Comparison between optical properties of sulfates and hydrogensulfates in halogen-bridged mixed-valence platinum(II, IV) complexes.
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概要
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Syntheses and optical properties of some new halogen-bridged mixed-valence platinum complexes analogous to Wolffram's Red Salt, [Pt(en)<SUB>2</SUB>][PtBr<SUB>2</SUB>(en)<SUB>2</SUB>](HSO<SUB>4</SUB>)<SUB>4</SUB> (PBHS), [Pt(en)<SUB>2</SUB>][PtI<SUB>2</SUB>(en)<SUB>2</SUB>](HSO<SUB>4</SUB>)<SUB>4</SUB>·4H<SUB>2</SUB>O (PIHS), and [Pt(en)<SUB>2</SUB>][PtX<SUB>2</SUB>](en)<SUB>2</SUB>](SO<SUB>4</SUB>)<SUB>2</SUB>·6H<SUB>2</SUB>O {X=Br(PBSW), I(PISW)}, are reported. The powder X-ray diffraction pattern shows that PBHS is isomorphous with [Pt(en)<SUB>2</SUB>][PtCl<SUB>2</SUB>(en)<SUB>2</SUB>](HSO<SUB>4</SUB>)<SUB>4</SUB> (PCHS), and that PBSW and PISW are isomorphous. The hydrogensulfates PBHS and PIHS crystallize from an aqueous sulfuric acid solution, whereas the sulfates PBSW and PISW crystallize from an aqueous solution. The single crystal absorption spectra of PBHS, PIHS, PBSW, and PISW have been investigated at 4.2 K. The intense optical absorption due to intervalence charge-transfer transition from Pt(II) to Pt(IV) has been observed for the light polarized parallel to the Pt chain axis (<I>E</I>//chain). From the comparison of the energy of the intervalence charge-transfer absorption edges in PBHS, PBSW, and PISW, one can conclude that the influence of the substitution of the counterions HSO<SUB>4</SUB><SUP>−</SUP> with SO<SUB>4</SUB><SUP>2−</SUP> on the Pt(II)–Pt(IV) mixed-valence state is no less better than that of the substitution of the bridging halogen. The role of the counterion on the mixed-valence state is explained by the hydrogen bond network (Pt–NH···counterion···HN–Pt) on individual chains.
- 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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Kojima Norimichi
Department Of Basic Science Graduate School Of Arts And Science The University Of Tokyo
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Matsushita Nobuyuki
Department Of Chemistry College Of Arts And Scieces The University Of Tokyo
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Ban Toshiro
Department Of Chemisity Faculty Of Science Kyoto University
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