Synthons and design in metal phosphates and oxalates with open architectures.

Abstract

We briefly describe the structures of open-framework metal phosphates with different dimensionalities, such as the one-dimensional linear-chain and ladder structures, two-dimensional layer structures and three-dimensional structures with channels. We demonstrate the role of the zero-dimensional four-membered ring monomer and of the one-dimensional ladder structure as the starting building units or synthons involved in the formation of the complex architectures. Thus, we show how the one-dimensional ladder structure transforms to two- and three-dimensional structures under mild conditions. The two-dimensional layer structures also transform to three-dimensional structures, while the zero-dimensional monomer transforms to layered and three-dimensional structures under ordinary reaction conditions. These transformations provide an insight into the possible pathways involved in the building up of the complex structures of metal phosphates. The isolation of amine phosphates during the hydrothermal synthesis of metal phosphates and also the facile reactions between amine phosphates and metal ions to yield a variety of open-framework materials have thrown light on the mechanism of formation and design of these structures. The existence of a hierarchy of open-framework metal oxalates and their ready formation by employing amine oxalates as intermediates provides additional support to the observations made earlier with regard to the phosphates.