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Title: A structural investigation of some compounds showing charge-transfer properties
Author: Murray-Rust, Peter
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 1967
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The technique of X-ray diffraction has been used to investigate compounds which show charge-transfer properties in the solid state. It is shown how the results of structure determination can, under favourable conditions, give information about charge-transfer processes. Two sets of compounds have been studied, both of which contain metal-chloride bonds. The first is a series of mixed-valence cobalt hexammine chlorocuprates in which the average oxidation state of the copper can take any value between 1 and 2. The structure of the single-valence (copper (I)) compound, [Co(NH3)6]4Cu5Cl17 was solved and data was also collected for a compound with Cu(I)/total Cu ~ 0.25. This was shown to have a structure to the single-valence copper (I) and copper (II) compounds and probable arrangements for the Cu(I) and Cu(II) ions are presented. It is shown that linear Cu-Cl-Cu bridges are almost certainly present and that these can account for the charge-transfer spectrum. A new chlorocuprate anion, [Cu5Cl16]11- was discovered, which has 23(T) symmetry.
Supervisor: Prout, Keith Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: X-ray crystallography ; Charge-transfer ; Paraquat ; metallohalide anions