Very-High-Spin Polyradicals

这一IQ奖由化学部门的有机动态计划和先进材料计划联合颁发，以支持Andrzej Rajca博士的继续研究。将支持两项主要工作：(1)极高自旋大环聚自由基体系的设计、合成和表征，以及(2)新型碳同素异构体和基于四邻苯基结构单元的高浓缩网络固体的合成和性质的计算和实验研究。在第一个研究领域，多自由基，所有的三芳基甲基醚都是由相应的三芳基甲基醚通过碱金属还原成碳多阴离子，然后再进行碘氧化而得到的。这些拉长的大环多自由基将具有十个以上的自旋耦合电子，并将被设计为最大限度地减少中断自旋耦合的缺陷。在第二个研究领域，使用MNDO、EHT和MM3方法的固态和分子计算将提供固体的热力学稳定性和能带结构性质。实验将评估网络固体的结构，包括它们对掺杂的响应。将合成固体的分子和聚合物片段，并研究它们的溶液氧化还原化学。了解大环多自由基的行为并控制自旋耦合缺陷将使研究人员能够将它们用作二维和三维网络多自由基的构建块，从而有可能成为具有高居里温度的有机铁磁体。高密度碳网络的合成和掺杂将有利于自由基离子和双阴离子分子固体的制备，这将导致具有导电性能的新材料的出现。

This award iq made jointly by the Organic Dynamic Program and the Advanced Materials Program in the Chemistry Division in support of the continuing research of Dr. Andrzej Rajca. Two major efforts will be supported; (1) the design, synthesis and characterization of very high spin macrocyclic poyradical systems, and (2) computational and experimental studies on the synthesis and properties of new carbon allotropes and highly condensed network solids based on tetra o-phenylene structural units. In the first research area, polyradicals, all of the triarylmethyl type will be prepared from the corresponding triarylmethyl-methyl ethers by alkali metal reduction to the carbopolyanions followed by iodine oxidation. These elongated macrocyclic polyradicals will have greater than ten spin-coupled electrons and will be designed to minimize defects which interrupt spin-coupling. In the second research area, solid-state and molecular calculations using MNDO, EHT, and MM3 methods will provide thermodynamic stabilities and band structure-properties of the solids. Experiments will evaluate the structures of the network solids, including their response to doping. Molecular and polymeric fragments of the solids will be synthesized, and their solution redox chemistry investigated. Understanding the behavior of macrocyclic polyradicals and controlling spin coupling defects will allow the researcher to use them as building blocks for two and three dimensional network polyradicals, with the potential to be organic ferromagnets with high Curie temperatures. Synthesis and doping of highly condensed carbon networks will facilitate preparation of radical ion-and dianion -based molecular solids which will lead to promising new materials with conducting properties.