Synthetic Control of Lanthanide Physical Properties Using Functionalized Metallacrowns

使用功能化金属冠合成控制镧系元素物理性质

• 批准号: 2154116
• 负责人: Vincent Pecoraro
• 金额: $ 56万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-15 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154116&HistoricalAwards=false
• 关键词: Synthetic; Control; Lanthanide; Physical; Properties

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.

在化学系化学结构、动力学和机理-B（CSDM-B）项目的支持下，文森特·L。密歇根大学安阿伯分校的佩科拉罗将研究新型金属基分子的合成，这些分子可能用于各种实际应用，例如发光成像、在广泛的技术重要范围内（150-400 K）的温度测量。作为这些研究的一个组成部分，佩科拉罗团队将努力对外加磁场内外的镧系离子的电子结构有一个基本的了解。这些研究将用于从理解量子计算机中使用的镧系元素分子产生量子比特到测量电子材料或细胞和组织的精确温度的应用。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进行的研究合作将扩大两国学员的经验。这些研究的结果将在全世界传播，并可提供与各种应用直接相关的基础科学基础，从白色发光二极管的开发到微电子学和细胞生物学和医学的约瑟夫森结。有针对性的金属冠也将用于计划在美国和欧洲进行的公共教育推广介绍/活动。 该提案的主要目标是在两个主要领域开发MCs：创新的发光剂和金属冠核树枝状聚合物。本研究的主要目的是进一步了解镧系元素的电子结构，并利用功能化金属冠醚的镧系元素的优异发光性能。包括科学合作，这将有助于扩大这项工作的影响，如生物成像或材料科学领域。由于MC可以包含不同的模块化组件，因此将使用相同/相似的支架来实现这些镧系金属冠醚系统的不同目标。这些系统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聚合物。重点将放在转移的Ga和Ln为基础的metallacrown发射体的激发能的红色，提供一个更生物相容的近红外发射研究的发色团。为了实现这一目标和其他目标，分子将被合成和纯化，以澄清这些镧系元素络合物的基本电子结构，例如使用斯塔克光谱学。该奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。

项目成果

Unique Dimerization Topology and Countercation Binding Modes in 12‐Metallacrown‐4 Compounds

• DOI: 10.1002/ejic.202200439
• 发表时间: 2022-09
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Elvin V. Salerno;Collin M. Foley;Vittoria Marzaroli;Bernadette L. Schneider;Max D. Sharin;J. Kampf;L. Marchiò;M. Zeller;R. Guillot;T. Mallah;M. Tegoni;V. Pecoraro;C. Zaleski

Lower Energy Excitation of Water Soluble Near‐Infrared Emitting Mixed‐Ligand Metallacrowns

水溶性近红外发射混合配体金属冠的低能量激发

• DOI: 10.1002/chem.202300226
• 发表时间: 2023
• 期刊: Chemistry – A European Journal
• 作者: Nguyen, Tu N.;Eliseeva, Svetlana V.;Martinić, Ivana;Carver, Peggy L.;Lathion, Timothée;Petoud, Stéphane;Pecoraro, Vincent L.
• 通讯作者: Pecoraro, Vincent L.