Formation of chalcogenide-templated inorganic clusters via building block control

Purcell, Jamie W. (2017) Formation of chalcogenide-templated inorganic clusters via building block control. PhD thesis, University of Glasgow.

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This body of work is concerned with the synthesis and characterisation of new inorganic clusters based on the [Mo2O2S2]2+ dimeric unit. By utilising simple chalcogenide building blocks, we have discovered several collections of new compounds and gained valuable insight into the self-assembly process that governs the formation of inorganic supramolecular materials.

Three clusters were successfully discovered and characterised with the tellurite anion, TeO32-, as the only template- the first confirmation that this species is is able to act as a template in this system with no other templating agents present. The template was observed to form five different building blocks with the dimer, which then combined to form the full clusters. While the basic architecture is consistent with precedents that had already been set for this chemistry, none of the building blocks had been observed before. This template was found to have a remarkable symmetry lowering effect on the structures, with the first fully inorganic chiral polyoxothiometalate cluster a part of this set.

When the squarate anion, C4O42-, a species already proven to template a vast array of structures in this system, was introduced to add an element of competition between the two templates, another new collection of four compounds was discovered. A valuable discovery here was that squarate was the preferred template, as shown by the fact that most of the building blocks from which these compounds were derived had been observed before in compounds where squarate was the only template present. Over the course of this investigation, it was observed that no variable has a greater influence over the reaction system than pH, and identifying the optimal pH ranges for each compound allowed for the creation of a rudimentary map of the parameter space that governs the self-assembly process

With the selenite anion being established as a viable POTM template in previous work, it was also added to the squarate anion so it could compete in a similar manner to tellurite. In addition to this, mononuclear molybdate anions were added to the system as a third potential templating agent in an effort to increase the competition even further. The results of these studies were the discovery of five new compounds, two from the dual-templated reactions, and three compounds from reactions with three templates present. These compounds were based on a common library of three building blocks, one of which was newly discovered with these compounds.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Inorganic chemistry, coordination chemistry, materials chemistry, structural determination, self-assembly, chalcogenides, polyoxometalates, inorganic synthesis, supramolecular chemistry.
Subjects: Q Science > QD Chemistry
Colleges/Schools: College of Science and Engineering > School of Chemistry
Supervisor's Name: Cronin, Prof. Lee
Date of Award: 2017
Embargo Date: 28 November 2021
Depositing User: Dr Jamie Purcell
Unique ID: glathesis:2017-8723
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 23 Feb 2018 15:27
Last Modified: 30 Nov 2020 10:31

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