Template-controlled reactivity in the organic solid state by principles of coordination-driven self-assembly

In this microreview, we show how principles of coordination-driven self-assembly can be used to direct chemical reactivity in the organic solid state. We also show how products obtained from the templated solid-state reactions can be used as organic building units of metal–organic frameworks and coordination capsules. Self-assembled structures based on dinuclear ZnII and AgI complexes are used to direct stereocontrolled [2+2] photodimerizations of vinylpyridines in the solid state in up to quantitative yield. The products are used as bi- and polytopic ligands of self-assembled coordination capsules and metal–organic frameworks. We also describe emerging metal-based approaches to conduct mechanochemical reactions in organic solids. In addition to the field of supramolecular coordination chemistry, these observations impact the field of green chemistry.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)