Catalysis in Single Crystalline Materials: From Discrete Molecules to Metal-Organic Frameworks

Catalysis is one of the key techniques for people's modern life. It has created numerous essential chemicals such as biomedicines, agricultural chemicals and unique materials. Heterogeneous catalysis is the new emerging method with reusable catalysts. Among heterogenous catalysis patterns developed so far, single crystalline catalysis has become the promising one owing to its high catalytic density and selectivity resulted by the inherent porosity, orderliness of the lattices and permeability. These crystalline catalysts could be used in various reactions such as photo-dimerization, Diels-Alder reaction, CO₂ transformation and so on. In this review, we highlighted the reported works about the single crystalline catalysts. Both discrete small molecules and metal-organic frameworks (MOFs) have been used to prepare single crystals for catalysis. For discrete molecules based crystalline catalysts, coordinated and covalent molecules have been used. There were more catalytic modes in crystalline MOF catalysts. Three patterns were identified in this review: single crystalline MOFs i) without catalytic sites, ii) with inherent catalytic features and iii) with introducing catalytic units by post synthetic modification. Based on these examples, this review committed to provide the inspirations for the further design and application of single crystalline materials.