Mathematics and art converge in the fractal forms that also abound in nature. We used molecular self-assembly to create a synthetic, nanometer-scale, Sierpinski hexagonal gasket. This nondendritic, perfectly self-similar fractal macromolecule is composed of bis-terpyridine building blocks that are bound together by coordination to 36 Ru and 6 Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.

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Hexameric metallomacrocycles are a new class of ordered rigid-macromolecules which possess unique structural, electronic, and physical characteristics. Directed- and self-assembly methods for the construction of these stable bis(terpyridine)-based materials are investigated by using both Fe(II) and Ru(II) as the coordinating metals. These heterometallomacrocycles and their homocounterparts are structurally compared, and their attendant electrochemical properties are analyzed and evaluated. These studies demonstrate the potential to create stable, nanoscale, doughnut-shaped, molecular assemblies with envisioned ramifications for energy storage and release, as well as nanoscale molecular electronic and magnetic devices.

[Chemical reaction: See text] Benzotriazole reagents for thioacylation (RCSBt), thiocarbamoylation (RR'NCSBt), aryl/alkoxythioacylation (ROCSBt), and aryl/alkylthiothioacylation (RSCSBt) are synthesized, and their utility is assessed by syntheses of representative heteroaryl thioureas 3a-g, thioamides 15a-s, thionoesters 16a-h, thiocarbamates 17a-e, dithiocarbamates 18a-d, thiocarbonates 19a-c, and dithiocarbonates 20a-c.

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