“Jumping” crystals: structures and properties of CuII complexes with N-methylimidazolyl- and N-methyltriazolyl-substituted nitronyl nitroxides View Full Text


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Article Info

DATE

2011-12

AUTHORS

V. I. Ovcharenko, E. V. Tretyakov, S. V. Fokin, E. Yu. Fursova, O. V. Kuznetsova, S. E. Tolstikov, G. V. Romanenko, A. S. Bogomyakov, R. Z. Sagdeev

ABSTRACT

To find the factors favorable for the appearance of chemomechanical activity of heterospin crystals, a series of new heterospin complexes were synthesized and characterized. It includes [Cu(tfac)2LIm2]·2CH2Cl2, [Cu(tfac)2LIm2]·2EtOH, [[Cu(pfu)2]2LIm3]·1/2CH2Cl2, [Cu(pfh)2LIm2]·1/2CH2Cl2, [Cu(piv)2LIm2]·2MeOH, [Co(piv)2LIm2], [\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ Cu(hfac)_2 L^{CD_3 } _2 $$\end{document}], [Cu(hfac)2LTr]2·CH2Cl2, and [Cu(hfac)2LTr2] (LIm, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ L^{CD_3 } $$\end{document}, and LTr are N-methylimidazolyl-, N-trideuteriomethylimidazolyl-, and N-methyltriazolyl-substituted nitronyl nitroxides, respectively; tfac, hfac, pfu, pfh, and piv are the charged coordinated diamagnetic ligands 1,1,5,5-tetrafluoropentane-2,4-dionate, 1,1,1,5,5,5-hexafluoropentane-2,4-dionate, 1,1,1,2,2,3,3,4,4,8,8,9,9,10,10,11,11,11-octadecafluoroundecane-5,7-dionate, 1,1,1,5,5,6,6,6-octafluorohexane-2,4-dionate, and 2,2-dimethylpropionate, respectively). The crystal and molecular structures of all compounds were determined. The results of the X-ray diffraction study of the complex [Ni(hfac)2LIm2] synthesized earlier are reported. In the solid state of the complexes [Cu(pfh)2LIm2] and [Co(piv)2LIm2], the paramagnetic ligands are cis-coordinated to the central atom in a monodentate fashion via the donor N atom of the imidazole ring. In the dinuclear complexes [[Cu(pfu)2]2LIm3] and [Cu(hfac)2LTr]2, the paramagnetic ligands are also in cis positions but act as bridges through coordination of the donor N atoms of the azole ring and the O atom of the nitronyl nitroxide moiety to different Cu2+ ions. In the solid complexes \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ Cu(hfac)_2 L^{CD_3 } _2 $$\end{document} , [Cu(hfac)2LTr2], [Cu(tfac)2LIm2]·2CH2Cl2, [Cu(tfac)2LIm2]·2EtOH, and [Cu(piv)2LIm2]·2MeOH, the nitronyl nitroxide radicals in the mononuclear heterospin molecules are in trans positions. The packing motif in the crystal structures of the complexes \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ Cu(hfac)_2 L^{CD_3 } _2 $$\end{document} , [Cu(tfac)2LIm2]·2CH2Cl2, and [Cu(tfac)2LIm2]·2EtOH is the same as that in the previously studied complexes [M(hfac)2LIm2] exhibiting chemomechanical activity. Among the complexes under consideration, only crystals of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ Cu(hfac)_2 L^{CD_3 } _2 $$\end{document} can exhibit chemomechanical activity, that is to make jumps upon heating or irradiation. The results of the present study suggest that the packing of the solid-state structure plays a key role in the generation of mechanical activity of the crystals. More... »

PAGES

2457-2469

References to SciGraph publications

  • 1986. Magnetochemistry in NONE
  • Identifiers

    URI

    http://scigraph.springernature.com/pub.10.1007/s11172-011-0381-7

    DOI

    http://dx.doi.org/10.1007/s11172-011-0381-7

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    7 schema:description To find the factors favorable for the appearance of chemomechanical activity of heterospin crystals, a series of new heterospin complexes were synthesized and characterized. It includes [Cu(tfac)2LIm2]·2CH2Cl2, [Cu(tfac)2LIm2]·2EtOH, [[Cu(pfu)2]2LIm3]·1/2CH2Cl2, [Cu(pfh)2LIm2]·1/2CH2Cl2, [Cu(piv)2LIm2]·2MeOH, [Co(piv)2LIm2], [\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ Cu(hfac)_2 L^{CD_3 } _2 $$\end{document}], [Cu(hfac)2LTr]2·CH2Cl2, and [Cu(hfac)2LTr2] (LIm, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ L^{CD_3 } $$\end{document}, and LTr are N-methylimidazolyl-, N-trideuteriomethylimidazolyl-, and N-methyltriazolyl-substituted nitronyl nitroxides, respectively; tfac, hfac, pfu, pfh, and piv are the charged coordinated diamagnetic ligands 1,1,5,5-tetrafluoropentane-2,4-dionate, 1,1,1,5,5,5-hexafluoropentane-2,4-dionate, 1,1,1,2,2,3,3,4,4,8,8,9,9,10,10,11,11,11-octadecafluoroundecane-5,7-dionate, 1,1,1,5,5,6,6,6-octafluorohexane-2,4-dionate, and 2,2-dimethylpropionate, respectively). The crystal and molecular structures of all compounds were determined. The results of the X-ray diffraction study of the complex [Ni(hfac)2LIm2] synthesized earlier are reported. In the solid state of the complexes [Cu(pfh)2LIm2] and [Co(piv)2LIm2], the paramagnetic ligands are cis-coordinated to the central atom in a monodentate fashion via the donor N atom of the imidazole ring. In the dinuclear complexes [[Cu(pfu)2]2LIm3] and [Cu(hfac)2LTr]2, the paramagnetic ligands are also in cis positions but act as bridges through coordination of the donor N atoms of the azole ring and the O atom of the nitronyl nitroxide moiety to different Cu2+ ions. In the solid complexes \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ Cu(hfac)_2 L^{CD_3 } _2 $$\end{document} , [Cu(hfac)2LTr2], [Cu(tfac)2LIm2]·2CH2Cl2, [Cu(tfac)2LIm2]·2EtOH, and [Cu(piv)2LIm2]·2MeOH, the nitronyl nitroxide radicals in the mononuclear heterospin molecules are in trans positions. The packing motif in the crystal structures of the complexes \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ Cu(hfac)_2 L^{CD_3 } _2 $$\end{document} , [Cu(tfac)2LIm2]·2CH2Cl2, and [Cu(tfac)2LIm2]·2EtOH is the same as that in the previously studied complexes [M(hfac)2LIm2] exhibiting chemomechanical activity. Among the complexes under consideration, only crystals of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ Cu(hfac)_2 L^{CD_3 } _2 $$\end{document} can exhibit chemomechanical activity, that is to make jumps upon heating or irradiation. The results of the present study suggest that the packing of the solid-state structure plays a key role in the generation of mechanical activity of the crystals.
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    84 schema:name “Jumping” crystals: structures and properties of CuII complexes with N-methylimidazolyl- and N-methyltriazolyl-substituted nitronyl nitroxides
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