Applying Contemporary Physical Organic Chemistry to Study Redox-Controlled Hydrogen Bonding Interactions.

利用电化学可调氢键复合物制备的主-客体复合物，由于其选择性、方向性和可调性，正迅速成为制造先进材料、传感器和机器和设备的重要构件。在拟议的工作计划中，我们的目标是利用合成化学和当代物理有机化学来创建新系统，并严格研究这些迷人的超分子组装体的基本识别特性。为了清楚起见，突出了以下任务：（1）我们将提高DAD-ADA基序中氧化还原调节的识别水平。DAD-ADA氢键模式是在生物系统中发现的常见基序。虽然在最近的文献中已经报道了这种类型的电化学可调氢键复合物的重要阵列，但这些系统报道的氧化还原增强结合的程度显著小于在生物系统中观察到的程度。如果要从这些系统制造实用的装置，这仍然是必须克服的主要障碍。在拟议的计划中，我们将开发更多的仿生主体/客体复合物，期望这些系统将导致迄今为止仅在生物系统中观察到的氧化还原调节水平的提高。(2)我们将量化结构，结合和氧化还原性质之间的关系。一旦合成了新的仿生受体并研究了它们的识别特性，我们将应用物理有机化学技术来帮助更详细地了解主体和客体的结构如何控制这些系统的结合事件和氧化还原特性。这对于解释观察到的趋势具有重要意义，也许更重要的是将提供预测能力，以帮助设计和将这些系统纳入仿生分子电子器件。(3)我们将使用实验/理论相结合的技术来探测分子识别在调节自由基阴离子物种的自旋密度中的作用。这种结合的方法将使我们能够访问实验无法获得的数据，这不仅可以提供一种方法来更深入地了解这些过程，而且还可以帮助我们设计更有效的系统。(4)我们将开发能够氧化还原可控的二元络合的受体。当前电化学可调谐氢键合主客体络合物的另一个主要不足是氧化还原调节通常限于弱状态和较强状态之间的调节。如果务实的设备是导致这些系统，这是至关重要的，系统与二进制开/关复合性能制造。为了实现这一点，我们将使用电化学来控制主客体之间的互补性。

Host-guest complexes fabricated using electrochemically tuneable hydrogen bonded complexes, due to their selectivity, directionality and tuneability, are rapidly emerging as important building blocks for the fabtication of advanced materials, sensors and machines and devices. In the proposed programme of work, we aim to use synthetic chemistry and contemporary physical organic chemistry to both create new systems and rigorously investigate the underlying fundamental recognition properties of these fascinating supramolecular assemblies. For clarity, the following tasks have been highlighted:(1) We will enhance the levels of redox modulated recognition in DAD-ADA motifs. The DAD-ADA hydrogen bond pattern is a common motif found in biological systems. Although a significant array of electrochemically tuneable hydrogen bonded complexes of this type have been reported in the recent literature, the degree of redox enhanced binding reported by these systems is significantly less than those observed in biological systems. This remains a major hurdle which must be overcome if pragmatic devices are to be fabricated from these systems. In the proposed programme, we will develop more biomimetic host/guest complexes in the expectation that these systems will lead to enhanced levels of redox modulation hitherto only observed in biological systems.(2) We will quantify the relationships between structure, binding and redox properties. Once the new biomimetic receptors have been synthesized and their recognition properties have been investigated, we will apply physical organic chemistry techniques to help provide a more detailed understanding of how the structures of the host and guest control the binding events and redox properties of these systems. This is of significant importance for explaining the trends observed, and perhaps more importantly will offer a predictive capacity to help design and incorporate these systems into biomimetic molecular electronics devices.(3) We will use a combined experimental/theoretical techniques to probe the role molecular recognition has in modulating the spin density of radical anion species. This combined methodology will allow us to access data that are unobtainable experimentally, this will not only afford a method to gain deeper insight into these processes, but could also help us to design more efficient systems. (4) We will develop receptors capable of redox controllable binary complexation. Another major shortfall of current electrochemically tuneable hydrogen bonded host guest complexes is the redox modulation is typically limited to modulation between weak and stronger states. If pragmatic devices are to result form these systems it is vital that systems with binary on/off complexation properties are fabricated. To achieve this, we will use of electrochemistry to control the complementarity between host and guest.