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Title: Computational design of iron(II) complexes with tuneable spin-state energetics
Author: Mattock, James David
ISNI:       0000 0004 7657 406X
Awarding Body: University of Sussex
Current Institution: University of Sussex
Date of Award: 2018
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Having established and studied some of the unique properties of boron, these were applied to homoaromatic systems in order to acquire a measure of control over the strength of the through-space interaction. It became evident that the structural isomerism made possible by inserting boron centres in place of the more traditional carbocations results in significantly varied properties in similar and closely-related compounds. The variation of the strength of aromaticity allows for a perturbation in the immediate electronic environment of donor atoms to metal centres thus leading to the modulation of the relative electronic energy difference of the different spin-states of the resulting complexes. The results suggest a possible application to controlled spin-state switching technologies, for instance in the design of spin-switchable materials including stable fully controllable room-temperature spin-crossover compounds. Chapter 1 includes a discussion of relevant literature setting the context. Chapter 2 comprises a concise summary of work undertaken with multiple experimental groups to identify and characterise properties of boron compounds, this using DFT methodologies to provide a rationale for experimentally observed phenomena. Chapter 3 describes the design of a set of homoaromatic candidates stabilised with NHCs and Chapter 4 focuses on functionalising these compounds with a view towards increased exploitability. Chapter 5 assesses the viability of using an electron localisation method to identify through-space interactions. Chapter 6 documents the optimisation of the singlet excited state of [Fe(Phen)2(NCS)2] via a novel method that circumvents the usual complications of optimising these complex excited states for SCO complexes with the [Fe(bipy)3]2+ complex being included as a control. The methodologies and compound design from the preceding Chapters are collated in Chapter 7 where a homoaromatic ligand set based on a boron derivative of the homotropylium cation is designed and characterised and then applied to create a perturbation to control the spin-state energetics of a defined system. This is followed by a brief description of the possible directions of future work.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD0450 Physical and theoretical chemistry