Finite molecular assemblies organic solid state

Finite molecular assemblies in the organic solid state toward engineering properties of solids, 40, 109... 

It is with these ideas in mind that we focus here on the design and construction of finite molecular assemblies in the organic solid state. Our intention is to provide an overview of finite assemblies with emphasis on properties that such assemblies may provide solids. We will begin by outlining general criteria for constructing finite molecular assemblies in both the solid state and solution, and then describe assemblies isolated and characterized in the solid state to date. We will then use recent advances in our laboratory to illustrate how finite assemblies can be used to control solid-state reactivity and direct the synthesis of molecules. 

The molecular assemblies described above have inspired us, in recent years, to develop finite assemblies in the solid state that exhibit chemical reactivity. Specifically, we,69 and others,70 have been utilizing principles of molecular recognition and self-assembly to develop a method to direct the formation of covalent bonds in organic solids. The method builds on the work of Schmidt on the reactivity of cinnamic acids in the organic solid state.45 Specifically, Schmidt has described topochemical postulates that dictate geometry criteria for a [2 + 2] photodimerization to occur in a solid. The postulates state that two carbon-carbon double (C=C) bonds should be aligned in parallel and separated by a distance <4.2 A to react. 

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