A-site-ordered perovskite Ce1/2Cu3Ti4O12 has been found to crystallize in two different forms, one with random and the other with ordered Ce/vacancy distribution at the A site of the prototype AA'3B4O12 structure. The random phase is isostructural with CaCu3Ti4O12, and the ordered phase is a new ordered derivative of the AA'3B4O12-type perovskite with two crystallographically distinct Cu sites. Although both phases form a G-type antiferromagnetic arrangement of Cu(2+) spins below 24 K, their magnetisms are quite different. A typical antiferromagnetic transition is observed in the random phase, whereas a small ferromagnetic moment appears below 24 K in the ordered phase, which rapidly decreases upon further cooling. A mean-field approximation approach revealed that this unusual behavior in the ordered phase is an L-type ferrimagnetism driven by the nonequivalent magnetizations of the two ferromagnetic Cu(2+) spin sublattices in the G-type spin structure. This unusual ferrimagnetism is a direct consequence of the Ce/vacancy ordering.

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http://dx.doi.org/10.1021/ic402616rDOI Listing

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