Theoretical studies of actinide complexation with macrocyclic ligands: identifying synthetic targets and real-world applications

锕系元素与大环配体络合的理论研究：识别合成靶点和实际应用

• 批准号: EP/J002208/2
• 负责人: Andrew Kerridge
• 金额: $ 30.45万
• 依托单位: Lancaster University
• 依托单位国家: 英国
• 项目类别: Fellowship
• 财政年份: 2014
• 资助国家: 英国
• 起止时间: 2014 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FJ002208%2F2
• 关键词: Theoretical; studies; actinide; complexation; macrocyclic

I propose to investigate the chemical interaction between uranyl and a series of porphyrins. Uranyl is an oxygen complex of the heavy element uranium and porphyrins are large, ringlike carbon-based molecules. Several of these chemical complexes have been created in laboratories, and I envisage the results of my research having applications as diverse as nuclear fuel enrichment, radiation detection, cancer therapy, and solar energy. In addition, my work will identify complexes that research chemists should focus their efforts on synthesising in the laboratory as well as demonstrating that state-of-the-art theoretical methods can and must be applied to these complexes in order to give a quantitative understanding of their chemical structure.The porphyrins can be considered as molecular rings, or macrocycles, with a central cavity in which other atoms and molecules can reside, and the variety of applications I have suggested is possible since they can be easily modified in order to change their properties:-Their size can be altered, so that they can be tailored to 'fit' with uranyl to varying degrees.-They can be modified so that they evaporate more readily when heated.-Related macrocycles enable one to choose the type of atom with which the uranyl directly interacts.-They can be altered so that the strength with which they bind uranyl can be varied.An important part of my proposed work is that it is computational: all of my direct research will be via simulation. Simulation plays a greater role in research into the actinide series of elements, which includes uranium, than in other areas of chemistry, since all actinides are radioactive, some of them extremely so, and there are very few facilities in the world where chemists can work with them. This means that less laboratory work can be performed, and so accurate simulation is a requirement in order to further our understanding of these elements.My proposed research employs extremely sophisticated theoretical techniques in order to study uranyl porphyrin complexes. Whilst there has been some previous simulation work on such complexes, it has been carried out using less accurate methods. The realisation of the potential applications that I have outlined are dependent on specific details of the interactions between the porphyrins and the uranyl. Such details are often unavailable directly from experiment; theoretical techniques with strong predictive capabilities are therefore a necessity. In my previous research I have shown that popular theoretical methods may not be capable of even qualitative descriptions of actinide complexes, particularly for the heavier actinides such as plutonium, and it is only in the present day that computational resources are available to conduct simulations capable of quantitative predictions on such relatively large complexes. As part of my proposed research I also intend to study the interactions of the porphyrins with other actinide elements. Other actinides can behave very differently to uranium, and understanding when and how they differ are fundamental questions in heavy element chemistry. The properties of the porphyrins that I have described allow many different aspects of these fundamental questions to be considered.In summary, the significant theoretical study that I propose here will complement the excellent experimental work being carried out both in universities and national laboratories in the United States. Whilst the primary goal of this work is the realisation of the applications I have outlined, it will also set new standards in the simulation of large molecular systems, and deepen our understanding of the chemistry of the actinide series.

我建议研究铀酰与一系列卟啉之间的化学作用。铀酰是重元素铀的氧络合物，而卟啉是大的环状碳基分子。其中几个化学复合体已经在实验室中创建，我预计我的研究结果将应用于核燃料浓缩、辐射检测、癌症治疗和太阳能。此外，我的工作将确定研究化学家应该集中精力在实验室中合成的络合物，并证明最先进的理论方法可以而且必须应用于这些络合物，以便对其化学结构进行定量了解。卟啉可以被认为是分子环或大环，其中有一个中心空腔，可以容纳其他原子和分子，我已经提出的各种应用是可能的，因为它们可以很容易地改变其性质：-它们的大小可以改变。这样它们就可以在不同程度上与铀酰相适应。-它们可以被修改，这样它们在受热时更容易蒸发。-相关的大环使人们能够选择铀酰直接与之相互作用的原子类型。-它们可以改变，以便它们与铀酰结合的强度可以改变。我提议的工作的一个重要部分是它是计算性的：我所有的直接研究都将通过模拟进行。与化学的其他领域相比，模拟在包括铀在内的鳗系元素的研究中发挥着更大的作用，因为所有的鳗系元素都是放射性的，其中一些是极具放射性的，而且世界上很少有化学家可以与之合作的设施。这意味着可以进行更少的实验室工作，因此需要准确的模拟来加深我们对这些元素的理解。我提出的研究采用了非常复杂的理论技术来研究铀酰卟啉配合物。虽然以前对这类复合体进行了一些模拟工作，但使用的方法不太精确。我所概述的潜在应用的实现取决于卟啉和铀酰之间相互作用的具体细节。这样的细节往往不能直接从实验中获得；因此，具有强大预测能力的理论技术是必要的。在我以前的研究中，我已经表明，流行的理论方法可能甚至无法定性地描述榄系元素络合物，特别是对于钚等较重的辐系元素，直到今天，才有计算资源可用于进行能够对相对较大的络合物进行定量预测的模拟。作为我提议的研究的一部分，我还打算研究卟啉与其他鳗系元素的相互作用。其他氡系元素的行为可能与铀非常不同，了解它们何时以及如何不同是重元素化学中的基本问题。我所描述的卟啉的性质允许考虑这些基本问题的许多不同方面。总而言之，我在这里提出的重要的理论研究将补充美国大学和国家实验室正在进行的出色的实验工作。虽然这项工作的主要目标是实现我所概述的应用，但它也将在大分子系统的模拟中设定新的标准，并加深我们对榄系元素系列化学的理解。

项目成果

Coordination Chemistry and QTAIM Analysis of Homoleptic Dithiocarbamate Complexes, M(S2CNiPr2)4 (M = Ti, Zr, Hf, Th, U, Np).

• DOI: 10.1021/acs.inorgchem.8b00077
• 发表时间: 2018-08
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Andrew C. Behrle;Alexander J. Myers;A. Kerridge;J. Walensky

Dithio- and Diselenophosphinate Thorium(IV) and Uranium(IV) Complexes: Molecular and Electronic Structures, Spectroscopy, and Transmetalation Reactivity.

• DOI: 10.1021/acs.inorgchem.5b01342
• 发表时间: 2015-12
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Andrew C. Behrle;A. Kerridge;J. Walensky

Ligand size dependence of U-N and U-O bond character in a series of uranyl hexaphyrin complexes: quantum chemical simulation and density based analysis.

• DOI: 10.1039/c6cp08783c
• 发表时间: 2017-03
• 期刊: Physical chemistry chemical physics : PCCP
• 作者: P. Di Pietro;A. Kerridge

Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

• DOI: 10.3390/inorganics3040482
• 发表时间: 2015-12-01
• 期刊: INORGANICS
• 影响因子: 2.9
• 作者: Beekmeyer, Reece;Kerridge, Andrew
• 通讯作者: Kerridge, Andrew

Emergence of comparable covalency in isostructural cerium(iv)- and uranium(iv)-carbon multiple bonds.

• DOI: 10.1039/c6sc00278a
• 发表时间: 2016-05-01
• 期刊: Chemical science
• 影响因子: 8.4
• 作者: Gregson M;Lu E;Tuna F;McInnes EJL;Hennig C;Scheinost AC;McMaster J;Lewis W;Blake AJ;Kerridge A;Liddle ST
• 通讯作者: Liddle ST