Novel Cyclodextrin-Based and Electroactive Rotaxanes

将继续研究轮烷的化学性质。Rotaxanes是 超分子，其中珠被线性亚基穿过。 两个庞大的基团在空间上阻止了珠的解离 （塞子）连接到线性亚单元的两端。一 这一工作大部分将用轮烷来完成， 所述环糊精用作珠粒。该项目将 研究基本相互作用的性质， 自组装的环糊精基的<$3！轮烷和<$4！轮烷， 具有两个或三个环糊精珠的结构， 分别在工作的第二方面，轮烷将被 其中环糊精珠粒完全包封 氧化还原活性基团。这些系统将允许对 溶剂重组在电子转移中重要性 反应.第三方面的工作将调查 电化学控制的位置的可能性 电子受体珠封装在具有两个不同的 捐献站 %%% 有机动力学计划的这笔赠款支持以下工作： Angel K教授迈阿密大学的凯弗。大 将制备由珠粒组成的分子系统 一个包裹着线状分子的分子。大体积基团 将被放置在字符串的两端，以防止解离 珠子形成这些大分子的组装过程 系统将进行研究。字符串的特定部分将被 氧化产生正电荷， 将在溶剂化的背景下评估此过程。 通过氧化控制珠沿着线的运动 或减少弦上的不同位置，从而改变 这些车站的收费将被研究。

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.