Abstract
In an extensive study of the preparation and solid-state reactivity of transition metal phosphine complexes it was found that nearest-neighbor interactions, nucleation, temperature, doping, polymorphism and crystal symmetry greatly influenced the course of the thermal solid state reactions. With the perspective of the solid state chemistry developed by Morawetz and Schmidt, the principles and techniques developed in our laboratory have been applied to the radiation-induced solid state polymerization of metal alkynoate complexes, leading to the first rationally designed synthesis of substituted polyacetylenes in the solid state. The structural principles which led to this synthesis are described herein. The reactivity of several different monomer phases is contrasted in the context of crystal structure, metal electronic structure and radiation sensitivity.