RUI: CAS: Solvent-Free Synthesis of Transition Metal Halide Clusters

RUI：CAS：过渡金属卤化物簇的无溶剂合成

• 批准号: 2247482
• 负责人: Dean Johnston
• 金额: $ 27.12万
• 依托单位: Otterbein College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-01 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247482&HistoricalAwards=false
• 关键词: RUI; CAS; Solvent; Free; Synthesis

With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Dean Johnston of Otterbein University will develop new synthetic routes to substituted transition metal halide cluster materials that have potential future applications in bioimaging, liquid crystal and optical devices, catalysis, oxygen sensing, and as X-ray contrast agents. This family of clusters is strongly phosphorescent and has unique electrochemical properties, making the clusters potentially useful for a wide range of applications. The central cluster core is very stable, making it an ideal building block for the creation of new chemical constructs that link cluster units to form chains or three-dimensional networks. It is important to note that current solution-based methods for preparing modified clusters are severely limited by the reactivity and solubility of the products, restricting the types of materials that can be generated and isolated. This project seeks to overcome obstacles associated with current synthetic techniques. The research team will use thermal heating and mechanical grinding of metal cluster salts to prepare novel materials with potential applications for optical devices and sensing. Undergraduate students at Otterbein University will engage with this project through summer research experiences and activities integrated into the Inorganic Chemistry laboratory, gaining valuable experience in independent research and the synthesis and characterization of inorganic materials. These research experiences will complement the activities of the Cardinal Science Scholars Program, an NSF-supported program of academic, co-curricular, and non-academic activities demonstrated to increase retention and graduation in science, technology, engineering, and mathematics (STEM).This research project is directed toward the preparation of metal cluster synthons that are intended to serve as building blocks for new molecules and materials and to allow for precise control over connectivity and dimensionality of cluster materials. Greater than ninety-five percent of all known metal halide cluster derivatives are homoleptic, illustrating the difficulty in selective ligand substitution using solution-based synthetic routes. The Johnston research team will prepare metal halide cluster salts where the cation is selected to react with the anionic cluster, using charge balance and the properties of the cation to control the stoichiometry of the reaction. Reactions will be initiated by thermal or mechanochemical means in the absence of solvent, thereby avoiding complications from solvent interference or solubility issues. The reactions and products will be analyzed using thermogravimetric analysis, in-situ Raman spectroscopy, and powder and single-crystal X-ray diffraction methods. The results of this research are expected to provide researchers in the field of inorganic cluster chemistry with synthetic tools and pathways to prepare new cluster-based materials.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.

在化学合成计划中，在化学分区的支持下，奥特比因大学的Dean Johnston教授将开发新的合成途径，以取代过渡金属卤化物簇材料，这些途径在生物成像，液晶和光学设备，催化，氧气，氧气传感以及X射线对比剂中具有潜在的未来应用。这个集群家族具有强烈的磷光，具有独特的电化学性能，使该簇可能对广泛的应用有用。中央集群核心非常稳定，这是创建新化学构建体的理想基础，这些化学构建体将群集单元连接到形成链或三维网络。重要的是要注意，当前基于解决方案的制备修饰簇的方法受到产品的反应性和溶解度受到严重限制，从而限制了可以生成和隔离的材料类型。该项目试图克服与当前合成技术相关的障碍。研究团队将使用热加热和金属簇盐的机械研磨，以准备具有光学设备和传感应用的新型材料。奥特贝因大学的本科生将通过夏季研究经验和活动融入无机化学实验室，从而获得该项目，从而获得独立研究以及无机材料的综合和表征的宝贵经验。这些研究经验将补充枢机科学学者计划的活动，由NSF支持的学术，上课程和非学术活动的计划，这些计划被证明可以增加科学，技术，技术，工程和数学（STEM）的保留和毕业。该研究项目可允许使用新的材料来制备构建和构建的构造和组成的构建群，并允许构建构建组成的组成和构建组合，并构建了构建的构建，并构建了构建的构建，并构建了构建的构建群，并提供了构建的构建。集群材料的维度。超过95％的所有已知金属卤化物簇衍生物都是同种剂，这说明了使用基于溶液的合成途径的选择性配体取代的困难。约翰斯顿研究小组将使用电荷平衡和阳离子的特性来控制阳离子与阴离子簇反应的金属卤化物簇盐，以控制反应的化学计量。在没有溶剂的情况下，将通过热或​​机械化学方法引发反应，从而避免了溶剂干扰或溶解度问题的并发症。将使用热重分析，原位拉曼光谱以及粉末和单晶X射线衍射方法对反应和产物进行分析。预计这项研究的结果将为无机集群化学领域的研究人员提供合成的工具和途径，以准备新的基于群集的材料。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛的影响来通过评估来提供支持的。