Theoretical study on high-spin to low-spin transition of {Fe(pyrazine)[Pt(CN)4]}: Guest-induced entropy decrease

Hideo Ando, Yoshihide Nakao, Hirofumi Sato, Masaaki Ohba, Susumu Kitagawa, Shigeyoshi Sakaki

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23 Citations (Scopus)


A porous coordination polymer (PCP), {FeII(pyrazine)[Pt II(CN)4]}, adsorbs CS2 molecules to induce spin transition from high-spin (HS) to low-spin (LS) state. To elucidate this mechanism, we investigated flexibility of the PCP framework, namely rotation of pyrazine ligands, with DFT method and evaluated the rotational entropy difference (ΔSrotHS-LS) between the HS and LS states with Fourier grid Hamiltonian method. The ΔSrotHS-LS value is considerably large in the absence of CS2. The CS2 adsorption occurs between two pyrazine ligands to suppress the pyrazine rotation in both states, which decreases ΔSrotHS-LS to induce the HS → LS transition at room temperature.

Original languageEnglish
Pages (from-to)399-404
Number of pages6
JournalChemical Physics Letters
Issue number4-6
Publication statusPublished - Aug 5 2011

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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