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Chiral Tetranuclear μ3-Alkoxo-Bridged Copper(Il) Complex with 2 + 4 Cubane-Like Cu4O4 Core Framework and Ferromagnetic Ground State.

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Title: Chiral Tetranuclear μ3-Alkoxo-Bridged Copper(Il) Complex with 2 + 4 Cubane-Like Cu4O4 Core Framework and Ferromagnetic Ground State.
Authors: Burkhardt, Anja1, Spielberg, Eike T.1, Görls, Helmar1, Plass, Winfried1 sekr.plass@uni-jena.de
Source: Inorganic Chemistry. 4/7/2008, Vol. 47 Issue 7, p2485-2493. 9p. 6 Diagrams, 2 Charts, 4 Graphs.
Subjects: Ferromagnetism, Chitosan, Copper compounds, Hydrogen bonding, Molecular association
Abstract: The sugar-modified Schiff base ligand benzyl 2-deoxy-2-salicylideneamino-c~-D-glucopyranoside H2L, prepared by condensation of salicylaldehyde and the monomeric chitosan analogue benzyl 2-deoxy-2-amino-a-D-glucopyranoside, reacts with copper(ll) acetate to form a self-assembled, alkoxo-bridged tetranuclear homoleptic copper(Il) complex [{Cu(L)}4] (4) with Cu404 heterocubane core. The chiral complex 4 crystallizes in the space group P212121. The tetranuclear complex 4 is composed of two dinuclear {Cu(L)}2 entities linked by the four u3-bridging C-3 alkoxide oxygen atoms of the sugar backbone. The preorganization of the dimeric {Cu(L)}2 entities is enforced by strong hydrogen bonds between the phenolate oxygen atom and the 0-4 hydroxy group of the two constituting chiral monomeric building blocks. Therefore the Cu404 core can be classified as a type I or 2 + 4 cubane. The chirality of the structure is confirmed by circular dichroism (CD) spectra, which reveal a significant dichroism associated with the copper centered transitions at around 600 nm. Temperature dependent magnetic susceptibility measurements indicate ferromagnetic exchange interactions in complex 4. Fitting of the experimental data with a two J model based on the 2 + 4 topology (H = - J1(S1S3 + S2S4) - J2(S1 + S3)(S2 + S4)) leads to exchange coupling constants of J1 = 64 and J2 = 4 cm1. The observed ferromagnetic coupling can be attributed to the very small Cu-O-Cu bridging angles within the Cu202 core of the constituting dimeric entities, which are a result of the conformational requirements introduced by the sugar backbone. 4 is not only the first example of an alkoxo- bridged tetranuclear copper(ll) complex with Cu404 core representing the 2 + 4 cubane class with ferromagnetic ground state but also a rare example for the class of molecules combining a ferromagnetic ground state with optical activity. The ferromagnetic S = 2 ground state of 4 is confirmed by magnetization measurements and ESR spectroscopy. [ABSTRACT FROM AUTHOR]
Copyright of Inorganic Chemistry is the property of American Chemical Society 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: Chiral Tetranuclear μ<subscript>3</subscript>-Alkoxo-Bridged Copper(Il) Complex with 2 + 4 Cubane-Like Cu<subscript>4</subscript>O<subscript>4</subscript> Core Framework and Ferromagnetic Ground State.
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  Data: <searchLink fieldCode="AR" term="%22Burkhardt%2C+Anja%22">Burkhardt, Anja</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Spielberg%2C+Eike+T%2E%22">Spielberg, Eike T.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Görls%2C+Helmar%22">Görls, Helmar</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Plass%2C+Winfried%22">Plass, Winfried</searchLink><relatesTo>1</relatesTo><i> sekr.plass@uni-jena.de</i>
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  Data: <searchLink fieldCode="JN" term="%22Inorganic+Chemistry%22">Inorganic Chemistry</searchLink>. 4/7/2008, Vol. 47 Issue 7, p2485-2493. 9p. 6 Diagrams, 2 Charts, 4 Graphs.
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  Data: <searchLink fieldCode="DE" term="%22Ferromagnetism%22">Ferromagnetism</searchLink><br /><searchLink fieldCode="DE" term="%22Chitosan%22">Chitosan</searchLink><br /><searchLink fieldCode="DE" term="%22Copper+compounds%22">Copper compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrogen+bonding%22">Hydrogen bonding</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+association%22">Molecular association</searchLink>
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  Label: Abstract
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  Data: The sugar-modified Schiff base ligand benzyl 2-deoxy-2-salicylideneamino-c~-D-glucopyranoside H2L, prepared by condensation of salicylaldehyde and the monomeric chitosan analogue benzyl 2-deoxy-2-amino-a-D-glucopyranoside, reacts with copper(ll) acetate to form a self-assembled, alkoxo-bridged tetranuclear homoleptic copper(Il) complex [{Cu(L)}4] (4) with Cu404 heterocubane core. The chiral complex 4 crystallizes in the space group P212121. The tetranuclear complex 4 is composed of two dinuclear {Cu(L)}2 entities linked by the four u3-bridging C-3 alkoxide oxygen atoms of the sugar backbone. The preorganization of the dimeric {Cu(L)}2 entities is enforced by strong hydrogen bonds between the phenolate oxygen atom and the 0-4 hydroxy group of the two constituting chiral monomeric building blocks. Therefore the Cu404 core can be classified as a type I or 2 + 4 cubane. The chirality of the structure is confirmed by circular dichroism (CD) spectra, which reveal a significant dichroism associated with the copper centered transitions at around 600 nm. Temperature dependent magnetic susceptibility measurements indicate ferromagnetic exchange interactions in complex 4. Fitting of the experimental data with a two J model based on the 2 + 4 topology (H = - J1(S1S3 + S2S4) - J2(S1 + S3)(S2 + S4)) leads to exchange coupling constants of J1 = 64 and J2 = 4 cm1. The observed ferromagnetic coupling can be attributed to the very small Cu-O-Cu bridging angles within the Cu202 core of the constituting dimeric entities, which are a result of the conformational requirements introduced by the sugar backbone. 4 is not only the first example of an alkoxo- bridged tetranuclear copper(ll) complex with Cu404 core representing the 2 + 4 cubane class with ferromagnetic ground state but also a rare example for the class of molecules combining a ferromagnetic ground state with optical activity. The ferromagnetic S = 2 ground state of 4 is confirmed by magnetization measurements and ESR spectroscopy. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
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  Data: <i>Copyright of Inorganic Chemistry is the property of American Chemical Society 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: 10.1021/ic701777t
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        Text: English
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        PageCount: 9
        StartPage: 2485
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      – SubjectFull: Ferromagnetism
        Type: general
      – SubjectFull: Chitosan
        Type: general
      – SubjectFull: Copper compounds
        Type: general
      – SubjectFull: Hydrogen bonding
        Type: general
      – SubjectFull: Molecular association
        Type: general
    Titles:
      – TitleFull: Chiral Tetranuclear μ3-Alkoxo-Bridged Copper(Il) Complex with 2 + 4 Cubane-Like Cu4O4 Core Framework and Ferromagnetic Ground State.
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            NameFull: Burkhardt, Anja
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            NameFull: Spielberg, Eike T.
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            NameFull: Görls, Helmar
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              M: 04
              Text: 4/7/2008
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              Y: 2008
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              Value: 47
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