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CSJ Journals

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2010, Vol.83, No.3

261-266
Selected Paper

Calorimetric Study of Correlated Ligand Dynamics in Mixed-Valence MMX Chain Complex [{Ni2(n-BuCS2)4}I]

Ikeuchi Satoaki 1 , 2 , Yamamura Yasuhisa 2 , Yoshida Yuji 3 , Mitsumi Minoru 3 , Toriumi Koshiro 3 , Saito Kazuya 2
1 Department of Chemistry, Graduate School of Science, Osaka University
2 Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba
3 Department of Material Science, University of Hyogo
https://doi.org/10.1246/bcsj.20090301

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Abstract
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Heat capacity of a mixed-valence complex having a one-dimensional chain structure, [{Ni2(n-BuCS2)4}I] (n-Bu = butyl group), was measured between 10 and 325 K by adiabatic calorimetry. Anomalies due to phase transitions were detected around 135 and 260 K. The anomaly around 260 K was of multiple-peaks. The excess entropy acquired below the phase transition around 260 K is much smaller than the simple estimate based on the structural disorder found in the crystal structure, implying the presence of motional correlation in dynamics of n-BuCS2 ligands. Through the comparison with the corresponding Pt complex, [{Pt2(n-BuCS2)4}I], the phase transition around 135 K is also discussed in relation to the absence in the present complex of a spin-Peierls transition observed in other members of Ni complexes with similar chain structures.

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