Molecular magnets based on chain polymer complexes of copper(II) bis(hexafluoroacetylacetonate) with isoxazolyl-substituted nitronyl nitroxides View Full Text


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Article Info

DATE

2011-12

AUTHORS

S. V. Fokin, S. E. Tolstikov, E. V. Tretyakov, G. V. Romanenko, A. S. Bogomyakov, S. L. Veber, R. Z. Sagdeev, V. I. Ovcharenko

ABSTRACT

First isoxazolyl-substituted nitronyl nitroxides (L and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$L^{Me_2 }$$\end{document}) were synthesized and characterized. Their reactions with Cu(hfac)2 and Mn(hfac)2 (hfac is hexafluoroacetylacetonate) afford the heterospin complexes [Cu(hfac)2L]n, [Cu2(hfac)4L]n, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu_2 (hfac)_4 L^{Me_2 } } \right]_n$$\end{document}, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu(hfac)_2 L^{Me_2 } } \right]_n$$\end{document}, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu(hfac)_2 L^{Me_2 } _2 } \right]$$\end{document}, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu(hfac)_2 L^{Me_2 } (MeCN)} \right]$$\end{document}, [Mn(hfac)2]3L4, and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Me(hfac)_2 L^{Me_2 } } \right]_2$$\end{document}. In the ligand L, the N atom of the isoxazole ring (NIz) has weak electron-donating properties. For example, the paramagnetic ligand in the chain polymer complex [Cu(hfac)2L]n acts as a bidentate bridging ligand coordinated through both O atoms of the nitronyl nitroxide group (ON-O); the NIz and OIz atoms are not involved in the coordination. The introduction of Me groups into the isoxazole substituent results in an increase in the electron density on the NIz atom and enables the synthesis of the chain polymer complex \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu(hfac)_2 L^{Me_2 } } \right]_n$$\end{document}, in which the bidentate bridging ligand \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$L^{Me_2 }$$\end{document} is coordinated through the ON-O and NIz atoms. In the mononuclear complexes \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu(hfac)_2 L^{Me_2 } _2 } \right]$$\end{document} and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu(hfac)_2 L^{Me_2 } (MeCN)} \right]$$\end{document}, the paramagnetic ligand is coordinated only through the NIz atom. The solid heterospin Mn complexes [Mn(hfac)2]3L4 and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Mn(hfac)_2 L^{Me_2 } } \right]_2$$\end{document} have a molecular structure. In these complexes, strong antiferromagnetic intracluster exchange interactions arise. The residual magnetic moments of the exchange clusters in the complex [Mn(hfac)2]3L4 are ferromagnetically coupled, resulting in the increase in the effective magnetic moment (μeff) of the complex with decreasing temperature in the range of 300—30 K. The thermomagnetic study of the complexes [Cu(hfac)2L]n, [Cu2(hfac)4L]n, and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu_2 (hfac)_4 L^{Me_2 } } \right]_n$$\end{document} in the range of 2–300 K revealed the ferromagnetic ordering at temperatures below 5 K. The ESR study of the solid complex \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Cu(hfac)_2 L^{Me_2 } } \right]_n$$\end{document} showed that the decrease in its μeff in the temperature range of 30–300 K is associated with the direct exchange interaction between the unpaired electrons of the nitronyl nitroxides of adjacent chains, whereas at temperatures below 30 K, only Cu2+ ions contribute to the magnetic susceptibility of the complex. More... »

PAGES

2470-2484

References to SciGraph publications

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URI

http://scigraph.springernature.com/pub.10.1007/s11172-011-0382-6

DOI

http://dx.doi.org/10.1007/s11172-011-0382-6

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https://app.dimensions.ai/details/publication/pub.1019815621


