Harnessing Pseudo One- and Two-Coordination for Reactivity and Magnetism

康奈尔大学化学与化学生物学系的凯尔兰开斯特在化学部化学结构、动力学机制-B（CSDM-B）项目的支持下，正在开发具有有趣的电子和结构性质的新型双配位和准单配位过渡金属配合物。 本研究的目标是利用这些超低配位过渡金属配合物的特性，发现用于基团转移反应的新催化剂，以及开发新的存储技术，即基于单分子磁体（SMM）的技术，以满足在逐渐变小的形状因子中增加数据存储容量的挑战。该项目协同无机合成，材料化学和物理化学的概念，非常适合作为化学研究生的教育培训。涉及K-12学生以及公众的外联活动也将得到该项目的支持。 最近的研究表明，开壳层低配位过渡金属配合物作为几个重要反应的廉价催化剂的潜力，并表现出令人鼓舞的SMM行为。本项目主要研究以下问题：1）大体积的1，8-二芳基取代咔唑能否用于合成杂配位的双配位过渡金属配合物？2)这些配体能支持伪单配位环境中的还原金属中心吗？3)二级相互作用在多大程度上稳定了反应性金属配体键？4)杂配性和金属特性在多大程度上可以用来调节配合物的电子结构并影响其磁性？该奖项反映了NSF的法定使命，并被认为是值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估的支持。

With support from the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) Program of the Chemistry Division, Kyle Lancaster of the Department of Chemistry and Chemical Biology at Cornell University is developing new classes of two- and pseudo-one-coordinate transition metal complexes with interesting electronic and structural properties. The goal of this research is to exploit the characteristics of these ultra-low-coordinate transition metal complexes for the discovery of new catalysts for group transfer reactions, as well as the development of new storage technologies, namely those based on single molecule magnets (SMMs), to meet the challenge of increasing data storage capacity in progressively smaller form factors. The project synergizes concepts of inorganic synthesis, materials chemistry, and physical chemistry, and is well suited as educational training for chemistry graduate students. Outreach activities involving K-12 students as well as the general public will also be supported by this project. Recent studies have showcased the potential of open-shell, low-coordinate transition metal complexes as inexpensive catalysts for several important reactions and have demonstrated encouraging SMM behavior. In this project, the following questions will be addressed: 1) can bulky 1,8-diarylsubstituted carbazoles be used to generally synthesize heteroleptic, two-coordinate transition metal complexes? 2) Can these ligands support reduced metal centers in pseudo-one-coordinate environments? 3) To what extent do secondary interactions stabilize reactive metal ligand linkages? 4) To what extent can heterolepticity and metal identity be used to tune the electronic structures of the complexes and influence their magnetic properties?This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.