具有零维至三维结构的无机-有机杂化亚硒酸钒的水热合成、晶体结构及磁性：(1,10-菲咯啉)₂V₂SeO₇、(2,2'-联吡啶)VSeO₄、(4,4'-联吡啶)V₂Se₂O₈及(4,4'-联吡啶)₂V₄Se₃O₁₅·H₂O
Hydrothermal syntheses, crystal structures, and magnetic properties of inorganic-organic hybrid vanadium selenites with zero- to three-dimensional structures: (1,10-phenanthroline)(2)V(2)SeO(7), (2,2'-bipyridine)VSeO(4), (4,4'-bipyridine)V(2)Se(2)O(8), and (4,4'-bipyridine)(2)V(4)Se(3)O(15).H(2)O.
作者信息
Dai Zhimin, Shi Zhan, Li Guanghua, Zhang Dong, Fu Wensheng, Jin Haiying, Xu Wei, Feng Shouhua
机构信息
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130023, P. R. China.
出版信息
Inorg Chem. 2003 Nov 17;42(23):7396-402. doi: 10.1021/ic030165j.
A family of inorganic-organic hybrid vanadium selenites with zero-, one-, two-, and three-dimensional structures, (1,10-phen)(2)V(2)SeO(7), (2,2'-bipy)VSeO(4), (4,4'-bipy)V(2)Se(2)O(8), and (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O (where phen = phenanthroline and bipy = bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Different bidentate organodiamine ligands and reactant concentrations were used in the four reaction systems, which are responsible for the variety of structural dimensions of the compounds. (1,10-phen)(2)V(2)SeO(7) crystallizes in a monoclinic system with space group P2(1)/n and cell parameters a = 8.6509(3) A,( )b = 7.8379(2) A, c = 34.0998(13) A, beta = 91.503(2) degrees, and Z = 4. (2,2'-bipy)VSeO(4) crystallizes in a monoclinic system with space group C2/c and cell parameters a = 17.0895(12) A, b = 14.7707(10) A, c = 11.7657(8) A, beta = 131.354(3) degrees, and Z = 8. (4,4'-bipy)V(2)Se(2)O(8) crystallizes in a triclinic system with space group Ponemacr; and cell parameters a = 7.1810(10) A, b = 10.8937(13) A, c = 11.1811(15) A, alpha = 115.455(3) degrees, beta = 107.582(3) degrees, gamma = 91.957(4) degrees, and Z = 2. (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O crystallizes in a monoclinic system with space group Pc and cell parameters a = 7.9889(9) A, b = 7.8448 A, c = 23.048(3) A, beta = 99.389(4) degrees, and Z = 2. (1,10-phen)(2)V(2)SeO(7) has an isolated structure, (2,2'-bipy)VSeO(4) has a chain structure, (4,4'-bipy)V(2)Se(2)O(8) has a layered structure, and (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O has a framework structure. The chains are constructed from VO(4)N(2) octahedra and SeO(3) pyramids, laced by organic ligands (2,2'-bipy). The layers consist of vanadium selenite chains (VO)(2)(SeO(3))(2), linked by 4,4'-bipy molecules. The framework is composed of vanadium selenite sheets V(4)Se(3)O(16), pillared by 4,4'-bipy molecules. All of the compounds are thermally stable to 300 degrees C, and the magnetic susceptibilities confirm the existence of tetravalent V atoms in the antiferromagnetic (4,4'-bipy)V(2)Se(2)O(8) complex and mixed tetravalent and pentavalent V atoms in the paramagnetic complex (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O.
通过水热法合成了一族具有零维、一维、二维和三维结构的无机 - 有机杂化亚硒酸钒，分别为(1,10 - 菲罗啉)₂V₂SeO₇、(2,2'-联吡啶)VSeO₄、(4,4'-联吡啶)V₂Se₂O₈和(4,4'-联吡啶)₂V₄Se₃O₁₅·H₂O（其中phen = 菲罗啉，bipy = 联吡啶），并通过单晶X射线衍射对其进行了表征。在四个反应体系中使用了不同的双齿有机二胺配体和反应物浓度，这导致了化合物结构维度的多样性。(1,10 - 菲罗啉)₂V₂SeO₇结晶于单斜晶系，空间群为P2(1)/n，晶胞参数a = 8.6509(3) Å，b = 7.8379(2) Å，c = 34.0998(13) Å，β = 91.503(2)°，Z = 4。(2,2'-联吡啶)VSeO₄结晶于单斜晶系，空间群为C2/c，晶胞参数a = 17.0895(12) Å，b = 14.7707(10) Å，c = 11.7657(8) Å，β = 131.354(3)°，Z = 8。(4,4'-联吡啶)V₂Se₂O₈结晶于三斜晶系，空间群为P1̅，晶胞参数a = 7.1810(10) Å，b = 10.8937(13) Å，c = 11.1811(15) Å，α = 115.455(3)°，β = 107.582(3)°，γ = 91.957(4)°，Z = 2。(4,4'-联吡啶)₂V₄Se₃O₁₅·H₂O结晶于单斜晶系，空间群为Pc，晶胞参数a = 7.9889(9) Å，b = 7.8448 Å，c = 23.048(3) Å，β = 99.389(4)°，Z = 2。(1,10 - 菲罗啉)₂V₂SeO₇具有孤立结构，(2,2'-联吡啶)VSeO₄具有链状结构，(4,4'-联吡啶)V₂Se₂O₈具有层状结构，(4,4'-联吡啶)₂V₄Se₃O₁₅·H₂O具有骨架结构。这些链由VO₄N₂八面体和SeO₃金字塔构成，并由有机配体(2,2'-联吡啶)连接。这些层由亚硒酸钒链[(VO)₂(SeO₃)₂]∞组成，由4,4'-联吡啶分子连接。骨架由亚硒酸钒片层[V₄Se₃O₁₆]∞组成，由4,4'-联吡啶分子支撑。所有化合物在300℃下热稳定，并且磁化率证实了反铁磁(4,4'-联吡啶)V₂Se₂O₈配合物中存在四价V原子，顺磁配合物(4,4'-联吡啶)₂V₄Se₃O₁₅·H₂O中存在混合的四价和五价V原子。
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