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

互锁分子是两个或更多离散分子通过机械键结合在一起的超分子结构。这种独特的键类型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打破。例如，链环中的机械键类似于链上的链环如何结合在一起。另一个互锁分子的例子是轮烷，它由一个哑铃状的分子穿过一个大的环状结构组成，称为大环。“哑铃”末端的两个组分比大环状结构的内径大，在两个分子之间形成了机械键。这些超分子物种已被用作分子机器，其中的分子组件对外部刺激做出反应。2016年诺贝尔化学奖被联合授予让-皮埃尔·索瓦奇、弗雷泽·斯托达特和伯纳德·费林加，以表彰他们对分子机器的设计和合成。此外，互锁分子还被应用于催化剂、染料和分子传感器等领域，大多数互锁结构是由有机分子(只含C、H、N、O原子)组成的，因此将磷等无机原子引入这些结构中是一个有趣的挑战。将磷引入有机分子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物种来实现的。正是这些有机反应经常被用来组成形成互锁分子的组分。这个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互锁分子。最终，这将导致含磷杂环被掺入互锁分子中。磷化学在催化中是普遍存在的，我们预计含磷互锁分子可以通过激活小分子如H2、CO2或NH3中的共价键在这一领域找到应用。本项目属于ESPRC主题，包括以下研究领域：-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