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Mechanochemicals synthesis and modification of spin crossover materials

Askew, Jed Hugh (2019) Mechanochemicals synthesis and modification of spin crossover materials. Doctor of Philosophy (PhD) thesis, University of Kent. (KAR id:82723)

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Abstract

Spin crossover (SCO) is a phenomenon of some first-row transition metal complexes in which magnetic, optical, and structural properties change as a result of external stimuli. The change in

obtaining a SCO-active material at the end. The pursuit of novel SCO-active materials is therefore extremely slow. Mechanochemistry is an alternative synthetic technique which has recently begun to be applied to a variety of different fields, driven by the extremely short reaction times alternative reaction products and the ever-increasing importance of green chemistry. The short reaction times make mechanochemistry an ideal solution to synthesis of novel SCO materials. This study explores the application of mechanochemical synthesis to SCO research for the first

as seen in Fe(phen)2(NCS)2, Fe(4-phpy)2[Ni(CN)4] and Fe(pz)[Au(CN2)2. However, the SCO properties of mechanochemical and solution-state synthesised [Fe(atrz)3]SO4 were

Additional investigation of the differences in properties between mechanochemical and solution-state synthetic products was undertaken in Chapter 3 and showed the effects of mechanochemical synthesis are not straightforward. Mechanochemical synthesis of both [Fe(atrz)3]SO4 and Fe(pz)[Au(CN)2]2 yielded particle sizes smaller than solution-state synthesis, but the transition temperature and SCO properties of only Fe(pz)[Au(CN)2]2 were effected. Mechanochemical synthesis of [Fe(atrz)3](BF4)2 yielded a previously observed but uncharacterised

Further application of mechanochemical techniques such as solid-state metathesis, were investigated as alternative synthetic routes within mechanochemical synthesis, Chapter 4, and mwas used to successfully exchange chloride anions for both bromide and iodide in the complex [Fe(atrz)3]Cl2. The anion exchange was undertaken by post-synthetic grinding of [Fe(atrz)3]Cl2 and

A screening protocol was devised, tested, and optimised for the identification of both thermochromic and non-thermochromic SCO-active materials prepared by mechanochemistry, Chapter 5. The different analytical techniques used for routine analysis of SCO materials were assessed for their speed, cost and the information they can provide, in an attempt to address the change in the rate-limiting step that occurs through the rapid synthesis of materials using mechanochemistry.

Item Type: Thesis (Doctor of Philosophy (PhD))
Thesis advisor: Shepherd, Helena
Thesis advisor: Holder, Simon
Uncontrolled keywords: SpinCrossover SCO mechanochemistry grinding
Divisions: Faculties > Sciences > School of Physical Sciences
SWORD Depositor: System Moodle
Depositing User: System Moodle
Date Deposited: 01 Sep 2020 15:10 UTC
Last Modified: 02 Sep 2020 14:11 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/82723 (The current URI for this page, for reference purposes)
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