J. Phys. Soc. Jpn. 78, 094704 (2009) [6 Pages]
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Calorimetric Study of MMX Chain Complexes Having Alkyl Groups, Ni2(EtCS2)4I and Ni2(n-PrCS2)4I

Satoaki Ikeuchi1,2, Yasuhisa Yamamura2, Yuji Yoshida3, Minoru Mitsumi3, Koshiro Toriumi3, and Kazuya Saito2
+ Affiliations
1Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-00432Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-85713Department of Material Science, University of Hyogo, Kamigori, Hyogo 678-1297
Received May 21, 2009; Accepted July 1, 2009; Published August 25, 2009

Heat capacities of halogen-bridged one-dimensional binuclear metal complexes (so-called MMX chain) having alkyl groups, Ni 2 (RCS 2 ) 4 I (R = Et and n -Pr), were measured by adiabatic and relaxation calorimetry. For each complex, a small broad thermal anomaly due to a spin-Peierls transition was observed around 40 K. For Ni 2 ( n -PrCS 2 ) 4 I, a first-order phase transition was observed at 205.6 K. The enthalpy and entropy of transition were estimated to be about 4.05 kJ mol -1 and 19.7 J K -1 mol -1 , respectively. The magnitude of thermal anomaly shows that the effect of molecular dynamics of ligand on the electronic state in one-dimensional chain is small for Ni complexes having localized electrons in comparison with Pt complexes.

©2009 The Physical Society of Japan
https://doi.org/10.1143/JPSJ.78.094704
KEYWORDS: spin-Peierls transition, MMX, mixed valence, heat capacity

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