Stable Localized 1,3-Diradicals Based on Boron and Heavier Main Group Elements

Guy Bertrand博士，加州大学河滨分校化学系，由化学系无机、生物无机和有机金属化学项目资助，研究基于硼和较重的主族元素的稳定的、局域化的1,3-二自由基。近年来，一些含有硼和磷原子交替的四元环化合物已被证明以单线态双自由基的形式存在。本项目旨在扩大这类化合物的范围，表现为双自由基，并确定控制双自由基性质的因素。改进PBPB双自由基的合成将被设计以提供一系列的化合物。这些将用于评估取代基对相对能量和对双自由基单线态/三重态间隙的影响。为了增加双自由基的性质，单线态双自由基会形成延伸的低聚物。最后，将寻找以硼、碳和其他14族原子为基础的新的二自由基族。综合研究将以理论预测为指导。可在标准实验室条件下处理的双自由基的可用性将提高实际应用的可能性，例如导电非金属材料。此外，该项目处于物理、有机和无机化学的交叉点，因此非常适合各级科学家的教育。反映加州大学河滨分校作为少数族裔服务机构的分类，多元化的学生团体将参与该项目。这项研究还将促进加州大学河滨分校和几所法国大学之间的合作研究和本科生、研究生和博士后的交流。

Dr. Guy Bertrand, Chemistry Department, University of California - Riverside, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for studies of stable, localized 1,3-diradicals based on boron and heavier main group elements. Recently some four-membered ring compounds containing alternating boron and phosphorus atoms have been shown to exist as singlet diradicals. This project aims to extend the range of such compounds that behave as diradicals and determine the factors that control the diradical character. Improved syntheses of PBPB diradicals will be devised to provide a range of compounds. These will be used to evaluate the influence of substituents on the relative energy and on the singlet/triplet gap of the diradicals. To increase the diradical character, singlet diradicals will be formed as extended oligomers. Finally, new families of diradicals based on boron, carbon, and other group 14 atoms will be sought. The synthetic investigations will be guided by theoretical predictions.The availability of diradicals that can be handled under standard laboratory conditions will raise the likelihood of practical applications, such as conductive non-metallic materials. Additionally, this project is at the interface between physical, organic and inorganic chemistry and is therefore well suited to the education of scientists at all levels. Reflecting the University of California - Riverside's classification as a minority serving institution, a diverse student body will be involved in the project. This research will also promote collaborative research and the exchange of undergraduates, graduates and postdoctoral fellows between UC Riverside and several French universities.