Heat Capacity of the Halogen-Bridged Mixed-Valence Complex Pt2(dta)4I (dta = CH3CS2-)†
- Yuji Miyazaki ,
- Qi Wang ,
- Akane Sato ,
- Kazuya Saito ,
- Masahiro Yamamoto ,
- Hiroshi Kitagawa ,
- Tadaoki Mitani , and
- Michio Sorai
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Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China, Department of Physical Materials Science, School of Materials Science, Japan Advanced Institute of Science and Technology, Tatsunokuchi, Ishikawa 923-1292, Japan, and Department of Chemistry, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan.
Abstract
Heat capacity of the halogen-bridged mixed-valence complex Pt2(dta)4I (dta = CH3CS2-) has been measured in the temperature region between 6 and 386 K. The complex exhibited a phase transition of order−disorder type at Ttrs = 373.4 K, from being arranged in an ordered helical form of four dta ligand planes around the central Pt−Pt axis to dynamically jumping between two orientations. Neither latent heat nor distinct thermal hysteresis was observed for the phase transition, suggesting that the phase transition is of higher-order rather than of first-order. The transition enthalpy and entropy were determined to be ΔtrsH = 1.91 ± 0.02 kJ mol-1 and ΔtrsS = 5.25 ± 0.07 J K-1 mol-1, respectively. The transition entropy close to R ln 2 (= 5.76 J K-1 mol-1), where R is the gas constant, implies that the twisting motion of the four dta ligands takes place in a synchronized way. No thermal anomaly was detected around 300 and 90 K, where a Mott transition from the one-dimensional metallic phase to the semiconducting phase and a spin-Peierls-like transition have been expected. The reason for the absence of these transitions in calorimetry is discussed briefly.
†
Contribution No. 51 from the Research Center for Molecular Thermodynamics.
‡
Osaka University.
§
Zhejiang University.
⊥
Japan Advanced Institute of Science and Technology.
‖
University of Tsukuba.
*
Corresponding author. Tel: +81-6-6850-5523. Fax: +81-6-6850-5526. E-mail: [email protected]
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- Kazuya Saito. Importance of Molecular Crystals. 2020,,, 199-220. https://doi.org/10.1007/978-981-15-9023-8_10
- Kazuya Saito. Chemical Physics of Molecular Condensed Matter. 2020,,https://doi.org/10.1007/978-981-15-9023-8
- Kazuya Saito. Melting of Molecular Crystals. 2020,,, 119-141. https://doi.org/10.1007/978-981-15-9023-8_6
- Kazuya Saito. Chemical Physics of Molecular Condensed Matter. 2020,,https://doi.org/10.1007/978-981-15-9023-8
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- Satoaki Ikeuchi, Yasuhisa Yamamura, Minoru Mitsumi, Koshiro Toriumi, Hideki Saitoh, Tooru Atake, Kazuya Saito. Effects of Alkyl Length in Ligands in Mixed Valence MMX Complexes: Properties of Pt 2 ( n -HexCS 2 ) 4 I ( n -Hex = n -Hexyl Group). Chemistry Letters 2009, 38 (12) , 1190-1191. https://doi.org/10.1246/cl.2009.1190
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- Atsushi Kobayashi, Aya Tokunaga, Ryuichi Ikeda, Hajime Sagayama, Yusuke Wakabayashi, Hiroshi Sawa, Masato Hedo, Yoshiya Uwatoko, Hiroshi Kitagawa. Pressure-Induced Metal–Semiconductor–Metal Transitions in an MMX-Chain Complex, Pt2(C2H5CS2)4I. European Journal of Inorganic Chemistry 2006, 2006 (18) , 3567-3570. https://doi.org/10.1002/ejic.200600506
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- Noriyoshi Kimura, Masahiro Yamashita, Ryuichi Ikeda. Metallic behaviour and molecular motions in a 1-D –Pt–Pt–I– type complex, Pt2(CH3CS2)4I, studied by solid-state 13C and 1H NMR. Chemical Physics Letters 2005, 406 (1-3) , 111-115. https://doi.org/10.1016/j.cplett.2005.02.104
- Shoji Yamamoto. Possible nonlinear excitations in quasi-one-dimensional halogen-bridged binuclear metal complexes. Physical Review B 2002, 66 (16) https://doi.org/10.1103/PhysRevB.66.165113
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