A structural investigation of some compounds showing charge-transfer properties

Thesis

Summary. 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, [Cu₅Cl

16]^11- was discovered, which has 23(T) symmetry.[See thesis for continuation of summary].

Authors: Murray-Rust, P; Peter Murray-Rust

• Publication date: 1967
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: Oxford University, UK
• Language: English
• Keywords: Charge-transfer; Paraquat; metallohalide anions; X-ray crystallography
• Subjects: X-ray crystallography