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Anion-driven supramolecular modulation of spin-crossover properties in mononuclear iron(III) Schiff-base complexes.

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Title: Anion-driven supramolecular modulation of spin-crossover properties in mononuclear iron(III) Schiff-base complexes.
Authors: Yu, Zong-Mei1 (AUTHOR), Zhao, Sheng-Ze1 (AUTHOR), Wang, Yu-Ting1 (AUTHOR), Xu, Peng-Yu1 (AUTHOR), Qin, Chun-Yan1 (AUTHOR), Li, Yong-Hua1 (AUTHOR) iamswang@njupt.edu.cn, Zhou, Xin-Hui1 (AUTHOR), Wang, Shi1 (AUTHOR)
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 11/14/2021, Vol. 50 Issue 42, p15210-15223. 14p.
Subjects: Space groups, Isomorphous structures, Magnetic susceptibility, Magnetic measurements, Crystal structure
Abstract: A series of Fe(III) complexes [Fe(5-F-sal-N-1,4,7,10)]Y (Y = PF6− for 1, Y = ClO4− for 2, Y = I− for 3 and Y = NO3− for 4) have been prepared. Single-crystal X-ray crystallographic studies show that complex 1 crystallizes in the orthorhombic Pna21 space group and complexes 2–4 have an isomorphous structure and crystallize in the same monoclinic space group, P21/n. Complexes 2–4 have two independent molecules (Fe1 and Fe2) in the unit cell. Magnetic susceptibility measurements demonstrated that complexes 1 and 3 showed a gradual one-step SCO behavior (T1/2 for 1 = 177 K and for 3 = 227 K) without thermal hysteresis. The magnetic behavior of 2 shows an incomplete two-step SCO process at T1/2 = 114 K and 170 K, respectively, while 4 is in a high-spin state at all measured temperatures. A careful evaluation of the supramolecular structures of these complexes revealed correlation between the supramolecular packing forces and their SCO behavior. The crystal structure of 1 consists of a three-dimensional (3D) extended network constructed from N–H⋯F and C–H⋯F hydrogen bonds, and C–H⋯π and C⋯C short contacts. In compounds 2–4, the crystal packing is governed by C⋯C, C–H⋯π and p–π interactions for the Fe1 centers and by C–H⋯π/O interactions for the Fe2 centers, which form 1D chains. Additional interactions (C–H⋯F and N–H⋯O/I) connect the neighboring chains and planes to form a complex supramolecular network. The anion⋯π interactions in 4 provide a means for preventing SCO occurring at low temperatures. This suggests that the supramolecular connectivity of the anions influences the magnetic properties. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Anion-driven supramolecular modulation of spin-crossover properties in mononuclear iron(III) Schiff-base complexes.
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  Data: <searchLink fieldCode="AR" term="%22Yu%2C+Zong-Mei%22">Yu, Zong-Mei</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zhao%2C+Sheng-Ze%22">Zhao, Sheng-Ze</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wang%2C+Yu-Ting%22">Wang, Yu-Ting</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Xu%2C+Peng-Yu%22">Xu, Peng-Yu</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Qin%2C+Chun-Yan%22">Qin, Chun-Yan</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Li%2C+Yong-Hua%22">Li, Yong-Hua</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> iamswang@njupt.edu.cn</i><br /><searchLink fieldCode="AR" term="%22Zhou%2C+Xin-Hui%22">Zhou, Xin-Hui</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wang%2C+Shi%22">Wang, Shi</searchLink><relatesTo>1</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 11/14/2021, Vol. 50 Issue 42, p15210-15223. 14p.
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  Data: <searchLink fieldCode="DE" term="%22Space+groups%22">Space groups</searchLink><br /><searchLink fieldCode="DE" term="%22Isomorphous+structures%22">Isomorphous structures</searchLink><br /><searchLink fieldCode="DE" term="%22Magnetic+susceptibility%22">Magnetic susceptibility</searchLink><br /><searchLink fieldCode="DE" term="%22Magnetic+measurements%22">Magnetic measurements</searchLink><br /><searchLink fieldCode="DE" term="%22Crystal+structure%22">Crystal structure</searchLink>
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  Data: A series of Fe(III) complexes [Fe(5-F-sal-N-1,4,7,10)]Y (Y = PF6− for 1, Y = ClO4− for 2, Y = I− for 3 and Y = NO3− for 4) have been prepared. Single-crystal X-ray crystallographic studies show that complex 1 crystallizes in the orthorhombic Pna21 space group and complexes 2–4 have an isomorphous structure and crystallize in the same monoclinic space group, P21/n. Complexes 2–4 have two independent molecules (Fe1 and Fe2) in the unit cell. Magnetic susceptibility measurements demonstrated that complexes 1 and 3 showed a gradual one-step SCO behavior (T1/2 for 1 = 177 K and for 3 = 227 K) without thermal hysteresis. The magnetic behavior of 2 shows an incomplete two-step SCO process at T1/2 = 114 K and 170 K, respectively, while 4 is in a high-spin state at all measured temperatures. A careful evaluation of the supramolecular structures of these complexes revealed correlation between the supramolecular packing forces and their SCO behavior. The crystal structure of 1 consists of a three-dimensional (3D) extended network constructed from N–H⋯F and C–H⋯F hydrogen bonds, and C–H⋯π and C⋯C short contacts. In compounds 2–4, the crystal packing is governed by C⋯C, C–H⋯π and p–π interactions for the Fe1 centers and by C–H⋯π/O interactions for the Fe2 centers, which form 1D chains. Additional interactions (C–H⋯F and N–H⋯O/I) connect the neighboring chains and planes to form a complex supramolecular network. The anion⋯π interactions in 4 provide a means for preventing SCO occurring at low temperatures. This suggests that the supramolecular connectivity of the anions influences the magnetic properties. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1039/d1dt02394b
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        Text: English
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        PageCount: 14
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      – SubjectFull: Space groups
        Type: general
      – SubjectFull: Isomorphous structures
        Type: general
      – SubjectFull: Magnetic susceptibility
        Type: general
      – SubjectFull: Magnetic measurements
        Type: general
      – SubjectFull: Crystal structure
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      – TitleFull: Anion-driven supramolecular modulation of spin-crossover properties in mononuclear iron(III) Schiff-base complexes.
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            NameFull: Yu, Zong-Mei
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              Text: 11/14/2021
              Type: published
              Y: 2021
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