples of heteroleptic self-assembly are described that include the quantitative preparation of a SierpiAski triangle. Addition of angled spacer moieties within polyterpyridine building blocks has generated a new family of 3D spherical materials that has facilitated the construction of hybrid fractal-dendritic materials that exhibit the unexpected concentration mediated, architectural transformations.