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

联锁分子是两个或多个离散分子通过机械键结合在一起的超分子结构。这种独特的键不涉及分子原子之间的直接键，只能通过破坏其中一个分子内的化学键来断开。例如，链烷中的机械键类似于链上的链接是如何结合在一起的。环锁分子的另一个例子是轮烷，它由一个哑铃形状的分子穿过一个被称为大环的大环结构组成。“哑铃”末端的两个组分大于大环结构的内径，在两个分子之间形成了机械键。这些超分子物种已经发现了作为分子机器的应用，其中分子成分对外部刺激作出反应。2016年诺贝尔化学奖由Jean-Pierre Sauvage、Fraser Stoddart和Bernard Feringa共同获得，以表彰他们“设计和合成分子机器”。此外，互锁分子已被用作催化剂、染料和分子传感器。大多数联锁结构是由有机分子组成的（只包含C、H、N、O原子），因此将磷等无机原子结合到这些结构中提出了一个有趣的挑战。磷与有机分子的结合本身已经成为一个研究领域，并导致了许多新的含磷杂环的发现。这是通过在众所周知的有机环化反应中使用简单和活性磷来实现的。正是这些有机反应经常被用来构成形成连锁分子的成分。该项目的目的是填补化学文献中的一个明显空白，并在众所周知的有机环化反应中使用简单和活性的磷物种来合成联锁分子。最终，这将导致含磷杂环结合到互锁分子中。磷化学在催化中无处不在，我们设想含磷互锁分子可以通过激活小分子（如H2， CO2或NH3）的共价键在这一领域找到应用。本项目属于ESPRC“制造未来”主题，研究方向为：合成超分子化学-合成配位化学-合成有机化学-催化

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