Silver carboxylates have played a major role in thermographic and photothermographic technology since the introduction of these imaging materials in the 1950s. The nature of the bonding in these coordination compounds is sufficient to describe many of the properties needed by the silver source in order to function successfully in these imaging systems. Understanding the entire range of physical and chemical properties of silver carboxylates enables new silver sources possessing novel properties to be designed. This report describes our continuing efforts to elucidate the nature of the inorganic reaction chemistries occurring within the imaging construction, including silver-containing intermediates, such as disilver phthalate. In addition, based on the solid state structure of long chain silver carboxylates, we now report how the solid state properties of the silver carboxylates can be intentionally engineered to form novel, asymmetric silver carboxylate dimers, and what role those new materials could play in the imaging reactions based on these compounds.