Synthetic Control of Lanthanide Physical Properties Using Functionalized Metallacrowns

在化学系化学结构、动力学和机理B(CSDM-B)计划的支持下，密歇根大学安娜堡分校的文森特·L·佩科拉罗教授将研究新型金属分子的合成，这些分子可用于各种实际应用，如发光成像、温度测量和在广泛的重要技术范围(150-400K)上的温度测量。作为这些研究的组成部分，Pecoraro团队将致力于对外加磁场和外加磁场中稀土离子的电子结构有一个基本的了解。这些研究将被用于一系列应用，从理解用于量子计算机的基于镧系分子的量子比特的产生，到测量电子材料或细胞和组织的精确温度。与奥尔良生物物理学分子中心(CBM)和巴黎萨克雷大学的科学家开展的研究合作将拓宽这两个国家受训人员的经验。这些研究的结果将在世界范围内传播，并可能提供与从白光发光二极管的开发到微电子学以及细胞生物学和医学的约瑟夫森结的各种应用直接相关的基础科学基础。在美国和欧洲计划的公共教育宣传介绍/活动中也将使用有针对性的金属制品。这项提议的主要目标是在两个主要领域发展多金属化合物：创新的发光剂和金属冠芯树枝状大分子。本研究方案的主要目的是进一步了解镧系元素的电子结构，并利用官能化的金属冠醚来开发镧系元素的优异发光性能。科学合作将有助于将这项工作的影响扩大到生物成像或材料科学等领域。由于金属陶瓷可以结合不同的模块化组件，相同/相似的支架将被用来实现这些镧系金属冠系统的不同目标。这些体系非常适合于制造创新的发光成像剂、新型纳米温度计和稳定的金属树枝状大分子。重点将是将Ga和Ln基金属冠状发射体的激发能转换为红色，以便为近红外发射研究提供更具生物兼容性的发色团。为了实现这一目标和其他目标，分子将被合成和提纯，以澄清这些稀土络合物的基本电子结构，例如使用斯塔克光谱。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。

With the support of the Chemical Structure, Dynamics, and Mechanisms-B (CSDM-B) Program in the Division of Chemistry, Professor Vincent L. Pecoraro of the University of Michigan, Ann Arbor will study the synthesis of new metal based molecules that may serve a variety of practical applications such as luminescent imaging, temperature measurements across a broad, technologically important range (150-400 K). As an integral part of these studies, the Pecoraro team will work to develop a fundamental understanding of the electronic structure of lanthanide ions in and out of applied magnetic fields. The studies will be utilized in applications ranging from understanding the production of qubits from lanthanide based molecules used in quantum computers, to measuring precise temperatures for electronic materials or cells and tissues. Research collaborations with scientists at the Centre Biophysique Moleculaire (CBM) in Orleans and University of Paris-Saclay will broaden the experience of trainees from both countries. The results of these studies will be disseminated worldwide and could provide basic science foundations directly relevant to applications varying from the development of white light emitting diodes, to microelectronics and to Josephson junctions for cell biology and medicine. The targeted metallacrowns will also be used in the public educational outreach presentations/activities planned both in the United States and Europe. The main objective of this proposal is the development of MCs in two main areas: innovative luminescent agents and metallacrown-cored dendrimers. The primary objective of this research proposal is to further the understanding of lanthanide electronic structure and to exploit the superb luminescence properties of the lanthanides using functionalized metallacrowns. Scientific collaborations are included that will help expand the impact of this work to areas such as biological imaging or material science. As MCs can incorporate different modular components, the same/similar scaffolds will be used to achieve the varied objectives of these lanthanides metallacrown systems. These systems are well suited to make innovative luminescent imaging agents, novel nanothermometers, and stable metallodendrimers. Emphasis will be placed on shifting the excitation energies for Ga- and Ln-based metallacrown emitters to the red, to provide a more biologically compatible chromophore for near infrared emission studies. To achieve this and other goals, molecules will be synthesized and purified in order to clarify the fundamental electronic structure of these lanthanide complexes, using, for example, Stark spectroscopy.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.