Tuning Magnetic Properties of Two-Coordinate Metal Complexes

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.