The coordination of transition metal cations to multifunctional organic anions has led to reports of a diverse assemblage of coordination polymers. There has been a promise that this divergent approach will result in the development of tunable, functional materials. Despite significant research efforts focused on the development of such materials for EMO applications (electronic, magnetic, optical) and porous materials for adsorption/absorption applications, this promise has remained largely unfulfilled. This presentation describes research directed toward the development of a new convergent approach to synthesize coordination polymers and discrete nanostructures. The fundamental premise is that preassembled, discrete coordination species can be linked via common organic coupling reactions to yield a new generation of coordination polymers, which cannot otherwise be generated by traditional methodologies.

Specifically, we report the successful synthesis and characterization of several discrete coordination species resulting from coupling organic species to transition metal complexes predisposed to certain organic coupling reactions. Our initial focus is on the application of organic transformations that have mild reaction conditions such as Click-reactions (e.g. the Huisgen 1,3-Dipolar Cycloaddition) and alkyne cross coupling reactions (e.g. Sonogoshira and Cadiot-Chodkiewicz reactions). We also report the synthesis and characterization of two new linear coordination polymers prepared by in-situ polymerization via a Glaser-Hay coupling (a homocoupling reaction, closely related to the Cadiot-Chodkiewicz heterocoupling reaction). Of particular interest is the synthesis of 1-D monocopper coordination polymers bridged by 4,4'-(1,3-butadiyne-1,4-diyl)bis-benzoate (Figure 1), which pack in such a way that large channels form with effective dimensions of minimally 1.2nm.