Phosphorus-containing interlocked molecules as frustrated Lewis pairs for small molecule activation

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Interlocked molecules are supramolecular architectures where two or more discrete molecules are bound together by a mechanical bond. This unique type of bond does not involve a direct bond between atoms of the molecules, and can only be broken by breaking a chemical bond within one of the molecules. For example, the mechanical bond in catenanes is analogous to how links on a chain are bound together. Another example of an interlocked molecule is a rotaxane, which consists of a dumbbell-shaped molecule threaded through a large cyclic structure, known as a macrocycle. The two components at the end of the "dumbbell" are larger than the internal diameter of the macrocyclic structure, creating a mechanical bond between the two molecules. These supramolecular species have found applications as molecular machines in which the molecular components respond to external stimuli. The 2016 Nobel Prize in Chemistry was awarded jointly to Jean-Pierre Sauvage, Fraser Stoddart and Bernard Feringa "for the design and synthesis of molecular machines". In addition, interlocked molecules have found applications as catalysts, dyes and molecular sensors.The majority of interlocked structures are made up of organic molecules (containing C, H, N, O atoms only), so the incorporation of inorganic atoms such as phosphorus into these architectures poses an interesting challenge. The incorporation of phosphorus into organic molecules has become an area of research in its own right, and has led to the discovery of many novel phosphorus-containing heterocycles. This has been achieved by the use of simple and reactive phosphorus species in well-known organic cyclisation reactions. It is these organic reactions that are often used to make up the components that form the interlocked molecules.The aim of this project is to close an obvious gap in the chemical literature, and to use simple and reactive phosphorus species in well-known organic cyclisation reactions to synthesise interlocked molecules. Ultimately, this will give rise to the incorporation of phosphorus-containing heterocycles into the interlocked molecules. Phosphorus chemistry is ubiquitous in catalysis, and we envisage that phosphorus-containing interlocked molecules could find applications in this field through the activation of covalent bonds in small molecules, such as H2, CO2 or NH3.This project falls into the "Manufacturing the Future" ESPRC theme and the following research areas:- Synthetic Supramolecular Chemistry- Synthetic Coordination Chemistry- Synthetic Organic Chemistry- Catalysis