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Dicopper(II) metallacyclophanes featuring acridine-based spacers: long-range magnetic coupling and selective catalytic oxidation of hydroquinone.

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Title: Dicopper(II) metallacyclophanes featuring acridine-based spacers: long-range magnetic coupling and selective catalytic oxidation of hydroquinone.
Authors: Kalinke, Lucas Hoffmann Greghi1 (AUTHOR), Souza, Maria Clara Orioli Emidio2 (AUTHOR), Romanholo, Pedro Victor Valadares2 (AUTHOR), Souza, Jackson Junior Santos de2 (AUTHOR), Roveda, Antonio Carlos3 (AUTHOR), Machado, Sergio Antonio Spinola3 (AUTHOR), Valdo, Ana Karoline Silva Mendanha4 (AUTHOR), Martins, Felipe Terra2 (AUTHOR), Rabelo, Renato2,5 (AUTHOR), Cano, Joan5 (AUTHOR) joan.cano@uv.es, Lloret, Francesc5 (AUTHOR), Julve, Miguel5 (AUTHOR), Sgobbi, Livia Flório2 (AUTHOR) livia_sgobbi@ufg.br, Cangussu, Danielle2 (AUTHOR) danielle_cangussu@ufg.br
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 7/7/2025, Vol. 54 Issue 25, p10097-10110. 14p.
Subjects: Catalytic oxidation, Hydroquinone, Copper compounds, Ferromagnetism, Magnetic coupling, Acridine derivatives, Cyclophanes
Abstract: The copper(II) complexes {Na4(H2O)8[Cu2(acriba)2(H2O)2]}n·4nH2O (1) and (Bu4N)4[Cu2(acriba)2]·5H2O (2) [H4acriba = N,N′-3,6-acridinebis(oxamic acid) and Bu4N+ = tetra-n-butylammonium cation] have been synthesized and characterized. Their crystal structures revealed the occurrence of [Cu2(acriba)2(H2O)2]4− (1) and [Cu2(acriba)2]4− (2) units of the [3,3] metallacyclophane-type which are built by two acridine linkers connected by two N–Cu–N bonds. The electroneutrality in 1 is achieved by their coordination to hydrated sodium(I) cations to afford a heterobimetallic sheet-like polymer, whereas that in 2 is ensured by bulky organic Bu4N+ cations to yield well-separated discrete dicopper(II) complexes. The spectrophotometric study of the catalytic activity of 1 and the related complex [Na6Cu2(mpyba)2Cl2(H2O)8]·7H2O (3) [H4mpyba = N,N′-2,6-pyridinebis(oxamic acid)] towards the oxidation of phenolic derivatives in aqueous solution showed a remarkable catalytic performance only for the hydroquinone with a better catalytic role in the case of 1. This superior catalytic behavior may be explained by the higher Lewis acidity of the Cu(II) ions derived from the inherent electronic delocalization of the extended aromatic acridine fragment compared to the pyridine one. The magnetic properties of 1 and 2 show weak intramolecular ferromagnetic interactions within their metallacyclophane units [J = +1.83 (1) and +1.72 cm−1 (2); H = −JSCu1·SCu2 where SCu1 = SCu2 = 1/2], their nature and magnitude being substantiated by theoretical calculations. These two examples illustrate the ability of the acridine moieties to mediate ferromagnetic interactions between copper(II) ions through the very long –Namidate–C–C–C–N–C–C–C–Namidate– exchange pathway in the context of the spin polarization mechanism. [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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  Label: Title
  Group: Ti
  Data: Dicopper(II) metallacyclophanes featuring acridine-based spacers: long-range magnetic coupling and selective catalytic oxidation of hydroquinone.
