Chemistry of open-shell correlated materials based on unsaturated hydrocarbons

基于不饱和烃的开壳层相关材料的化学

• 批准号: EP/S026339/1
• 负责人: Matthew Rosseinsky
• 金额: $ 97.25万
• 依托单位: University of Liverpool
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2019
• 资助国家: 英国
• 起止时间: 2019 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FS026339%2F1
• 关键词: Chemistry; open; shell; correlated; materials

This is a long-range basic research project that targets the synthesis of a new crystalline materials family whose chemical, electronic and magnetic properties will create opportunities in fundamental science. To date, such advances have mainly been made in inorganic materials. This project will extend that opportunity to materials where the electronically active component is an organic anion.Our understanding of materials such as silicon and copper relies on a description of the electrons in which they do not interact strongly with each other. The electronic behaviour of materials in which the electrons do interact strongly, known as correlated materials, differs from such classical free electron materials. Correlated materials have been a fruitful source of new electronic and magnetic ground states and properties. This behaviour has overwhelmingly been observed in inorganic systems, because of the capability offered by inorganic solid state materials chemistry to position multiple distinct metal cations and thus predictably arrange spins, orbitals and charges. We have no such synthetic capability or crystal chemical understanding for organic correlated electron materials. The one example of success is the fulleride superconductors such as K3C60, where the underlying crystal chemistry is based on sphere packing that is directly analogous to well-studied inorganic systems, enabling extensive synthetic control and property design.While currently offering an outstanding range of properties, all-inorganic systems are restricted to the atoms provided by the periodic table, whose crystal and electronic structures are controlled by the ionic size and orbital characteristics of those elements. If we could achieve similar general control of structures based on electronically active organic species, such as anions derived by reduction of unsaturated molecules studied here, the resulting structural and electronic properties would be determined by the molecular size, shape and electronic structure. In contrast to the inorganic ionic systems, these steric and electronic structures of the organic molecules that would be the building blocks of such materials are controllable by synthetic chemistry.In two recent papers in Nature Chemistry, we have reported chemical synthesis approaches that produce crystalline salts of reduced unsaturated aromatic molecules and access new electronic states, including a candidate for the quantum spin liquid ground state in a three-dimensional pi-electron based material. This advance demonstrates the potential to create a family of tuneable crystalline organic electronic materials beyond the fullerides. The project will establish this family, allowing the positioning of electronically and sterically tuneable building blocks to control electronic, magnetic, optical and charge storage properties.This will be achieved by developing the synthetic chemistry capability to produce crystalline materials from a broad range of unsaturated organic molecules. To generate materials of comparable compositional and structural complexity to the inorganic systems, we will apply and expand this chemistry to materials with multiple metal sites and with more than one molecular component. This will allow us to control extended electronic structure by positioning of and charge transfer between the molecular units to target geometrically frustrated magnetic lattices and mobile charges in quantum spin liquids as examples of the new electronic ground states this chemistry will enable. The compositions, charge states and structures of the resulting hydrocarbon salts will reveal the charge storage potential of this family of materials.We will use informatics techniques to guide efficient exploration of the chemical space, and apply a range of structural, thermodynamic, spectroscopic, electronic and magnetic measurement techniques with our international collaborators to identify the new electronic states that arise.

这是一个长期的基础研究项目，旨在合成新的晶体材料家族，其化学、电子和磁性特性将为基础科学创造机会。迄今为止，这些进展主要是在无机材料方面取得的。该项目将把这个机会扩展到电子活性成分是有机阴离子的材料。我们对硅和铜等材料的理解依赖于对电子的描述，在电子中它们彼此之间不发生强烈相互作用。电子发生强烈相互作用的材料（称为相关材料）的电子行为与此类经典的自由电子材料不同。相关材料是新的电子和磁性基态和特性的丰富来源。这种行为在无机系统中已被广泛观察到，因为无机固态材料化学能够定位多种不同的金属阳离子，从而可预测地排列自旋、轨道和电荷。我们对有机相关电子材料没有这样的合成能力或晶体化学理解。成功的一个例子是富勒烯超导体，例如 K3C60，其基础晶体化学基于球体堆积，直接类似于经过充分研究的无机系统，可实现广泛的合成控制和性能设计。目前提供一系列出色的性能，全无机系统仅限于周期表中提供的原子，其晶体和电子结构由这些元素的离子大小和轨道特征控制。如果我们能够实现基于电子活性有机物质的结构的类似一般控制，例如通过还原本文研究的不饱和分子而衍生的阴离子，则所得的结构和电子特性将由分子大小、形状和电子结构决定。与无机离子系统相比，有机分子的空间和电子结构（将成为此类材料的组成部分）是可以通过合成化学控制的。在《自然化学》最近的两篇论文中，我们报道了产生结晶盐的化学合成方法减少不饱和芳香族分子并获得新的电子态，包括三维π电子材料中量子自旋液态基态的候选者。这一进展证明了创造除富勒烯之外的一系列可调谐晶体有机电子材料的潜力。该项目将建立这个系列，允许定位电子和空间可调的构建块来控制电子、磁性、光学和电荷存储特性。这将通过开发合成化学能力来实现，以从广泛的不饱和有机物中生产晶体材料分子。为了生成与无机系统具有可比较的成分和结构复杂性的材料，我们将应用这种化学并将其扩展到具有多个金属位点和多个分子组分的材料。这将使我们能够通过分子单元之间的定位和电荷转移来控制扩展的电子结构，以量子自旋液体中的几何受挫磁晶格和移动电荷为目标，作为这种化学将实现的新电子基态的例子。所得烃盐的组成、电荷状态和结构将揭示该族材料的电荷存储潜力。我们将利用信息学技术指导化学空间的有效探索，并应用一系列结构、热力学、光谱、电子学方法与我们的国际合作者合作的磁性测量技术，以确定出现的新电子态。

项目成果

High-Throughput Discovery of a Rhombohedral Twelve-Connected Zirconium-Based Metal-Organic Framework with Ordered Terephthalate and Fumarate Linkers.

• DOI: 10.1002/anie.202108150
• 发表时间: 2021-12-20
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Tollitt, Adam M.;Vismara, Rebecca;Daniels, Luke M.;Antypov, Dmytro;Gaultois, Michael W.;Katsoulidis, Alexandros P.;Rosseinsky, Matthew J.
• 通讯作者: Rosseinsky, Matthew J.