Developing Metallacrown Scaffolds for Luminescence, Magnetism and Supramolecular Chemistry

在这个由化学部化学结构、动态和机理B计划资助的项目中，密歇根大学安娜堡分校化学系的文森特·佩科拉罗教授正在开发被称为金属高环化合物的新类别的金属大环化合物。这些类型的络合物在磁性和成像方面表现出重要的技术性能。它们在近红外发光传感器、无机发光二极管和条形码标签以及量子计算方面具有潜在的应用。这些显像剂是可申请专利的，目前正在讨论细胞固定和坏死分析的许可问题。该项目位于有机、无机化学和生物化学的交界处。它非常适合于各级和跨国科学家的教育。它也是玛丽·居里国际研究人员交流计划的基础，该计划将欧洲各地的初级科学家带到美国进行培训，并将文森特·佩科拉罗教授团队的学生带到欧洲。涉及K-12学生和在科学方面代表性不足的学生的外联活动也是该资助项目的一部分。金属冠显示了丰富的光物理性质，包括报道的在近红外光谱区发射的最高量子产率和最高亮度的稀土分子络合物。此外，包裹在抗磁性金属冠中的双核稀土元素显示出适合作为量子比特开发量子计算机的能隙。这项拟议的工作利用这些性质来生成用于成像应用的发光树枝状大分子和Janus树状大分子。简单的金属冠状图案也将被用作节点，以开发可用于传感应用的发光金属有机骨架。这些研究拓宽了树枝状大分子和金属有机骨架的合成可能性，导致了具有磁性或发光性质的新结构类型的出现。

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Vincent Pecoraro of the Department of Chemistry at the University of Michigan, Ann Arbor is developing new classes of metallamacrocylic complexes called metallacrowns. These classes of complexes exhibit technologically important properties in magnetism and imaging. They have potential applications in near-infrared luminescent sensors, inorganic light emitting diodes and bar code labels, and quantum computing. The imaging agents are patentable and discussions are underway for licensing for cell fixation and necrosis assays. The project lies at the interface of organic, inorganic, and biological chemistry. It is well suited to the education of scientists at all levels and across international boundaries. It also serves as the basis for a Marie Curie International Research Staff Exchange Scheme program that brings junior scientists across Europe to the US for training and students from Professor Vincent Pecoraro's group to Europe. Outreach activities involving K-12 students and for students underrepresented in science are also part of the funded project. Metallacrowns display a rich array of photophysical properties, including the highest reported quantum yields and brightness for molecular Lanthanide complexes emitting in the near infrared spectral region. In addition, binuclear lanthanides encapsulated within diamagnetic metallacrowns show energy gaps that are appropriate for exploitation as qubits for the development of quantum computers. The proposed work exploits these properties to generate luminescent dendrimers and Janus dendrimers for imaging applications. The simple metallacrown motif will also be used as nodes to develop luminescent metal organic frameworks that may be used for sensing applications. These studies broaden the range of synthetic possibilities for both dendrimers and metal organic frameworks by leading to new structure types with either magnetic or luminescent properties.