Investigation on structures, luminescent and magnetic properties of Ln III –M (M = Fe II HS , Co II ) coordination polymers

  • Zhao X
  • Cui P
  • Zhao B
 et al. 
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The structures, luminescent and magnetic properties of three series of coordination polymers with formulas-{[Fe(3)Ln(2)(L(1))(6)(H(2)O)(6)].xH(2)O}(n) (Ln = Pr-Er; 1-9), {[Co(3)Ln(2)(L(1))(6)(H(2)O)(6)].yH(2)O}(n) (Ln = Pr-Dy, Yb; 10-17) and {[Co(2)Ln(L(2))(HL(2))(2)(H(2)O)(7)].zH(2)O}(n) (Ln = Eu-Yb; 18-25) (H(2)L(1) = pyridine-2,6-dicarboxylic acid, H(3)L(2) = 4-hydroxyl-pyridine-2,6-dicarboxylic acid) were systematically explored in this contribution. [Fe(II)(HS)-L(1)-Ln(III)] (1-9) and [Co(II)-L(1)-Ln(III)] (10-17) series are isostructural, and display 3D porous networks with 1D nanosized channels constructed by Fe/Co-OCO-Ln linkages. Furthermore, two types of "water" pipes are observed in 1D channels. [Co(II)-L(2)-Ln(III)] (18-25) series exhibit 2D open frameworks based on double-stranded helical motifs, which are further assembled into 3D porous structures by intermolecular hydrogen bonds between hydroxyl groups. The variety of the resulting structures is mainly due to the HO-substitution effect. These 3D coordination polymers show considerably high thermal stability, and do not decomposed until 400 degrees C. The high-spin Fe(II) ion in [Fe(II)(HS)-L(1)-Ln(III)] was confirmed by X-ray photoelectron spectroscopy, Mossbauer spectroscopy and magnetic studies. The luminescent spectra of coordination polymers associated with Sm(III), Eu(III), Tb(III) and Dy(III) were systematically investigated, and indicate that different d-metal ions in d-f systems may result in dissimilar luminescent properties. The magnetic properties of [Fe(II)(HS)-L(1)-Ln(III)] (3, 6, 7, 9, 13), [Co(II)-L(1)-Ln(III)] (15-17) and [Co(II)-L(2)-Ln(III)] (19-24) coordination polymers were also studied, and the chi(M)T values decrease with cooling. For the single ion behavior of Co(II) and Ln(III) ions, the magnetic coupling nature between Fe(II)(HS)/Co(II) and Ln(III) ions cannot be clearly depicted as antiferromagnetic coupling.

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  • Xiao-Qing Zhao

  • Ping Cui

  • Bin Zhao

  • Wei Shi

  • Peng Cheng

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