Understanding metallophilic interactions
dc.contributor.advisor
Cockroft, Scott
en
dc.contributor.advisor
Love, Jason
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dc.contributor.author
Zheng, Qingshu
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dc.contributor.sponsor
European Research Council
en
dc.date.accessioned
2018-11-19T11:44:04Z
dc.date.available
2018-11-19T11:44:04Z
dc.date.issued
2018-11-29
dc.description.abstract
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.
en
dc.identifier.uri
http://hdl.handle.net/1842/33237
dc.language.iso
en
dc.publisher
The University of Edinburgh
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dc.source.uri
2019-11-29
en
dc.subject
metallophilic interactions
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dc.subject
M–M interactions
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dc.subject
aurophilic interactions
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dc.subject
platinum–platinum interactions
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dc.subject
Pt-containing complexes
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dc.title
Understanding metallophilic interactions
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dc.type
Thesis or Dissertation
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dc.type.qualificationlevel
Doctoral
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dc.type.qualificationname
PhD Doctor of Philosophy
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