Reactive solid-state materials: From molecular co-crystals to functional solids

The high degree of regularity and surprising flexibility of organic solids can offer synthetic access to molecules difficult to achieve otherwise. Chemical reactivity within organic solids can meet the degree of molecular organization conferred by enzymes. However, it remains difficult to control reactivity in the solid state owing to the sensitivity of crystal architecture on molecular structure.;In this thesis, principles of crystal engineering are exploited to control solid-state reactivity in the form of the [2+2] photodimerization. In particular, metal-mediated template-controlled solid-state synthesis is used as a means to: (i) affect photophysical properties of organic solids, (ii) construct reactive host-guest complexes and (iii) achieve reactivity of terminal olefins. The approach is based on coordination-driven self-assembly and employs coordination bonds to control reactivity in solids. The modularity of the approach is exploited to achieve homologous reactivity among a series of solids based on metal-organic Schiff-base Zn (II) complexes. Moreover, the modular reactivity is utilized as a foundation to fine-tune the fluorescence properties of such solids. The approach is also shown to afford solids that exhibit single-crystal-to-single-crystal reactivity. The construction of these solids bears relevance to the field of material science owing to an ability to merge reactivity and fluorescence into one material.;The metal-mediated solid-state synthesis approach is extended further to the construction of complex reactive host-guest supramolecular assemblies such as a 1D coordination polymer and metallosupramolecular complexes. The approach led to the synthesis of solids in which reactivity (e.g. [2+2] photodimerization) alters the bulk properties of the host-guest behavior. The results are promising and applications of such solids could be realized in the fields of supramolecular and host-guest chemistry.;The metal-mediated reactivity approach has also been applied to terminal olefins, which result in the stereocontrolled and quantitative formation of head-to-head photoproducts.