Molecular Thermodynamics for Functional Metal-Complexes

Sorai Michio

doi:10.4019/bjscc.61.17

Better understanding of materials should be achieved by complementarily employing experimental techniques which lead to either microscopic or macroscopic aspect. The specific characteristic of thermodynamics is the absence of any selection rule or selectivity. This makes a sharp contrast with various spectroscopies in which particular nuclide and/or particular modes are selectively sensed. This review demonstrates calorimetric investigations of spin-spin interaction in transition-metal complexes and the phase transitions occurring in molecule-based materials in which electrons are directly involved. Important roles played by molecular thermodynamics are illustrated for the following subjects: (i) Spin-spin interactions in tri-nuclear metal-complex, (ii) ferromagnetic phase transition in molecule-based magnets, (iii) determination of structure in a low-dimensional assembled-metal complex, (iv) change of electronic state due to molecular motion in an organometallic compound, (v) phase transitions due to spin-crossover phenomena, (vi) phase transition due to intramolecular electron transfers in mixed-valence complexes, and (vii) phase transition due to thermochromic phenomena. Since a change in the electronic state is strongly coupled with a change in the lattice, the transition mechanisms always include interplays with various molecular motions in the lattice.

Molecular Thermodynamics for Functional Metal-Complexes

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