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    "description": "First isoxazolyl-substituted nitronyl nitroxides (L and \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$L^{Me_2 }$$\\end{document}) were synthesized and characterized. Their reactions with Cu(hfac)2 and Mn(hfac)2 (hfac is hexafluoroacetylacetonate) afford the heterospin complexes [Cu(hfac)2L]n, [Cu2(hfac)4L]n, \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu_2 (hfac)_4 L^{Me_2 } } \\right]_n$$\\end{document}, \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu(hfac)_2 L^{Me_2 } } \\right]_n$$\\end{document}, \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu(hfac)_2 L^{Me_2 } _2 } \\right]$$\\end{document}, \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu(hfac)_2 L^{Me_2 } (MeCN)} \\right]$$\\end{document}, [Mn(hfac)2]3L4, and \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Me(hfac)_2 L^{Me_2 } } \\right]_2$$\\end{document}. In the ligand L, the N atom of the isoxazole ring (NIz) has weak electron-donating properties. For example, the paramagnetic ligand in the chain polymer complex [Cu(hfac)2L]n acts as a bidentate bridging ligand coordinated through both O atoms of the nitronyl nitroxide group (ON-O); the NIz and OIz atoms are not involved in the coordination. The introduction of Me groups into the isoxazole substituent results in an increase in the electron density on the NIz atom and enables the synthesis of the chain polymer complex \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu(hfac)_2 L^{Me_2 } } \\right]_n$$\\end{document}, in which the bidentate bridging ligand \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$L^{Me_2 }$$\\end{document} is coordinated through the ON-O and NIz atoms. In the mononuclear complexes \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu(hfac)_2 L^{Me_2 } _2 } \\right]$$\\end{document} and \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu(hfac)_2 L^{Me_2 } (MeCN)} \\right]$$\\end{document}, the paramagnetic ligand is coordinated only through the NIz atom. The solid heterospin Mn complexes [Mn(hfac)2]3L4 and \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Mn(hfac)_2 L^{Me_2 } } \\right]_2$$\\end{document} have a molecular structure. In these complexes, strong antiferromagnetic intracluster exchange interactions arise. The residual magnetic moments of the exchange clusters in the complex [Mn(hfac)2]3L4 are ferromagnetically coupled, resulting in the increase in the effective magnetic moment (\u03bceff) of the complex with decreasing temperature in the range of 300\u201430 K. The thermomagnetic study of the complexes [Cu(hfac)2L]n, [Cu2(hfac)4L]n, and \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu_2 (hfac)_4 L^{Me_2 } } \\right]_n$$\\end{document} in the range of 2\u2013300 K revealed the ferromagnetic ordering at temperatures below 5 K. The ESR study of the solid complex \\documentclass[12pt]{minimal}\n\t\t\t\t\\usepackage{amsmath}\n\t\t\t\t\\usepackage{wasysym}\n\t\t\t\t\\usepackage{amsfonts}\n\t\t\t\t\\usepackage{amssymb}\n\t\t\t\t\\usepackage{amsbsy}\n\t\t\t\t\\usepackage{mathrsfs}\n\t\t\t\t\\usepackage{upgreek}\n\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\n\t\t\t\t\\begin{document}$$\\left[ {Cu(hfac)_2 L^{Me_2 } } \\right]_n$$\\end{document} showed that the decrease in its \u03bceff in the temperature range of 30\u2013300 K is associated with the direct exchange interaction between the unpaired electrons of the nitronyl nitroxides of adjacent chains, whereas at temperatures below 30 K, only Cu2+ ions contribute to the magnetic susceptibility of the complex.", 
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The solid heterospin Mn complexes [Mn(hfac)2]3L4 and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\left[ {Mn(hfac)_2 L^{Me_2 } } \right]_2$$\end{document} have a molecular structure. In these complexes, strong antiferromagnetic intracluster exchange interactions arise. The residual magnetic moments of the exchange clusters in the complex [Mn(hfac)2]3L4 are ferromagnetically coupled, resulting in the increase in the effective magnetic moment (μeff) of the complex with decreasing temperature in the range of 300—30 K. 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