两例弯曲型二酸Zn(Ⅱ)、Cd(Ⅱ)配合物的合成,结构与荧光性质 |
Synthesis, Structures and Photoluminescence of Two Zinc and Cadmium V-shaped Dicarboxylates |
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摘要: 本文以弯曲型二酸2,2′-azanediyldibenzoic acid(H2L)为配体,溶液法合成了2个新的配合物[Zn2(L)2(H2O)2]·H2O (1)和[(NH4)2 Cd(L)2]·C2H5OH (2)。通过X射线单晶衍射分别测定了他们的结构:配合物1属于单斜晶系,空间群为P21/c,a=1.487 9(2) nm,b=0.898 9(1) nm,c=1.210 0(2) nm,β=99.211(2)°,V=1.597 3(3) nm3。配体L的羧酸根均为单齿配位,桥连2个锌离子,形成一个零维的[2+2]扭曲环状结构,并由氢键作用连接成二维结构。配合物2属于正交晶系,空间群为Pbcn,a=2.060 2(2) nm,b=1.281 9(1) nm,c=2.246 1(1) nm,V=5.931 9(6) nm3。Cd(Ⅱ)取较少见的羧酸根螯合八配位结构,L与Cd(Ⅱ)也形成了二核环状结构,并通过共用1个镉离子而形成一维的阴离子链,抗衡阳离子为NH4+。链间通过π…π作用堆积成三维结构。此外,还并测定了配体及配合物的荧光性质。 |
关键词: 弯曲型二酸 晶体结构 d10金属配合物 荧光性质 |
基金项目: |
Abstract: Two new coordination complex are synthesized through solvent-volatilization method from reaction of V-shaped 2,2′-azanediyldibenzoic acid (H2L) with Zn(Ⅱ) or Cd(Ⅱ) salts, namely [Zn2(L)2(H2O)2]·H2O (1) and [(NH4)2 Cd(L)2]·C2H5OH (2). Crystal structural analyses reveals that 1 belongs to space group P21/c with a=1.487 9(2) nm, b=0.898 9(1) nm, c=1.210 0(2) nm, β=99.211(2)°, V=1.597 3(3) nm3. Each Zn(Ⅱ) ion is bridged by two L ligands in the monodentate-monodentate mode to form a neutral ring-like dimer. Complex 2 crystallizes in the space group Pbcn, with a=2.060 2(2) nm, b=1.281 9(1) nm, c=2.246 1(1) nm, V=5.931 9(6) nm3. The Cd(Ⅱ) atom in 2 is coordinated by eight oxygen atoms from four bis(bidentate) L ligands. Ring-like units are formed due to the μ-bridge mode of L, and a one-dimensional anion chain is built by sharing a Cd(Ⅱ) ion between the units. Furthermore, element analyses, IR spectra and solid-state photoluminescence properties are also reported. CCDC: 613076, 1; 613077, 2. |
Keywords: V-shaped dicarboxylate crystal structure d10 metal complex photoluminescence |
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林勇,陈梓云,余小岚,陈小明.两例弯曲型二酸Zn(Ⅱ)、Cd(Ⅱ)配合物的合成,结构与荧光性质[J].无机化学学报,2006,22(8):1467-1472. |
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