Tuning Magnetic Properties of Two-Coordinate Metal Complexes

线性二配位过渡金属配合物是一类罕见但有吸引力的化合物，由于它们的反应性和显着的磁性。最近的报告表明，这种复合物的能力，作为单分子磁体（SMM）。SMM是充当单独磁体的分子，因为它们在去除外部磁场时保持其磁性。SMM在信息存储、量子计算和分子自旋电子学中具有重要的应用价值。目标-该项目的目的是使用计算方法来确定哪些线性双坐标结构将具有最理想的SMM属性，然后合成和优化它们。因此，整个项目将包括计算部分和实验部分。该项目第一部分的目的是使用计算方法分析线性双配位M（I）和M（II）过渡金属配合物的磁性。- 计算模拟将在以前文献中发现的线性复合物的晶体结构和几何修饰的结构上运行，以确定其电子结构，配体-金属相互作用和磁性的变化。结构将被系统地研究，以确定磁性如何随着几何形状的改变而变化的任何趋势。这些趋势将用于确定什么结构将提供最理想的SMM特性。该项目的第二部分将集中在合成的建议结构和表征，以确认其SMM properties.Methods-计算化学将包括基于Hartree-Fock理论，密度泛函理论（DFT），自洽场（SCF）和微扰理论的方法。合成将需要使用空气和水分敏感的化合物，如卡宾，低配位金属和低氧化态金属，因此必须使用惰性条件-表征将涉及光谱技术（NMR，EPR，Evans方法）和X射线晶体学，然后与Murugesu教授（渥太华大学）合作使用SQUID磁力计测量磁性。该项目福尔斯属于EPSRC的主题“物理科学”，并有助于“计算和理论化学”和“凝聚态物质：磁性和磁性材料”的研究领域。

Background Linear two-coordinate transition metal complexes are a rare but attractive class of compounds due to their reactivity and remarkable magnetic properties. Recent reports demonstrated the ability of such complexes to act as single molecular magnets (SMMs). SMMs are molecules which act as individual magnets as they maintain their magnetism upon removal of an external magnetic field. SMMs are desirable for their applications in information storage, quantum computing and molecular spintronics. Objectives- The aim of the project is to use computational methods to determine which linear two-coordinate structures will have the most desirable SMM properties, then synthesise and characterise them. So overall the project will consist of a computational part and an experimental part.- The aim for the first part of the project is to analyse the magnetic properties of linear two-coordinate M(I) and M(II) transition metal complexes using computational methods. - Computational simulations will be run on the crystal structures of linear complexes found in previous literature and on geometrically modified structures to determine changes in their electronic structure, ligand-metal interactions and magnetic properties.- Structures will be studied systematically to determine any trends in how magnetic properties change with geometry modifications. These trends will be used to determine what structures will give the most desirable SMM properties.- The second part of the project will be focused on synthesis of proposed structures and characterization to confirm their SMM properties.Methods- Computational chemistry will include methods based on Hartree-Fock theory, density functional theory (DFT), self-consistent field (SCF) and perturbation theory.- Synthesis will require use of air and moisture sensitive compounds, such as carbenes, low-coordinate metals and low oxidation state metals, so inert conditions must be used- Characterization will involve spectroscopic techniques (NMR, EPR, Evans method) and X-ray crystallography, followed by measurements of magnetic properties with a SQUID magnetometer in collaboration with Prof. Murugesu (University of Ottawa). The project falls under the EPSRC theme of "Physical Sciences" and contributes to "Computational and theoretical chemistry" and "Condensed matter: magnetism and magnetic materials" research areas.