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

Kazuyuki Takahashi; Mitsunobu Okai; Tomoyuki Mochida; Takahiro Sakurai; Hitoshi Ohta; Takashi Yamamoto; Yasuaki Einaga; Yoshihito Shiota; Kazunari Yoshizawa; Hisashi Konaka; Akito Sasaki

doi:10.1021/acs.inorgchem.7b02721

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 Fe^II Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine

Kazuyuki Takahashi, Mitsunobu Okai, Tomoyuki Mochida, Takahiro Sakurai, Hitoshi Ohta, Takashi Yamamoto, Yasuaki Einaga, Yoshihito Shiota, Kazunari Yoshizawa, Hisashi Konaka, Akito Sasaki

Department of Fundamental Organic Chemistry

Research output: Contribution to journal › Article › peer-review

17 Citations (Scopus)

Abstract

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 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 [Fe^II(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.

Original language	English
Pages (from-to)	1277-1287
Number of pages	11
Journal	Inorganic chemistry
Volume	57
Issue number	3
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02721
Publication status	Published - Feb 5 2018

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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Takahashi, K., Okai, M., Mochida, T., Sakurai, T., Ohta, H., Yamamoto, T., Einaga, Y., Shiota, Y., Yoshizawa, K., Konaka, H., & Sasaki, A. (2018). 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 Fe^II Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine. Inorganic chemistry, 57(3), 1277-1287. https://doi.org/10.1021/acs.inorgchem.7b02721

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 Fe^II Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine. / Takahashi, Kazuyuki; Okai, Mitsunobu; Mochida, Tomoyuki et al.
In: Inorganic chemistry, Vol. 57, No. 3, 05.02.2018, p. 1277-1287.

Research output: Contribution to journal › Article › peer-review

Takahashi, K, Okai, M, Mochida, T, Sakurai, T, Ohta, H, Yamamoto, T, Einaga, Y, Shiota, Y , Yoshizawa, K, Konaka, H & Sasaki, A 2018, '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 Fe^II Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine', Inorganic chemistry, vol. 57, no. 3, pp. 1277-1287. https://doi.org/10.1021/acs.inorgchem.7b02721

Takahashi K, Okai M, Mochida T, Sakurai T, Ohta H, Yamamoto T et al. 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 Fe^II Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine. Inorganic chemistry. 2018 Feb 5;57(3):1277-1287. doi: 10.1021/acs.inorgchem.7b02721

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title = "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",

abstract = "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.",

author = "Kazuyuki Takahashi and Mitsunobu Okai and Tomoyuki Mochida and Takahiro Sakurai and Hitoshi Ohta and Takashi Yamamoto and Yasuaki Einaga and Yoshihito Shiota and Kazunari Yoshizawa and Hisashi Konaka and Akito Sasaki",

note = "Funding Information: This work was partially supported by a Grant-in-Aid for Scientific Research (C) (No. 25410068) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. A part of this work was conducted at the Advanced Characterization Nanotechnology Platform of the University of Tokyo, supported by the “Nanotechnology Platform” of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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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

N1 - Funding Information: This work was partially supported by a Grant-in-Aid for Scientific Research (C) (No. 25410068) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. A part of this work was conducted at the Advanced Characterization Nanotechnology Platform of the University of Tokyo, supported by the “Nanotechnology Platform” of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan. Publisher Copyright: © 2018 American Chemical Society.

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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