Synthetic Phosphorus Chemistry: The Systematic Development of Phosphorus-Containing Molecules and Polymers

这项研究计划的目标是系统地发展磷及其化合物的化学。磷是一种重要的元素，不仅是生命所必需的，而且被用于大量的商业产品。我们工作的主要目标是开发含有磷作为主链关键成分的聚合物。今天使用的大多数聚合物都是由含有碳、氧和/或氮原子的链组成的，这些原子具有明确的序列。由于磷的氧化状态、配位数和成键环境的广泛范围，将磷引入聚合物中提供了额外的化学功能。因此，含磷大分子具有独特的物理性能和化学功能，这是纯有机聚合物无法实现的。例如，磷可以可逆地结合到金属上，从而潜在地提供了进入聚合物开关的途径。尽管含磷聚合物的前景令人兴奋，但它们仍然极其罕见。含磷聚合物广泛使用的关键挑战是缺乏将无机元素结合到长链中的一般合成路线。烯烃的C=C键的加成聚合可能是工业聚合物生产中最重要的方法，用于制造聚乙烯、聚丙烯、聚苯乙烯、丙烯和特氟龙，仅举几例。长期以来，人们一直认为含杂原子的多键不适合加成聚合方法。我们首次将加成聚合延伸到P=C键。在这样做的过程中，我们发现P=C键是各种新分子和材料的有趣的构建块。P=C分子和聚合物的发展构成了这项提议的一个关键主题，包括在自我修复材料等新领域。我们还将开发聚异戊二烯和相关双烯的杂原子类似物的一个全新领域。聚异戊二烯是一种天然橡胶，是一种非常重要的商业产品，可以追溯到固特异的发现。通过聚合磷版本的天然橡胶，我们正在开辟天然橡胶功能版本(包括阻燃)的巨大可能性。在最后一个追求领域，我们正在开发具有独特光物理性质的p-共轭聚合物。这些材料中磷的存在可以起到化学开关的作用，从而通过与某些金属分析物的结合来开启和关闭聚合物的发光。因此，这些材料作为传感器很有吸引力。最后，本文提出的工作进一步扩展了磷的迷人化学。这项工作将增加无机化学和聚合物科学的基础知识，并将为未来的技术应用提供基础。

This goal of this research proposal is to systematically develop the chemistry of phosphorus and its compounds. Phosphorus is an important element, not only being essential for life but being used in a wealth of commercial products. The primary objective of our work is to develop polymers that contain phosphorus as a key component of the main chain. Most polymers in use today are comprised of chains containing carbon, oxygen, and/or nitrogen atoms in well-defined sequences. The incorporation of phosphorus into a polymer provides a additional chemical functionality due to its wide range of oxidation states, coordination numbers and bonding environments. Thus, phosphorus-containing macromolecules possess unique physical properties and chemical functionality that are not possible with solely organic polymers. For instance, phosphorus can reversibly bind to metals, thereby potentially providing access to a polymeric on-off switch. Despite the exciting prospects for phosphorus-containing polymers, they are still extremely rare. The key challenge to the widespread usage of P-containing polymers is the lack of general synthetic routes to incorporate inorganic elements into long chains. The addition polymerization of the C=C bond of olefins is perhaps the most important method of industrial polymer production being used to make polyethylene, polypropylene polystyrene, acrylics, and Teflon, to name a few. It was long believed that heteroatom-containing multiple bonds were not suited for addition polymerization methods. We were the first to extend addition polymerization to P=C bonds. In doing so, we discovered that P=C bonds are fascinating building blocks for a variety of new molecules and materials. The development of P=C molecules and polymers comprises a key topic of this proposal, including in new areas such as self-healing materials. We will also develop an entirely new area of heteroatom analogues of poly(isoprene) and related dienes. Polyisoprene is natural rubber, a hugely important commercial going back to the discovery of Goodyear. By polymerizing phosphorus-versions of natural rubber, we are opening up huge possibilities of functional versions of natural rubber (including flame retardancy). In a final area of pursuit, we are developing p-conjugated polymers with unique photophysical properties. The presence of phosphorus in these materials can function as a chemical switch whereby the luminescence of the polymer may be turned on and off through the binding to certain metal analytes. Thus, these materials are attractive as sensors. In closing, the work proposed herein further expands the fascinating chemistry of phosphorus. This work will lead to gains in fundamental knowledge of inorganic chemistry and polymer science, and will provide a foundation for future technological applications.