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• W4386324644 abstract "Cs 2 [ Au I X 2 ][ Au III X 4 ](X = Cl, Br, and I) is well known for the perovskite-type gold mixed-valence system. Recently, we have succeeded in synthesizing all of the hetero-halogen bridged gold mixed-valence complexes having perovskite-type structure, Cs 2 [ Au I X 2 ][ Au III Y 4 ] (X, Y = Cl, Br, I), in an organic solvent. In this synthesizing process, we could independently control the coordinated halogens, X and Y. This hetero-halogen-bridged gold mixed-valence system was confirmed by means of Raman spectroscopy. From the analysis of 197 Au Mössbauer spectra, the charge transfer interaction between Au I and Au III has systematically been investigated. From the analysis of single-crystal 197 Au Mössbauer spectra of Cs 2 [ Au I I 2 ][ Au III I 4 ], the sign of electric field gradient ( EFG ) for Au I in [ Au I I 2 ] − and Au III in [ Au III X 4 ] − were determined to be negative and positive, respectively. It is obvious that the contributions of 6p z and 6p x,y dominate the sign of EFG for Au I in [ Au I I 2 ] − and Au III in [ Au III X 4 ] − , respectively. Cs 2 [ Au I X 2 ][ Au III X 4 ](X = Cl, Br, I) undergo the pressure-induced Au valence transition from the mixed valence state ( Au I , Au III ) to the single valence state ( Au II ) which is coupled with a structural phase transition. In the pressure region below the Au valence transition, these complexes show a metallic behavior due to the dynamical two-electron exchange (valence skipping) between the Au I and Au III sites, which was strongly supported by the electrical resistivity, 197 Au Mössbauer spectroscopy, Raman spectroscopy, and single-crystal X-ray diffraction analysis under high pressures for Cs 2 [ Au I Cl 2 ][ Au III Cl 4 ]. In the case of Cs 2 [ Au I I 2 ][ Au III I 4 ], the single valence phase of Au II was confirmed by the 197 Au Mössbauer spectroscopy at 12.5 GPa and 4.2 K. Moreover, we investigated the Au valence state and the charge transfer interaction between the Au I and Au III sites for the layered perovskite-type Au mixed-valence complex system, [ NH 3 ( CH 2 ) n NH 3 ] 2 [( Au I I 2 )( Au III I 4 )( I 3 ) 2 ] (n = 7, 8)." @default.
• W4386324644 created "2023-09-01" @default.
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• W4386324644 creator A5041513914 @default.
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• W4386324644 date "2023-08-31" @default.
• W4386324644 modified "2023-09-30" @default.
• W4386324644 title "<scp> ¹⁹⁷ Au </scp> Mössbauer Spectroscopy of Gold Mixed‐Valence Complexes, Cs ₂ [ <scp> Au ^I X ₂ </scp> ][ <scp> Au ^III Y ₄ </scp> ](X, Y = Cl, Br, I) and [ <scp> NH ₃ </scp> ( <scp> CH ₂ </scp> ) <scp> _n NH ₃ </scp> ] ₂ [( <scp> Au ^I I ₂ </scp> )( <scp> Au ^III I ₄ </scp> ) ( <scp> I ₃ </scp> ) ₂ ] (n = 7, 8)" @default.
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• W4386324644 doi "https://doi.org/10.1002/9783527824953.ch8" @default.
• W4386324644 hasPublicationYear "2023" @default.
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