High-pressure synthesis of metallic perovskite ruthenate CaCu 3Ga2Ru2O12

Song Ho Byeon; Seoung Soo Lee; John B. Parise; Patrick M. Woodward; Nam Hwi Hur

doi:10.1021/cm049265t

High-pressure synthesis of metallic perovskite ruthenate CaCu ₃Ga₂Ru₂O₁₂

Song Ho Byeon
, Seoung Soo Lee
, John B. Parise
, Patrick M. Woodward
, Nam Hwi Hur

Geosciences

Kyung Hee University
Ohio State University
Korea Research Institute of Standards and Science

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

Abstract

A new perovskite ruthenate, CaCu₃Ga₂Ru ₂O₁₂, has been synthesized at 12.5 GPa and 1200 °C and recovered to room pressure and temperature conditions. This oxide is isostructural with CaCu₃Ti₄O₁₂ and CaCu ₃Ru₄O₁₂, crystallizing in space group Im3 with Ga and Ru cations disordered over the octahedral sites. CaCu₃Ga ₂Ru₂O₁₂ exhibits a temperature-independent Pauli-paramagnetic and metallic character, indicating delocalized electrons for both Cu and Ru. Bond valence calculations based on the refined structure give oxidation states of 2.31 and 4.53 for copper and ruthenium cations, respectively. The itinerant electron behavior is thought to originate from a significant oxidation of Cu(II) by Ru(V). Such a situation corresponds to Cu(II)-O-Ru(V) ↔ Cu(III)-O-Ru(IV) valence degeneracy. This places CaCu ₃Ga₂Ru₂O₁₂ among an unusual and interesting group of perovskites that show heteronuclear valence degeneracy.

Original language	English
Pages (from-to)	3697-3701
Number of pages	5
Journal	Chemistry of Materials
Volume	16
Issue number	19
DOIs	https://doi.org/10.1021/cm049265t
State	Published - Sep 21 2004

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@article{b5b157ada08246c68f7bbef88dff6079,

title = "High-pressure synthesis of metallic perovskite ruthenate CaCu 3Ga2Ru2O12",

abstract = "A new perovskite ruthenate, CaCu3Ga2Ru 2O12, has been synthesized at 12.5 GPa and 1200 °C and recovered to room pressure and temperature conditions. This oxide is isostructural with CaCu3Ti4O12 and CaCu 3Ru4O12, crystallizing in space group Im3 with Ga and Ru cations disordered over the octahedral sites. CaCu3Ga 2Ru2O12 exhibits a temperature-independent Pauli-paramagnetic and metallic character, indicating delocalized electrons for both Cu and Ru. Bond valence calculations based on the refined structure give oxidation states of 2.31 and 4.53 for copper and ruthenium cations, respectively. The itinerant electron behavior is thought to originate from a significant oxidation of Cu(II) by Ru(V). Such a situation corresponds to Cu(II)-O-Ru(V) ↔ Cu(III)-O-Ru(IV) valence degeneracy. This places CaCu 3Ga2Ru2O12 among an unusual and interesting group of perovskites that show heteronuclear valence degeneracy.",

author = "Byeon, \{Song Ho\} and Lee, \{Seoung Soo\} and Parise, \{John B.\} and Woodward, \{Patrick M.\} and Hur, \{Nam Hwi\}",

year = "2004",

month = sep,

day = "21",

doi = "10.1021/cm049265t",

language = "English",

volume = "16",

pages = "3697--3701",

journal = "Chemistry of Materials",

issn = "0897-4756",

number = "19",

}

TY - JOUR

T1 - High-pressure synthesis of metallic perovskite ruthenate CaCu 3Ga2Ru2O12

AU - Byeon, Song Ho

AU - Lee, Seoung Soo

AU - Parise, John B.

AU - Woodward, Patrick M.

AU - Hur, Nam Hwi

PY - 2004/9/21

Y1 - 2004/9/21

N2 - A new perovskite ruthenate, CaCu3Ga2Ru 2O12, has been synthesized at 12.5 GPa and 1200 °C and recovered to room pressure and temperature conditions. This oxide is isostructural with CaCu3Ti4O12 and CaCu 3Ru4O12, crystallizing in space group Im3 with Ga and Ru cations disordered over the octahedral sites. CaCu3Ga 2Ru2O12 exhibits a temperature-independent Pauli-paramagnetic and metallic character, indicating delocalized electrons for both Cu and Ru. Bond valence calculations based on the refined structure give oxidation states of 2.31 and 4.53 for copper and ruthenium cations, respectively. The itinerant electron behavior is thought to originate from a significant oxidation of Cu(II) by Ru(V). Such a situation corresponds to Cu(II)-O-Ru(V) ↔ Cu(III)-O-Ru(IV) valence degeneracy. This places CaCu 3Ga2Ru2O12 among an unusual and interesting group of perovskites that show heteronuclear valence degeneracy.

AB - A new perovskite ruthenate, CaCu3Ga2Ru 2O12, has been synthesized at 12.5 GPa and 1200 °C and recovered to room pressure and temperature conditions. This oxide is isostructural with CaCu3Ti4O12 and CaCu 3Ru4O12, crystallizing in space group Im3 with Ga and Ru cations disordered over the octahedral sites. CaCu3Ga 2Ru2O12 exhibits a temperature-independent Pauli-paramagnetic and metallic character, indicating delocalized electrons for both Cu and Ru. Bond valence calculations based on the refined structure give oxidation states of 2.31 and 4.53 for copper and ruthenium cations, respectively. The itinerant electron behavior is thought to originate from a significant oxidation of Cu(II) by Ru(V). Such a situation corresponds to Cu(II)-O-Ru(V) ↔ Cu(III)-O-Ru(IV) valence degeneracy. This places CaCu 3Ga2Ru2O12 among an unusual and interesting group of perovskites that show heteronuclear valence degeneracy.

UR - https://www.scopus.com/pages/publications/4544308204

U2 - 10.1021/cm049265t

DO - 10.1021/cm049265t

M3 - Article

AN - SCOPUS:4544308204

SN - 0897-4756

VL - 16

SP - 3697

EP - 3701

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 19

ER -

High-pressure synthesis of metallic perovskite ruthenate CaCu ₃Ga₂Ru₂O₁₂

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