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  Data: <searchLink fieldCode="AR" term="%22Kalinke%2C+Lucas+Hoffmann+Greghi%22">Kalinke, Lucas Hoffmann Greghi</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Souza%2C+Maria+Clara+Orioli+Emidio%22">Souza, Maria Clara Orioli Emidio</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Romanholo%2C+Pedro+Victor+Valadares%22">Romanholo, Pedro Victor Valadares</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Souza%2C+Jackson+Junior+Santos+de%22">Souza, Jackson Junior Santos de</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Roveda%2C+Antonio+Carlos%22">Roveda, Antonio Carlos</searchLink><relatesTo>3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Machado%2C+Sergio+Antonio+Spinola%22">Machado, Sergio Antonio Spinola</searchLink><relatesTo>3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Valdo%2C+Ana+Karoline+Silva+Mendanha%22">Valdo, Ana Karoline Silva Mendanha</searchLink><relatesTo>4</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Martins%2C+Felipe+Terra%22">Martins, Felipe Terra</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Rabelo%2C+Renato%22">Rabelo, Renato</searchLink><relatesTo>2,5</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Cano%2C+Joan%22">Cano, Joan</searchLink><relatesTo>5</relatesTo> (AUTHOR)<i> joan.cano@uv.es</i><br /><searchLink fieldCode="AR" term="%22Lloret%2C+Francesc%22">Lloret, Francesc</searchLink><relatesTo>5</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Julve%2C+Miguel%22">Julve, Miguel</searchLink><relatesTo>5</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Sgobbi%2C+Livia+Flório%22">Sgobbi, Livia Flório</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> livia_sgobbi@ufg.br</i><br /><searchLink fieldCode="AR" term="%22Cangussu%2C+Danielle%22">Cangussu, Danielle</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> danielle_cangussu@ufg.br</i>
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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>. 7/7/2025, Vol. 54 Issue 25, p10097-10110. 14p.
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  Data: <searchLink fieldCode="DE" term="%22Catalytic+oxidation%22">Catalytic oxidation</searchLink><br /><searchLink fieldCode="DE" term="%22Hydroquinone%22">Hydroquinone</searchLink><br /><searchLink fieldCode="DE" term="%22Copper+compounds%22">Copper compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Ferromagnetism%22">Ferromagnetism</searchLink><br /><searchLink fieldCode="DE" term="%22Magnetic+coupling%22">Magnetic coupling</searchLink><br /><searchLink fieldCode="DE" term="%22Acridine+derivatives%22">Acridine derivatives</searchLink><br /><searchLink fieldCode="DE" term="%22Cyclophanes%22">Cyclophanes</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The copper(II) complexes {Na4(H2O)8[Cu2(acriba)2(H2O)2]}n·4nH2O (1) and (Bu4N)4[Cu2(acriba)2]·5H2O (2) [H4acriba = N,N′-3,6-acridinebis(oxamic acid) and Bu4N+ = tetra-n-butylammonium cation] have been synthesized and characterized. Their crystal structures revealed the occurrence of [Cu2(acriba)2(H2O)2]4− (1) and [Cu2(acriba)2]4− (2) units of the [3,3] metallacyclophane-type which are built by two acridine linkers connected by two N–Cu–N bonds. The electroneutrality in 1 is achieved by their coordination to hydrated sodium(I) cations to afford a heterobimetallic sheet-like polymer, whereas that in 2 is ensured by bulky organic Bu4N+ cations to yield well-separated discrete dicopper(II) complexes. The spectrophotometric study of the catalytic activity of 1 and the related complex [Na6Cu2(mpyba)2Cl2(H2O)8]·7H2O (3) [H4mpyba = N,N′-2,6-pyridinebis(oxamic acid)] towards the oxidation of phenolic derivatives in aqueous solution showed a remarkable catalytic performance only for the hydroquinone with a better catalytic role in the case of 1. This superior catalytic behavior may be explained by the higher Lewis acidity of the Cu(II) ions derived from the inherent electronic delocalization of the extended aromatic acridine fragment compared to the pyridine one. The magnetic properties of 1 and 2 show weak intramolecular ferromagnetic interactions within their metallacyclophane units [J = +1.83 (1) and +1.72 cm−1 (2); H = −JSCu1·SCu2 where SCu1 = SCu2 = 1/2], their nature and magnitude being substantiated by theoretical calculations. These two examples illustrate the ability of the acridine moieties to mediate ferromagnetic interactions between copper(II) ions through the very long –Namidate–C–C–C–N–C–C–C–Namidate– exchange pathway in the context of the spin polarization mechanism. [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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RecordInfo BibRecord:
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    Identifiers:
      – Type: doi
        Value: 10.1039/d5dt01037c
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 14
        StartPage: 10097
    Subjects:
      – SubjectFull: Catalytic oxidation
        Type: general
      – SubjectFull: Hydroquinone
        Type: general
      – SubjectFull: Copper compounds
        Type: general
      – SubjectFull: Ferromagnetism
        Type: general
      – SubjectFull: Magnetic coupling
        Type: general
      – SubjectFull: Acridine derivatives
        Type: general
      – SubjectFull: Cyclophanes
        Type: general
    Titles:
      – TitleFull: Dicopper(II) metallacyclophanes featuring acridine-based spacers: long-range magnetic coupling and selective catalytic oxidation of hydroquinone.
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              M: 07
              Text: 7/7/2025
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