Alkyl Group as Entropy Reservoir in an MMX Chain Complex, Pt2(n-PenCS2)4I†
- Kazuya Saito ,
- Satoaki Ikeuchi ,
- Yasuhiro Nakazawa ,
- Akane Sato ,
- Minoru Mitsumi ,
- Takami Yamashita ,
- Koshiro Toriumi , and
- Michio Sorai
Abstract
Heat capacity of halogen-bridged one-dimensional binuclear metal complex (so-called MMX chain) having four n-pentyl groups, Pt2(n-PenCS2)4I, was measured by adiabatic calorimetry. A first-order phase transition was observed at 207.4 K when measurement was made after cooling from room temperature. The enthalpy and entropy of transition were determined to be 10.19 kJ mol-1 and 49.1 J K-1 mol-1, respectively. A monotropic phase transition was observed at 324 K on heating, and the entropy of transition was essentially null. The sample once heated above 324 K never returned to the initial phase at room temperature and underwent a higher-order phase transition at 173 K and a first-order phase transition at 220.5 K. The enthalpy and entropy of the first-order phase transition were estimated to be 11.6 kJ mol-1 and 52.4 J K-1 mol-1, respectively. The magnitude of the entropy gain at the phase transition from the initial room-temperature phase to the high-temperature phase at 324 K shows that in Pt2(n-PenCS2)4I a large amount of entropy reserved in alkyl chain is transferred to dithiocarboxylato groups upon the phase transition, as in the cases of Pt2(n-PrCS2)4I and Pt2(n-BuCS2)4I.
†
Contribution No. 90 from the Research Center for Molecular Thermodynamics.
*
Corresponding author. Present Address: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan. E-mail: kazu[email protected]
‡
Osaka University.
§
Tokyo Institute of Technology.
‖
Present Address: Research Center for Spectrochemistry, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
⊥
University of Hyogo.
Cited By
This article is cited by 20 publications.
- Michio Sorai, Yasuhiro Nakazawa, Motohiro Nakano, and Yuji Miyazaki . Update 1 of: Calorimetric Investigation of Phase Transitions Occurring in Molecule-Based Magnets. Chemical Reviews 2013, 113 (1) , PR41-PR122. https://doi.org/10.1021/cr300156s
- Minoru Mitsumi, Takami Yamashita, Yuko Aiga, Koshiro Toriumi, Hiroshi Kitagawa, Tadaoki Mitani, and Mohamedally Kurmoo . On the Nature of the Multiple Ground States of the MMX Mixed-Valence Chain Compound, [PtII/III2(n-PenCS2)4I]∞. Inorganic Chemistry 2011, 50 (10) , 4368-4377. https://doi.org/10.1021/ic102461z
- Atsushi Kobayashi, Shinji Kitao, Makoto Seto, Ryuichi Ikeda and Hiroshi Kitagawa . 129I Mössbauer Spectroscopic Study of a Metallic MMX Chain System. Inorganic Chemistry 2009, 48 (16) , 8044-8049. https://doi.org/10.1021/ic9007558
- Minoru Mitsumi, Yuji Yoshida, Akihisa Kohyama, Yasutaka Kitagawa, Yoshiki Ozawa, Mototada Kobayashi, Koshiro Toriumi, Makoto Tadokoro, Naoshi Ikeda, Mitsutaka Okumura and Mohamedally Kurmoo . Syntheses, Structures and Solid-State Properties of MMX Mixed-Valence Chains, [NiII/III2(RCS2)4I]∞ (R = Et, n-Pr and n-Bu): Evidence of a Spin-Peierls Transition. Inorganic Chemistry 2009, 48 (14) , 6680-6691. https://doi.org/10.1021/ic900630a
- Arrigo Calzolari, Simone S. Alexandre, Felix Zamora and Rosa Di Felice . Metallicity in Individual MMX Chains. Journal of the American Chemical Society 2008, 130 (16) , 5552-5562. https://doi.org/10.1021/ja800358c
- Michio Sorai,, Motohiro Nakano, and, Yuji Miyazaki. Calorimetric Investigation of Phase Transitions Occurring in Molecule-Based Magnets. Chemical Reviews 2006, 106 (3) , 976-1031. https://doi.org/10.1021/cr960049g
