Abstract
The formation of a complete solid solution between acetylacetonate (acac) complexes of chromium and gallium, (Cr1−xGax)(acac)3 for 0.1<x<0.9, has been investigated through the co-synthesis method. Well-crystallised, subliming solids are found to form for each nominal value of x, with thermal analysis confirming each composition to have a congruent melting point, making it a substitutional complex. Whereas the pure complexes (i.e. the end members of the solid solution, x=0 and x=1) are both centrosymmetric, a composition-dependent crystallographic phase transition to a non-centrosymmetric structure is found to occur for compositions with 0.4<x<0.9. Such a “re-entrant” crystallographic transition is interpreted to be due to the drive to overcome the disorder present in certain centrosymmetric chromium-rich compositions, by going over to a non-centrosymmetric structure with a doubling of the unit cell. The substitutional complex is shown to lead to a substitutional oxide with the β-gallate structure.
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