title: Temperature-induced intersite charge transfer involving Cr ions in A-site-ordered perovskites ACu(3)Cr(4)O(12) (A=La and Y).
abstract: Changes in the valence state of transition-metal ions in oxides drastically modify the chemical and physical properties of the compounds. Intersite charge transfer (ISCT), which involves simultaneous changes in the valence states of two valence-variable transition-metal cations at different crystallographic sites, further expands opportunities to show multifunctional properties. To explore new ISCT materials, we focus on A-site-ordered perovskite-structure oxides with the chemical formula AA'3 B4 O12 , which contain different transition-metal cations at the square-planar A' and octahedral B sites. We have obtained new A-site-ordered perovskites LaCu3 Cr4 O12 and YCu3 Cr4 O12 by synthesis under high-pressure and high-temperature conditions and found that they showed temperature-induced ISCT between A'-site Cu and B-site Cr ions. The compounds are the first examples of those, in which Cr ions are involved in temperature-induced ISCT. In contrast to the previously reported ISCT compounds, LaCu3 Cr4 O12 and YCu3 Cr4 O12 showed positive-thermal-expansion-like volume changes at the ISCT transition.
authors: Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan), Fax: (+81) 774-38-3118.
authors: Shoubao
authors: S
authors: Zhang
authors: Takashi
authors: T
authors: Saito
authors: Masaichiro
authors: M
authors: Mizumaki
authors: Yuichi
authors: Y
authors: Shimakawa
keywords: charge transfer; high-pressure synthesis; perovskite phases; valence degeneracy