Synthetic, Structural and Reactivity Studies on Supramolecules Obtained from Catechol Functionalized Macrocycles. Studies in Nb/S Chemistry

Dimitri Coucouvanis博士，密歇根大学化学系，由无机，生物无机和有机物项目支持 化学部的一个部门，负责合成、结构和反应性 邻苯二酚功能化超分子的研究 大环化合物 感兴趣的系统包括儿茶酚官能化的 能够进行分子内反应的四氮杂大环配合物 在pH变化时的电子转移， 根据冠醚中结合的物质改变它们的功能 分子的一部分，以及光学活性的“螺旋桨”分子， 可以用作能够在细胞中进行不对称诱导的载体， 烯烃的环氧化。 分子“反应器”， 用于存储电子和激活小分子的亚基 分子也将被合成， 描绘的。硫和硒配位体的化学 铌和钽络合物及其与杂联烯的反应性， 烯烃、炔烃、二氧化硫和分子氢也将被 探讨了 分子结构包括复合物的合成， 多功能系统，旨在将一个边界 底物分子，就像酶在生命系统中的作用一样。 金属大环，将金属离子结合到大环中的系统 结构，是这些所谓的“超分子”系统的例子。 这些分子可以用作基本分子器件， 在光化学诱导电荷分离中的潜在应用， 光开关、催化氧化还原过程、电子存储或基底 分子活化

Dr. Dimitri Coucouvanis, Department of Chemistry, University of Michigan, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division to perform synthetic, structural and reactivity studies on supramolecules obtained from catechol functionalized macrocycles. The systems of interest include catechol-functionalized tetraazamacrocyclic complexes capable of undergoing intramolecular electron transfer upon changes in pH, supramolecular crown ethers which change their function depending on what is bound in the crown ether portion of the molecule, and optically active `propeller` molecules which could be useful as supports capable of asymmetric induction in the epoxidation of olefins. Molecular `reactors` which contain separate subunits for both the storage of electrons and the activation of small molecules will also be synthesized and their reactivity patterns delineated. The chemistry of coordinated sulfur and selenium ligands in niobium and tantalum complexes and their reactivity with heteroallenes, alkenes, alkynes, sulfur dioxide and molecular hydrogen will also be explored. Molecular architecture involves the synthesis of complex, multi-functional systems which are designed to transform a bound substrate molecule, much the way enzymes function in living systems. Metallomacrocycles, systems which incorporate metal ions into large ring structures, are examples of these so called `supramolecular` systems. These molecules may function as elementary molecular devices with potential applications in photochemically induced charge separation, photoswitching, catalytic redox processes, electron storage, or substrate molecule activation.