Novel Cyclodextrin-Based and Electroactive Rotaxanes

我们将探讨轮烷的化学性质。轮烷是一种超分子，其中一个头由一个线性亚基串成。头解离是由两个大的组（塞）连接到线性亚基的两端立体防止。这项工作的很大一部分将用环糊精作为珠状物的轮烷来完成。该项目将研究导致基于环糊精的自组装的基本相互作用的性质ı3！轮烷和ı4！轮烷，分别含有两个或三个环糊精珠的结构。在第二个方面的工作，轮烷将被合成环糊精头完全封装氧化还原活性基团。这些系统将允许评估溶剂重组在电子转移反应中的重要性。工作的第三个方面将研究电化学控制电子受体头的位置的可能性，该电子受体头封装在具有两个不同供体站的线程上。这项来自有机动力学项目的资助用于支持迈阿密大学安吉尔·k·凯弗教授的工作。将制备由包覆线性弦分子的头分子组成的大分子体系。大的组将被放置在绳子的两端，以防止分离的头。组装过程形成这些大分子系统将被研究。管柱的特定部分将被氧化以产生正电荷，并且将在溶剂化的背景下评估头对这一过程的影响。将研究通过氧化或还原导线上的不同站，从而改变这些站的电荷，来控制导线沿导线的运动。

The chemistry of rotaxanes will be pursued. Rotaxanes are supramolecules in which a bead is threaded by a linear subunit. Bead dissociation is sterically prevented by two bulky groups (stoppers) attached to both ends of the linear subunit. A substantial portion of this work will be done with rotaxanes in which cyclodextrins are used as the beads. This project will investigate the nature of the fundamental interactions leading to self-assembly of cyclodextrin-based ı3!rotaxanes and ı4!rotaxanes, structures with either two or three cyclodextrin beads, respectively. In a second aspect of the work, rotaxanes will be synthesized where the cyclodextrin bead completely encapsulates a redox-active group. These systems will allow an evaluation of the importance of solvent reorganization in electron transfer reactions. The third aspect of the work will investigate the possibility of electrochemically controlling the position of an electron acceptor bead encapsulated on a thread with two different donor stations. %%% This grant from the Organic Dynamics Program supports the work of Professor Angel K. Kaifer at the University of Miami. Large molecular systems will be prepared that are composed of a bead molecule which encapsulates a linear string molecule. Bulky groups will be placed at the ends of the string to prevent dissociation of the bead. The assembly process to form these large molecular systems will be studied. A particular portion of the string will be oxidized to generate a positive charge and the effect of the bead on this process will be evaluated in the context of solvation. Control of the movement of the bead along the string by oxidizing or reducing different stations on the string, and thereby changing charge at these stations, will be studied.