CAREER: Exocyclic Imine Ligands for Electron Transfer

该奖项部分由2021年美国救援计划法案（公法117-2）资助。在化学系化学合成项目的支持下，孟菲斯大学化学系的肯莎·玛丽·克拉克（Kensha Marie Clark）将从事由氧化还原活性外环亚胺配体桥接的双金属和多金属配合物的合成。此外，还将研究这些化合物的电子和磁性能。电子应该很容易流过这些物质。因此，它们将被用于构建分子线和磁性有序材料，这些材料在能量传递、电子设备和高级计算逻辑门中具有广泛的应用。一项教育计划的目标是保留孟菲斯大学化学和其他科学专业的学生，为本科学生在普通化学序列的预科和过渡到有机化学的过程中提供支持。这些活动包括一系列旨在为学生提供第一次研究经验的训练营。本项目旨在利用π共轭外环α-二亚胺衍生的桥接配体所赋予的电子特性来开发新的电子材料。该项目利用过渡金属配合物的氧化还原非清白性，目的是：(1)预测电子和磁性行为，(2)探索配体促进的金属间相互作用，以及(3)设计新的功能分子。这些体系的优势在于共轭α-二亚胺的前沿轨道和过渡金属的d轨道的能量接近，这是过渡金属供体和桥体之间电子转移的非相干跳变机制的先决条件。该配体含有芘和芘基团，具有可预测的电子行为，可用于加强金属中心之间的电子跳变和控制分子配合物中的磁有序。具有内置方向性和合理设计的磁性分子的分子线是合成的目标。该奖项反映了美国国家科学基金会的法定使命，并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，被认为值得支持。

This award is funded in part under the American Rescue Plan Act of 2021 (Public Law 117-2).With support from the Chemical Synthesis program of the Division of Chemistry, Kensha Marie Clark of the Chemistry Department at the University of Memphis will engage in the synthesis of bimetallic and multi-metallic complexes bridged by redox-active, exocyclic imine ligands. In addition, the electronic and magnetic properties of these compounds will be studied. Electrons should readily flow through these species. Consequently, they will be deployed for construction of molecular wires and magnetically ordered materials, which have a range of applications in energy transfer, electronic devices, and logic gates for advanced computing. An educational plan targets the retention of University of Memphis chemistry and other science majors by providing support for undergraduate students during matriculation in the general chemistry sequence and during their transition into organic chemistry. These activities include a series of bootcamps that are designed to provide the students with a first research experience.This project aims to develop new electronic materials by exploiting the electronic properties imparted by bridging ligands that are derived from π-conjugated exocyclic α-diimines. The project capitalizes on redox non-innocence in transition metal complexes for the purpose of: (1) predicting electronic and magnetic behavior, (2) exploring ligand facilitated intermetallic interactions, and (3) designing of new functional molecules. The advantage of these systems stems from the energetic closeness of the frontier orbitals of conjugated α-diimines and d-orbitals of transition metals, a prerequisite for the incoherent hopping mechanism of electron transfer between the transition metal donor and the bridge. The ligands, which contain pyracene and pyrene moieties, have predictable electronic behavior that is to be utilized to enforce electron-hopping between metal centers and to control magnetic ordering in molecular complexes. Molecular wires engineered with built-in directionality and rationally designed magnetic molecules are being targeted for synthesis.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.