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Principles based on overlaps and interactions between bonding and antibonding orbitals are known to control chemical reactivity. This Perspective discusses how, for reactions and kinetics of bioinorganic species, particular pathways are also exchange-enhanced — that is, favoured by an increase in the number of unpaired and spin-identical electrons on a metal centre.
When it comes to porosity, the materials that spring to mind are typically one-, two- or three-dimensional extended networks. In this Perspective, discrete organic molecules are discussed that form porous solids — either owing to hollow molecular structures or simply through inefficient packing — with different properties from those of extended networks.
The active sites of enzymes have been widely used as the inspiration for the preparation of self-assembled catalysts. This Perspective describes a more recently adopted approach to catalyst assembly that makes use of the same interactions, but takes its inspiration from more traditional organometallic and organocatalytic approaches.
Sunlight is potentially an ideal green 'reagent' for chemical synthesis, but poor absorption by organic substrates makes direct solar photochemistry generally inefficient. Here, recent progress in the use of the simple organometallic complexes to harness the power of the sun is summarized, and prospects for the future of this exciting field highlighted.
A new concept termed 'robust dynamics' is presented as the intellectual centerpiece to the union between metal–organic frameworks (MOFs) and mechanically interlocking molecules. Robust dynamics allows highly flexible entities, which are bound covalently to MOF backbones, to carry out repeated movements without affecting the integrity of the overall structure.