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Author
Title Magnetic Anisotropy of Transition Metal Complexes
URL
Publication Date
Degree Level doctoral
University/Publisher University of Manchester
Abstract Magnetic Anisotropy of Transition Metal Complexes: a thesis submitted to the University of Manchester for the degree of Doctor of Philosophy in the Faculty of Engineering and Physical Sciences.The study of magnetic anisotropy in molecular systems permeates the physical sciences and finds application in areas as diverse as biomedical imaging and quantum information processing. The ability to understand and subsequently to design improved agents requires a detailed knowledge of their fundamental operation. This work outlines the background theory of the electronic structure of magnetic molecules and provides examples, for elements across the Periodic Table, of how it may be employed to aid in the understanding of magnetically anisotropic molecules.The magnetic anisotropies of a series of dimetallic NiII2 complexes and a RuIII2MnII triangle are determined through multi-frequency Electron Paramagnetic Resonance (EPR) spectroscopy and ab initio calculations. The magnetic anisotropy of the former is found to be on the same order of magnitude as the isotropic exchange interactions, while that of the latter is found to be caused by large antisymmetric exchange interactions involving the RuIII ions.An intuitive electrostatic strategy for the prediction of the magnetic anisotropy of DyIII complexes is presented, allowing facile determination of magnetic anisotropy for low symmetry molecules.Through the presentation of the first near-linear pseudo-two-coordinate 4f-block complex, a new family of DyIII complexes with unprecedented Single Molecule Magnet (SMM) properties is proposed. Design criteria for such species are elucidated and show that in general any two-coordinate complex of DyIII is an attractive synthetic target.The exchange interaction between two DyIII ions is directly measured with multi-frequency EPR spectroscopy, explaining the quenching of the slow magnetic relaxation in the pure species compared to the SMM properties of the diluted form. The interpretation of this complex system was achieved with supporting ab initio calculations.Nicholas F. ChiltonFebruary 2015
Contributors MCINNES, ERIC EJL; Winpenny, Richard; Mcinnes, Eric
Language en
Country of Publication uk
Format 189 page(s)
Record ID oai:escholar.manchester.ac.uk:uk-ac-man-scw-261585
Repository manchester
Date Retrieved
Date Indexed 2019-01-09

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…statement The author of this thesis (including any appendices and/or schedules to this thesis) owns certain copyright or related rights in it (the “Copyright”) and s/he has given The University of Manchester certain rights to use such…

…policy on Presentation of Theses. 11 12 Acknowledgements Firstly I would like to thank The University of Manchester for a President’s Doctoral Scholarship, which has given me the opportunity to perform this work. Furthermore, none of this would have…

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