A Contribution of Coulomb Interactions to Two-step Crystal Structural Phase Transformation Coupled to the Significant Change in Spin Crossover Behavior for a Series of Charged FeII Complexes from 2,6-bis(2-methylthiazol-4-yl)pyridine
| Autor: | Mitsunobu Okai, Takahiro Sakurai, Takashi Yamamoto, Yasuaki Einaga, Hitoshi Ohta, Hisashi Konaka, Yoshihito Shiota, Akito Sasaki, Kazuyuki Takahashi, Tomoyuki Mochida, Kazunari Yoshizawa |
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| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
010405 organic chemistry
Enthalpy Stacking Crystal structure 010402 general chemistry 01 natural sciences Magnetic susceptibility 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry Spin crossover Lattice (order) Pyridine Coulomb Physical and Theoretical Chemistry |
| Zdroj: | Inorganic Chemistry. 57(3):1277-1287 |
| ISSN: | 0020-1669 |
| Popis: | A Series of [Fe-II(L)(2)](BF4)(2) compounds were structurally and physically characterized (L = 2,6-bis(2-methylthiazol-4-yl)pyridine). A crystal structure phase transformation from dihydtate compound 1 to anhydrous compound 3 through partially hydrated compounds 2 and 2' upon dehydration was found. Compounds 1 and 3 exhibited a gradual spin crossover (SCO) conversion, whereas compounds 2 and 2' demonstrated two-step and one-step abrupt SCO transitions, respectively. An X-ray single-crystal structural analysis revealed that one-dimensional and two-dimensional Fe cation networks linked by π stacking and sulfur-sulfur interactions. Were formed in 1 and 3, respectively. A thermodynamic analysis of the magnetic susceptibility for 1, 2', and 3 suggests that the enthalpy differences may govern SCO transition behaviors in the polymorphic compounds 2' and 3. A structural comparison between 1 and 3 indicates that the SCO behavior variations and crystal structure transformation in the present [Fe-II(L)(2)](BF4)(2) compounds can be interpreted by the relationship between the lattice enthalpies mainly arising froth Coulomb interactions between the Fe cations and BF4 anions as in typical ionic crystals. |
| Databáze: | OpenAIRE |
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