Synthesis and Study of Dynamic Halogen Bonding [1]Rotaxanes for Anion Recognition and Sensing

本论文的研究课题是动态卤键[1]轮烷的合成与阴离子识别传感研究。本项目福尔斯属于EPSRC物理科学研究主题和合成超分子化学研究领域。作为牛津大学啤酒研究小组的一员，我正在努力增加对生物系统中分子识别过程的理解，以便能够生产新的分子传感器，开关和设备。我的研究项目的目标是构建分子lasso型[1]轮烷，其在阴离子识别时被设计为经历延伸和收缩的平移动态穿梭行为。这涉及新化合物的合成以及使用NMR、UV-可见光、荧光和电化学技术，以研究互锁结构和阴离子识别后的动态穿梭行为。另一个目的是对[1]轮烷进行改性以使其在水中可操作。互锁分子由于其独特的三维空腔结构而被研究作为阴离子识别的主体系统，这些空腔可以以高亲和力结合互补阴离子。结合小分子识别和分子运动，进一步探索了分子机器等互锁系统在纳米技术中令人兴奋的潜在应用。由于阴离子在一系列生物过程中的重要性，阴离子传感器引起了极大的兴趣，这开辟了一系列全新的潜在应用。这种应用将需要系统在水性环境中起作用。因此，该研究项目的一部分可能涉及[1]轮烷的改性，以使其在水中可溶且稳定。卤素键合是一种分子间相互作用，在固态体系中已被广泛研究，但在溶液化学中了解较少。然而，富电子阴离子被认为与卤素具有强烈的相互作用，并充当卤素键合受体。使用阴离子作为卤素键合系统的一部分，可以使它成为[1]轮烷形成的模板。此外，卤素键合已成功地用于能够在水中操作的阴离子主体系统中。尽管人们对互锁结构有很大的兴趣，但[1]轮烷的例子仍然很少，特别是与[2]轮烷的例子相比。因此，成功合成用于阴离子识别和传感的新型动态卤素键合[1]轮烷将使人们对这类互锁结构及其潜在应用有新的认识。

The current topic of my research project is the synthesis and study of dynamic halogen bonding [1]rotaxanes for anion recognition and sensing. This project falls within the EPSRC physical science research theme and synthetic supramolecular chemistry research area. As part of the Beer Research Group at the University of Oxford, I am working towards increasing the understanding of molecular recognition processes in biological systems in order to be able to produce new molecular sensors, switches and devices. The objectives of my research project are to construct molecular lasso-type [1]rotaxanes which upon anion recognition are designed to undergo extended and contracted translational dynamic shuttling behaviour. This involves the synthesis of novel compounds as well as using NMR, UV-visible, fluorescence and electrochemical techniques in order to study the interlocked structure and the dynamic shuttling behaviour upon anion recognition. A further objective is the modification of a [1]rotaxane in order to make it operational in water. Interlocked molecules are being studied as host systems for anion recognition due to their unique structures containing three dimensional cavities which can bind complementary anions with high affinity. Combining small molecule recognition with molecular motion further explores the exciting potential nanotechnological applications of such interlocked system as molecular machines. Anion sensors are of great interest due to the importance of anions in a range of biological processes, which opens up a whole new range of potential applications. Such applications would require the system to function in an aqueous environment. Part of the research project could therefore involve the modification of a [1]rotaxane in order for it to be soluble and stable in water. Halogen bonding is a type of intermolecular interaction that has been widely studied in solid state systems but is less understood for solution chemistry. However, electron rich anions are thought to have strong interactions with halogens and act as halogen-bonding acceptors. Using the anion as part of the halogen-bonding system could then allow it to template the formation of a [1]rotaxane. Halogen bonding has furthermore been successfully used in anion host systems, which are capable of operating in water. Despite the great interest in interlocked structures, examples of [1]rotaxanes are still rare especiallycompared to examples of [2]rotaxanes. A successful synthesis of a novel dynamic halogen bonding [1]rotaxane for anion recognition and sensing would therefore allow new insights into this class of interlocked structures and its potential applications.