Synthesis and electrical conductivity of a new family of Pt mixed valence complexes : Pt6(NH3)14Cl10X4 (X=ClO4, BF4, and PF6).
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概要
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A new family of Pt mixed valence complexes: Pt<SUB>6</SUB>(NH<SUB>3</SUB>)<SUB>14</SUB>Cl<SUB>10</SUB>X<SUB>4</SUB> (X=ClO<SUB>4</SUB>, BF<SUB>4</SUB>, and PF<SUB>6</SUB>) was synthesized from the Magnus green salt (MGS) by the partial oxidation using an oxidant of H<SUB>2</SUB>O<SUB>2</SUB> or by electrochemical method. On partial oxidation, the 1/6 of Cl<SUP>−</SUP> ligands in MGS are randomly replaced by NH<SUB>3</SUB> ligands and simultaneously counter ions X are introduced. These complexes comprise of one-dimensional chains with direct contact between Pt atoms and consequently a quasi-one-dimensional band made up of 5d<SUB>z2</SUB> orbital of Pt is formed. The average valence of Pt is +2.33 and the distance between Pt atoms along a chain is shorter than or comparable to that of K<SUB>2</SUB>[Pt(CN)<SUB>4</SUB>]Br<SUB>0.3</SUB>·<I>x</I>H<SUB>2</SUB>O (KCP). The electrical conductivity σ of these complexes was measured from 80 K to r.t. The σ(r.t.) is rather high in spite of the measurement on the powder pressed pellets. This suggests that σ along a chain direction may be as high as that of KCP if single crystals can be obtained. The conductivity data were fitted using a gap energy with various temperature dependence. In the complex with X=PF<SUB>6</SUB>, there may be a phase transition caused by ordering of PF<SUB>6</SUB><SUP>−</SUP> ions at about 110 K.
- 公益社団法人 日本化学会の論文
著者
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Tsujikawa Ikuji
Department Of Chemisity Faculty Of Science Kyoto University
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Tanaka Masako
Department Of Applied Physics Osaka City University:(present Address) Department Of Physics Tohoku U
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TSUJIKAWA Ikuji
Department of Chemistry, Faculty of Science, Kyoto University
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