- Yukihiro Yoshida, Hiroshi Kitagawa. One-dimensional electronic systems: metal-chain complexes and organic conductors. Chemical Communications 2020, 56 (70) , 10100-10112. https://doi.org/10.1039/D0CC04124F
- Xuelin Wang, Zhicheng Tan, Quan Shi, Guanglong Zou. Low-temperature heat capacities and thermodynamic functions of four-ring chain difluoromethyleneoxy liquid crystalline compounds with different alkyl terminal chain. Journal of Thermal Analysis and Calorimetry 2016, 125 (1) , 537-545. https://doi.org/10.1007/s10973-016-5370-5
- Katarzyna Anna Ślepokura. Reversible chair ↔ skew conformational interconversion of 1,3,2-dioxaphosphorinane ring in the solid state. Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials 2016, 72 (1) , 117-125. https://doi.org/10.1107/S2052520615020259
- Minoru Mitsumi. Crystal Structures and Properties of MMX-Chain Compounds Based on Dithiocarboxylato-Bridged Dinuclear Complexes. 2013,,, 151-205. https://doi.org/10.1007/978-3-7091-1317-2_9
- , . Material Designs and New Physical Properties in MX- and MMX-Chain Compounds. 2013,,https://doi.org/10.1007/978-3-7091-1317-2
- Gonzalo Givaja, Pilar Amo-Ochoa, Carlos J. Gómez-García, Félix Zamora. Electrical conductive coordination polymers. Chem. Soc. Rev. 2012, 41 (1) , 115-147. https://doi.org/10.1039/C1CS15092H
- Alejandro Guijarro, Oscar Castillo, Lorena Welte, Arrigo Calzolari, Pablo J. Sanz Miguel, Carlos J. Gómez-García, David Olea, Rosa di Felice, Julio Gómez-Herrero, Felix Zamora. Conductive Nanostructures of MMX Chains. Advanced Functional Materials 2010, 20 (9) , 1451-1457. https://doi.org/10.1002/adfm.200901901
- Satoaki Ikeuchi, Yasuhisa Yamamura, Yuji Yoshida, Minoru Mitsumi, Koshiro Toriumi, Kazuya Saito. Calorimetric Study of Correlated Ligand Dynamics in Mixed-Valence MMX Chain Complex [{Ni 2 ( n -BuCS 2 ) 4 }I]. Bulletin of the Chemical Society of Japan 2010, 83 (3) , 261-266. https://doi.org/10.1246/bcsj.20090301
- 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
- Satoaki Ikeuchi, Yasuhisa Yamamura, Yuji Yoshida, Minoru Mitsumi, Koshiro Toriumi, Kazuya Saito. Calorimetric Study of MMX Chain Complexes Having Alkyl Groups, Ni 2 (EtCS 2 ) 4 I and Ni 2 ( n -PrCS 2 ) 4 I. Journal of the Physical Society of Japan 2009, 78 (9) , 094704. https://doi.org/10.1143/JPSJ.78.094704
- Yoshitaka Shimizu, Yoko Ohte, Yasuhisa Yamamura, Kazuya Saito. Is the liquid or the solid phase responsible for the low melting points of ionic liquids? Alkyl-chain-length dependence of thermodynamic properties of [Cnmim][Tf2N]. Chemical Physics Letters 2009, 470 (4-6) , 295-299. https://doi.org/10.1016/j.cplett.2009.01.085
- Hisaaki Tanaka, Hideshi Nishiyama, Shin-ichi Kuroda, Takami Yamashita, Minoru Mitsumi, Koshiro Toriumi. ESR observation of optically generated solitons in the quasi-one-dimensional iodo-bridged diplatinum complex Pt 2 ( n -pentylCS 2 ) 4 I . Physical Review B 2008, 78 (3) https://doi.org/10.1103/PhysRevB.78.033104
- Hisaaki Tanaka, Shin-ichi Kuroda, Takami Yamashita, Minoru Mitsumi, Koshiro Toriumi. ESR studies of the spin dynamics in quasi-one-dimensional iodo-bridged diplatinum complex Pt 2 ( n − pentyl C S 2 ) 4 I . Physical Review B 2006, 73 (24) https://doi.org/10.1103/PhysRevB.73.245102
- Satoaki Ikeuchi, Yuji Miyazaki, Sadamu Takeda, Tomoyuki Akutagawa, Sadafumi Nishihara, Takayoshi Nakamura, Kazuya Saito. Cooperativity of dynamics of 18-crown-6 molecule forming one-dimensional chain in Cs2(18-crown-6)3[Ni(dmit)2]2. The Journal of Chemical Physics 2005, 123 (4) , 044514. https://doi.org/10.1063/1.1979481