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Title: Understanding metallophilic interactions
Author: Zheng, Qingshu
ISNI:       0000 0004 7654 6843
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2018
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Metallophilic (metal-metal) interactions are weak interactions between closed-shell (d10, s2) or pseudo-closed-shell (d8) metal cations. This type of interaction is generally believed to be responsible for various intriguing structures, luminescence, catalysis and magnetism. To gain a better understanding of metallophilic interactions, both experimental and computational investigations have been carried out in this thesis. Chapter 1 gave an up-to-date literature review on the definition, significance, and methods of estimating metallophilic interactions. The disputed nature and strength of metallophilic interactions encouraged us to further understand them. Chapter 2 focused on aurophilic interactions between AuI cations. Aurophilic interactions were observed in the solid state, but not well expressed in solution. Further experimental and computational results suggested that the strength of aurophilic interactions were weaker than electrostatic interactions. The nature of aurophilic interactions arose from orbital interactions rather than dispersion. Chapter 3 presented the study of metallophilic interactions between group 10 metal centres, including PtII-PtII, PdII-PdII and NiII-NiII. A series of cyclometalated square-planar metal complexes with different metals or substituents were prepared. PtII-PtII interactions were found to be stronger than PdII-PdII and NiII-NiII interactions. The dimerization constants of the Pt-containing complexes increased in line with increasing electron-withdrawing ability. Chapter 4 investigated the solvent-induced and thermally dependent colour changes of the Pt-containing complexes synthesised in chapter 3. Metallophilic interactions were proposed to be important in influencing the luminescence properties.
Supervisor: Cockroft, Scott ; Love, Jason Sponsor: European Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: metallophilic interactions ; M-M interactions ; aurophilic interactions ; platinum-platinum interactions ; Pt-containing complexes