CAREER: Employing ligand exchange reactions involving hypervalent compounds of iodine and other main-group elements in the synthesis of dynamic and functional polymers

在这个由化学学部大分子、超分子和纳米化学项目资助的项目中，南卫理公会大学（SMU）的Nicolay Tsarevsky教授正在开发动态聚合物的制备策略，这些聚合物能够交换它们的构建块，在化学、光或热处理下降解，自我修复或锁定它们的结构。聚合物是长链有机分子，在日常生活的许多方面都使用塑料，包括食品包装，汽车和航空航天运输的结构材料，以及轻质电子设备。材料科学的主要目标之一是开发高效，易于操作和廉价的方法来制备具有预定结构和成分的定义良好的聚合物，因为这些可以转化为特定应用的材料，例如自修复材料，复合材料，涂层以及用于药物输送或组织工程的材料。察雷夫斯基教授正在研究含有重元素的化合物是如何形成特殊类型的化学键的，这种键被称为高价键，在加热或光照射下很容易断裂。为了拓宽化学教育，察列夫斯基教授正在开发跨学科的科学-人文课程；如。“舞台上的科学”和“艺术中的化学与技术：从古代到工业革命”，探索普通公众科学教育的方法，并在新大开展“化学夏令营”。在这个项目中，Tsarevsky教授正在研究如何利用配体在碘、锑、铋、硒和碲的高价化合物[特别是- I（III）、Sb(V)、Bi(V)、Se（IV）和Te(IV)]中的交换反应来合成具有可控大分子结构的动态共价聚合物。目前正在详细研究这些材料的形成及其交换构件、降解和重新组装或自我修复的能力。所提出的动态聚合物的一个重要特征是，如果需要，它们有可能转化为具有永久链接的固定结构。Tsarevsky教授也在研究如何利用这些高价化合物将亲核试剂转化为自由基。所得到的功能自由基可与多种底物反应，包括聚合物或具有某些不饱和的植物油和脂肪酸，以及石墨材料，生成各种功能反应材料和复合材料。为了获得对控制交换反应动力学和热力学以及高价键均裂反应的因素的基本理解，正在进行许多模型反应，其中结构和组成变量正在系统地变化。

In this project funded by the Macromolecular, Supramolecular, and Nanochemistry Program of the Division of Chemistry, Professor Nicolay Tsarevsky of Southern Methodist University (SMU) is developing strategies for the preparation of dynamic polymers that are able to exchange their building blocks, be degraded upon chemical, light or thermal treatment, self-repair, or lock in their structures. Polymers are long chain organic molecules and are found in many facets of everyday life that utilize plastics, including food packaging, structural materials for automotive and aerospace transportation, and lightweight electronic devices. One of the main goals of materials science is to develop efficient, easy to conduct, and inexpensive methods for the preparation of well-defined polymers with predetermined structures and compositions, because these can be translated into materials for specific applications, such as self-healing materials, composites, coatings, and materials for drug delivery or tissue engineering. Professor Tsarevsky is studying how compounds that contain heavy elements form special types of chemical bonds, named hypervalent, that can easily be cleaved upon heating or irradiation with light. To broaden chemistry education, Professor Tsarevsky is developing interdisciplinary science-humanities courses; e.g. "Science on the Stage" and "Chemistry and Technology in Art: From Antiquity to the Industrial Revolution," exploring methods for general public science education, and developing a "Chemistry Summer Camp" at SMU.In this project, Professor Tsarevsky is studying how to use exchange reactions of ligands in hypervalent compounds of iodine, antimony, bismuth, selenium and tellurium [specifically- I(III), Sb(V), Bi(V), Se(IV), and Te(IV)] for the synthesis of dynamic covalent polymers, with controlled macromolecular architecture. The formation of these materials as well as their ability to exchange building blocks, to degrade and be re-assembled or self-repair, are being studied in detail. An important feature of the proposed dynamic polymers is that they have the potential to be converted to fixed structures with permanent links if and when needed. Professor Tsarevsky is also studying how these hypervalent compounds can be used to conver nucleophiles into radicals. The resulting functional radicals can react with a number of substrates, including polymers or plant oils and fatty acids with some unsaturation, and graphitic materials to yield various functional reactive materials and composites. To gain fundamental understanding of the factors that govern the kinetics and thermodynamics of the exchange reactions, as well as those of hypervalent bond homolysis, a number of model reactions are being conducted, in which structure and composition variables are being systematically varied.