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 Zn II and Ag I 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)