RUI:CAS:Reaction Dynamics of Anderson-Type Polyoxometalate Ions in Aqueous Solution: Relating Solid-State Structures with Solution-State Properties

在化学部化学结构、动力学和机理B(CSDM-B)计划和既定的刺激竞争研究计划(EPSCoR)的支持下，克雷顿大学化学和生物化学系的Eric Villa专注于确定简单的多金属氧酸盐离子(主要是阴离子金属氧化物簇合物)的结构特征如何影响它们在水溶液中的反应活性。这些多金属氧酸盐(POM)离子的应用范围很广，其性能包括抗病毒/抗肿瘤活性、酸催化、水氧化催化、磁共振造影剂、发光和磁性材料，以及潜在的放射性废物处理。这项研究的目的是了解POMS在水溶液中如何反应，以及是什么控制它们在溶液中的反应活性。该项目产生的数据将使POMS能够更好地适应这些重要的应用。该项目面向本科生进行基础研究，并对他们进行无机化学方面的培训，其中包括几种分析技术和仪器方法。本科生还将参与建立和实施以无机化学为重点的中学化学夏令营。本项目致力于了解Anderson型POM离子(XMo6O24z-)在水溶液中的稳定性和反应性。在这里，主要目标是确定X原子同一性的变化如何改变离子在水溶液中的性质，以便能够关联结构-性质关系。安德森式的POM只有三种结构氧，使其成为本科生研究人员了解水溶液反应性复杂性的理想结构。重要的是，POMS在水介质中的一般反应性趋势还没有被清楚地确定，并且仍然有许多悬而未决的问题：1)什么类型的氧位置交换最快？2)什么只影响单个位置而不是什么影响整个单元？3)什么结构性质(键长、电荷状态或质子化)与反应性相关？4)观察到的趋势有多普遍？5)关键的是，可以很容易地预测POMS在水中的反应性吗？6)最后，单一的、有针对性的金属取代如何影响POM与放射性阳离子的替代物形成稳定络合物的能力以用于修复目的？安德森式的小型POMS将允许本科生研究人员自信地探索上述问题，收集的数据将允许更好地调整这些离子以适应他们令人印象深刻的一系列应用。该奖项反映了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 support from the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) Program of the Chemistry Division and the Established Program to Stimulate Competitive Research (EPSCoR), Eric Villa of the Department of Chemistry and Biochemistry at Creighton University is focused on determining how the structural features of simple polyoxometalate ions (predominately-anionic metal-oxide clusters) affect their reactivity in aqueous solution. The range of applications for these polyoxometalate (POM) ions is wide, with properties including antiviral/antitumor activity, acid catalysis, water oxidation catalysis, MRI contrast agents, luminescent and magnetic materials, and potentially radioactive waste treatment. The goal of this research is to understand how POMs react in aqueous solution and what controls their reactivity in solution. The resulting data from this project will allow for POMs to be better tuned for these important applications. This project engages undergraduate students in fundamental research and gains them training in inorganic chemistry, which includes several analytical techniques and instrumental methods. Undergraduate students will also be involved in the set-up and delivery of a middle school chemistry summer camp focusing on inorganic chemistry. This project focuses on understanding the stability and reactivity of Anderson-type POM ions (XMo6O24z-) in aqueous solution. Here, the primary goal is to pinpoint how changes in the identity of atom X alters the ion’s properties in aqueous solution to be able to correlate structure-property relationships. The Anderson-type POM has only three types of structural oxygen, making it an ideal structure for undergraduate researchers to appreciate the complexities of aqueous solution reactivity. Importantly, the general reactivity trends of POMs in aqueous media have not been clearly identified and still have many unanswered questions: 1) What types of oxygen sites exchange the fastest? 2) What affects only a single site versus what affects the entire unit? 3) What structural properties (bond lengths, charge state or protonation) correlate with reactivity? 4) How general are the trends observed? 5) Critically, can the reactivity of POMs in water be easily predicted? 6) Finally, how do single, targeted metal substitutions affect the ability of the POM to make stable complexes with surrogates of radioactive cations for remediation purposes? The small Anderson-type POMs will allow undergraduate researchers to confidently probe the above questions and the data collected will allow for the ability to better tune these ions to their impressive set of applications.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.