抄録
A series of [FeII(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 dihydrate 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 [FeII(L)2](BF4)2 compounds can be interpreted by the relationship between the lattice enthalpies mainly arising from Coulomb interactions between the Fe cations and BF4 anions as in typical ionic crystals.
| 元の言語 | 英語 |
|---|---|
| ページ（範囲） | 1277-1287 |
| ページ数 | 11 |
| ジャーナル | Inorganic Chemistry |
| 巻 | 57 |
| 発行部数 | 3 |
| DOI | |
| 出版物ステータス | 出版済み - 2 5 2018 |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Inorganic Chemistry
これを引用
Contribution of Coulomb Interactions to a Two-Step Crystal Structure Phase Transformation Coupled with a Significant Change in Spin Crossover Behavior for a Series of Charged FeII Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine. / Takahashi, Kazuyuki; Okai, Mitsunobu; Mochida, Tomoyuki; Sakurai, Takahiro; Ohta, Hitoshi; Yamamoto, Takashi; Einaga, Yasuaki; Shiota, Yoshihito; Yoshizawa, Kazunari; Konaka, Hisashi; Sasaki, Akito.
：: Inorganic Chemistry, 巻 57, 番号 3, 05.02.2018, p. 1277-1287.研究成果: ジャーナルへの寄稿 › 記事
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TY - JOUR
T1 - Contribution of Coulomb Interactions to a Two-Step Crystal Structure Phase Transformation Coupled with a Significant Change in Spin Crossover Behavior for a Series of Charged FeII Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine
AU - Takahashi, Kazuyuki
AU - Okai, Mitsunobu
AU - Mochida, Tomoyuki
AU - Sakurai, Takahiro
AU - Ohta, Hitoshi
AU - Yamamoto, Takashi
AU - Einaga, Yasuaki
AU - Shiota, Yoshihito
AU - Yoshizawa, Kazunari
AU - Konaka, Hisashi
AU - Sasaki, Akito
PY - 2018/2/5
Y1 - 2018/2/5
N2 - A series of [FeII(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 dihydrate 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 [FeII(L)2](BF4)2 compounds can be interpreted by the relationship between the lattice enthalpies mainly arising from Coulomb interactions between the Fe cations and BF4 anions as in typical ionic crystals.
AB - A series of [FeII(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 dihydrate 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 [FeII(L)2](BF4)2 compounds can be interpreted by the relationship between the lattice enthalpies mainly arising from Coulomb interactions between the Fe cations and BF4 anions as in typical ionic crystals.
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U2 - 10.1021/acs.inorgchem.7b02721
DO - 10.1021/acs.inorgchem.7b02721
M3 - Article
VL - 57
SP - 1277
EP - 1287
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 3
ER -