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(NH<sub>3</sub>)<sub>6</sub>]<sub>4</sub>Cu<sub>5</sub>Cl<sub>17</sub> 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, [Cu<sub>5</sub>Cl</sub>16</sub>]<sup>11-</sup> was discovered, which has 23(T) symmetry.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:604358 |
| Date | January 1967 |
| Creators | Murray-Rust, Peter |
| Contributors | Prout, Keith |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://ora.ox.ac.uk/objects/uuid:a5979458-2d50-4bfc-b728-de1f4e0bf14d |
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