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Pressure‐Induced Metal–Semiconductor–Metal Transitions in an MMX‐Chain Complex, Pt 2 (C 2 H 5 CS 2 ) 4 I
Author(s) -
Kobayashi Atsushi,
Tokunaga Aya,
Ikeda Ryuichi,
Sagayama Hajime,
Wakabayashi Yusuke,
Sawa Hiroshi,
Hedo Masato,
Uwatoko Yoshiya,
Kitagawa Hiroshi
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600506
Subject(s) - chemistry , mmx , metal , valence (chemistry) , crystallography , halogen , semiconductor , transition metal , electrical resistivity and conductivity , platinum , analytical chemistry (journal) , materials science , physics , catalysis , biochemistry , alkyl , optoelectronics , organic chemistry , chromatography , quantum mechanics , computer science , operating system
The electrical conductivity and X‐ray diffraction measurements were performed for a highlyconductive halogen‐bridged binuclear‐metal mixed‐valence complex (the so‐called MMX chain), Pt 2 (C 2 H 5 CS 2 ) 4 I, under high pressure up to 2.5 GPa. The complex exhibited pressure‐induced metal–semiconductor–metal transitions at 0.5 and 2.1 GPa. The X‐ray diffuse scatterings were observed at k = n + 0.5 ( n : integer) under ambient pressure, which are derived from the charge‐density wave (CDW: ··· Pt 2+ –Pt 2+ ··· I–Pt 3+ –Pt 3+ –I ··· ) fluctuation in the MMX chain. Above 0.5 GPa, where the pressure‐induced metal–semiconductor transition occurred, these scatterings disappeared. The electronic phases under high pressure ( P ) were found to be attributable to the metallic averaged‐valence state (AV: –Pt 2.5+ –Pt 2.5+ –I–Pt 2.5+ –Pt 2.5+ –I–) with CDW fluctuation of P < 0.5 GPa, semiconducting charge‐polarization state (CP: ··· Pt 2+ –Pt 3+ –I ··· Pt 2+ –Pt 3+ –I ··· ) of 0.5 < P < 2.1 GPa, and metallic AV state of P > 2.1 GPa. The electronic state of Pt 2 (C 2 H 5 CS 2 ) 4 I is very sensitive to pressure, which implies that the phase competition among the CP, CDW, and AV phases is present in the MMX chain. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)