高等学校化学学报

高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (S1): 327.

• Chemistry in Materials Sciences • 上一篇    下一篇

Self-assembly of an Unprecedented Cynao-bridged One-dimensional 4f-3d Complex[Eu(DMF)4(H2O)2Cr(CN)6] H2O

KOU Hui-Zhong1, GAO Song1, YU Kai-Bei2   

  1. 1. Materials Chemistry and Applications, Peking University, Beijing 100871;
    2. Chengdu Center for Analysis and Measurement, Academic Sinica, Chengdu 610041
  • 出版日期:2000-12-31 发布日期:2000-12-31

Self-assembly of an Unprecedented Cynao-bridged One-dimensional 4f-3d Complex[Eu(DMF)4(H2O)2Cr(CN)6] H2O

KOU Hui-Zhong1, GAO Song1, YU Kai-Bei2   

  1. 1. Materials Chemistry and Applications, Peking University, Beijing 100871;
    2. Chengdu Center for Analysis and Measurement, Academic Sinica, Chengdu 610041
  • Online:2000-12-31 Published:2000-12-31

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摘要：

Recently, there has been considerable interest in cyano-bridged lanthanide(Ⅲ) hexacyanometalate(Ⅲ) complexes LnM(CN)6·nH2O (M=Fe, Cr and Co) because of their potential as catalytic, semiconductive, and magnetic materials.[1-8] In this study, we employed N,N-dimethylformamide (DMF) as a hybrid ligand to construct a bimetallic complex[Eu(DMF)4(H2O)2Cr(CN)6]·H2O. It was synthesized as yellow crystals by the self-assembly of anhydrous EuCl3 and (Bu4N)3[Cr(CN)6] in MeOH and DMF. Single-crystal X-ray diffraction analysis shows that it consists of a cyano-bridged chain structure. The Eu atom is eight-coordinate with a distorted bicapped square antiprism geometry. Six oxygen atoms of two water molecules and four DMF molecules and two nitrogen atoms of the bridging CN ligands are bound to Eu with the Eu-O distance ranging from 2.368(7) to 2.447(8) Å. The bridging cyanides coordinate to the Europium(Ⅲ) ion[N(l)-Eu=2.543(9) Å and N(3)-EuA=2.543(8) Å] in a bent fashion with the bond angles of 164.0(9) for C(1)-N(1)-Nd and 155.1(7)。for C(3)-N(3)-EuA (A denotes the symmetry transformation:-x+l,y-l/2,-z+3/2). Each Cr(CN)6 coordinates to two Eu(Ⅲ) ions using two cis cyanide ligands, while each Eu(DMF)4(H2O)2 group connects two Cr(CN)6 moieties in a cis fashion, giving rise to an unprecedented chain structure. Crystal data:monoclinic, space group P21/c, a=13.151(2), b=12.905(2), c=19.186(2) Å, β=109.70(1)°, V=3065.5(7) Å3,Z=4, ρobs=1.531 Mg m-3, S=1.024,R1=0.0540, Rw=0.1616.

Abstract:

Recently, there has been considerable interest in cyano-bridged lanthanide(Ⅲ) hexacyanometalate(Ⅲ) complexes LnM(CN)6·nH2O (M=Fe, Cr and Co) because of their potential as catalytic, semiconductive, and magnetic materials.[1-8] In this study, we employed N,N-dimethylformamide (DMF) as a hybrid ligand to construct a bimetallic complex[Eu(DMF)4(H2O)2Cr(CN)6]·H2O. It was synthesized as yellow crystals by the self-assembly of anhydrous EuCl3 and (Bu4N)3[Cr(CN)6] in MeOH and DMF. Single-crystal X-ray diffraction analysis shows that it consists of a cyano-bridged chain structure. The Eu atom is eight-coordinate with a distorted bicapped square antiprism geometry. Six oxygen atoms of two water molecules and four DMF molecules and two nitrogen atoms of the bridging CN ligands are bound to Eu with the Eu-O distance ranging from 2.368(7) to 2.447(8) Å. The bridging cyanides coordinate to the Europium(Ⅲ) ion[N(l)-Eu=2.543(9) Å and N(3)-EuA=2.543(8) Å] in a bent fashion with the bond angles of 164.0(9) for C(1)-N(1)-Nd and 155.1(7)。for C(3)-N(3)-EuA (A denotes the symmetry transformation:-x+l,y-l/2,-z+3/2). Each Cr(CN)6 coordinates to two Eu(Ⅲ) ions using two cis cyanide ligands, while each Eu(DMF)4(H2O)2 group connects two Cr(CN)6 moieties in a cis fashion, giving rise to an unprecedented chain structure. Crystal data:monoclinic, space group P21/c, a=13.151(2), b=12.905(2), c=19.186(2) Å, β=109.70(1)°, V=3065.5(7) Å3,Z=4, ρobs=1.531 Mg m-3, S=1.024,R1=0.0540, Rw=0.1616.

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