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Structural insights into the counterion effects on the manganese(iii) spin crossover system with hexadentate Schiff-base ligands.

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Title: Structural insights into the counterion effects on the manganese(iii) spin crossover system with hexadentate Schiff-base ligands.
Authors: Wang, Shi1, Xu, Wu-Tan1, He, Wen-Rui1, Takaishi, Shinya2, Li, Yong-Hua1, Yamashita, Masahiro2, Huang, Wei1,3
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 4/7/2016, Vol. 45 Issue 13, p5676-5688. 13p.
Subjects: Counter-ions, Manganese compounds, Spin crossover, Schiff bases, Molecular structure of ligands
Abstract: A series of new salts [Mn(5-MeO-sal-N-1,5,8,12)]Y (Y = ClO4 for 1, Y = BF4 for 2, Y = NO3 for 3 and Y = CF3SO3 for 4) based on the six-coordinated mononuclear manganese(iii) Schiff-base complex cation [Mn(5-MeO-sal-N-1,5,8,12)]+, has been investigated to determine the impact of counter anion effects, intramolecular ligand distortion and intermolecular supramolecular structures on the spin crossover (SCO) behavior. The SCO in salt 1 has resulted in a crystallographic observation of the coexistence of high-spin (HS, S = 2) and low-spin (LS, S = 1) manganese(iii) complex cations in equal proportions around 100 K. At room temperature, the two crystallographically distinct manganese centers are both close to the complete HS state. Only one of the two slightly different units undergoes SCO in the temperature range 300–180 K, whereas the other remains in the HS state down to 20 K. For salts 2 and 3, crystal structural analysis indicates change in the anion from ClO4− to BF4− and NO3− was led to the close arrangement of the cations and the stacking between phenyl groups from the ligands. With CF3SO3− as the counterion, although the cations and the anions separate clearly in one direction, the close arrangement of cations in other directions precludes the spin transformation of the Mn(iii) cations. Magnetic measurements on 2–4 indicate that the manganese(iii) complex cations remain in the HS state in the temperature range 2–300 K. [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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Items – Name: Title
  Label: Title
  Group: Ti
  Data: Structural insights into the counterion effects on the manganese(iii) spin crossover system with hexadentate Schiff-base ligands.
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  Data: <searchLink fieldCode="AR" term="%22Wang%2C+Shi%22">Wang, Shi</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Xu%2C+Wu-Tan%22">Xu, Wu-Tan</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22He%2C+Wen-Rui%22">He, Wen-Rui</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Takaishi%2C+Shinya%22">Takaishi, Shinya</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Li%2C+Yong-Hua%22">Li, Yong-Hua</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Yamashita%2C+Masahiro%22">Yamashita, Masahiro</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Huang%2C+Wei%22">Huang, Wei</searchLink><relatesTo>1,3</relatesTo>
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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>. 4/7/2016, Vol. 45 Issue 13, p5676-5688. 13p.
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  Data: <searchLink fieldCode="DE" term="%22Counter-ions%22">Counter-ions</searchLink><br /><searchLink fieldCode="DE" term="%22Manganese+compounds%22">Manganese compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Spin+crossover%22">Spin crossover</searchLink><br /><searchLink fieldCode="DE" term="%22Schiff+bases%22">Schiff bases</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure+of+ligands%22">Molecular structure of ligands</searchLink>
– Name: Abstract
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  Data: A series of new salts [Mn(5-MeO-sal-N-1,5,8,12)]Y (Y = ClO4 for 1, Y = BF4 for 2, Y = NO3 for 3 and Y = CF3SO3 for 4) based on the six-coordinated mononuclear manganese(iii) Schiff-base complex cation [Mn(5-MeO-sal-N-1,5,8,12)]+, has been investigated to determine the impact of counter anion effects, intramolecular ligand distortion and intermolecular supramolecular structures on the spin crossover (SCO) behavior. The SCO in salt 1 has resulted in a crystallographic observation of the coexistence of high-spin (HS, S = 2) and low-spin (LS, S = 1) manganese(iii) complex cations in equal proportions around 100 K. At room temperature, the two crystallographically distinct manganese centers are both close to the complete HS state. Only one of the two slightly different units undergoes SCO in the temperature range 300–180 K, whereas the other remains in the HS state down to 20 K. For salts 2 and 3, crystal structural analysis indicates change in the anion from ClO4− to BF4− and NO3− was led to the close arrangement of the cations and the stacking between phenyl groups from the ligands. With CF3SO3− as the counterion, although the cations and the anions separate clearly in one direction, the close arrangement of cations in other directions precludes the spin transformation of the Mn(iii) cations. Magnetic measurements on 2–4 indicate that the manganese(iii) complex cations remain in the HS state in the temperature range 2–300 K. [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/c5dt04824a
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        Text: English
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        PageCount: 13
        StartPage: 5676
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      – SubjectFull: Counter-ions
        Type: general
      – SubjectFull: Manganese compounds
        Type: general
      – SubjectFull: Spin crossover
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      – SubjectFull: Schiff bases
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      – SubjectFull: Molecular structure of ligands
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      – TitleFull: Structural insights into the counterion effects on the manganese(iii) spin crossover system with hexadentate Schiff-base ligands.
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            NameFull: Wang, Shi
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            NameFull: Xu, Wu-Tan
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            NameFull: He, Wen-Rui
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              M: 04
              Text: 4/7/2016
              Type: published
              Y: 2016
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