CAREER: Exocyclic Imine Ligands for Electron Transfer

职业：用于电子转移的环外亚胺配体

• 批准号: 2344621
• 负责人: Kensha Clark
• 金额: $ 70万
• 依托单位: University of Mississippi
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-09-15 至 2028-09-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2344621&HistoricalAwards=false
• 关键词: CAREER; Exocyclic; Imine; Ligands; Electron

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.

该奖项的部分资金来自《2021年美国救援计划法案》(公法117-2)。在化学系化学合成计划的支持下，孟菲斯大学化学系的肯莎·玛丽·克拉克将参与合成由氧化还原活性的外环亚胺配体连接的双金属和多金属络合物。此外，还将研究这些化合物的电子和磁性。电子应该可以轻易地流经这些物种。因此，它们将被用于构建分子线和磁性有序材料，这些材料在能量转移、电子器件和先进计算的逻辑门中有广泛的应用。一项教育计划旨在留住孟菲斯大学化学和其他科学专业的学生，方法是在普通化学顺序的预科阶段和向有机化学的过渡期间为本科生提供支持。这些活动包括一系列训练营，旨在为学生提供第一次研究体验。该项目旨在通过利用π-共轭外环α-双亚胺衍生的桥联配体所赋予的电子性质来开发新的电子材料。该项目利用过渡金属络合物中的氧化还原非无害性来：(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。这些体系的优点来自于共轭α-二亚胺的前线轨道和过渡金属的d-轨道的能量接近，这是过渡金属施主和桥之间电子转移的非相干跳跃机制的先决条件。含有吡喃和芘部分的配体具有可预测的电子行为，可用于加强金属中心之间的电子跃迁和控制分子络合物中的磁性有序。具有内置方向性和合理设计的磁性分子的分子线正在成为合成的目标。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。