Barthelet K, Riou D, Nogues M, Férey G
Institut Lavoisier-Franklin, Université de Versailles-St. Quentin en Yvelines, 45 Av. des Etats-Unis, France.
Inorg Chem. 2003 Mar 10;42(5):1739-43. doi: 10.1021/ic026175m.
(V(III)(OH))(2)[C(6)H(2)(CO(2))(4)].4H(2)O (labeled MIL-60) and V(III)(OH)[(2)(O(2)C)C(6)H(2)(COOH)(2)].H(2)O (labeled MIL-61) were hydrothermally synthesized from mixtures of VCl(3), 1,2,4,5-benzenetetracarboxylic acid, and water heated for 3 days at 473 K. The structure of MIL-60 was solved from single-crystal X-ray diffraction data in the triclinic centrosymmetric P1 (No. 2) space group with lattice parameters a = 6.3758(5) A, b = 6.8840(5) A, c = 9.0254(5) A, alpha = 69.010(2) degrees, beta = 85.197(2) degrees, gamma = 79.452(2) degrees, V = 363.53(5) A(3), and Z = 1. The structure of MIL-61 was ab initio determined from an X-ray powder diffraction pattern. MIL-61 crystallizes in the Pnma (No. 62) orthorhombic space group with lattice parameters a = 14.8860(1) A, b = 6.9164(1) A, c = 10.6669(2) A, V = 1098.23(3) A(3), and Z = 4. Both structures contain the same inorganic building block that consists of trans chains of V(III)O(4)(OH)(2) octahedra. The three-dimensional frameworks of MIL-60 and MIL-61 are constituted by the linkage of these chains via the organic molecules so delimiting the channels or cages where the water molecules are encapsulated. The magnetic behavior of these two phases is presented: MIL-60 is paramagnetic, and MIL-61 antiferromagnetically orders below T(N) = 55(5) K.
(V(III)(OH))(2)[C(6)H(2)(CO(2))(4)].4H(2)O（标记为MIL - 60）和V(III)(OH)[(2)(O(2)C)C(6)H(2)(COOH)(2)].H(2)O（标记为MIL - 61）由VCl(3)、1,2,4,5 - 苯四羧酸和水的混合物在473 K下加热3天通过水热法合成。MIL - 60的结构由三斜中心对称P1（编号2）空间群中的单晶X射线衍射数据解析得出，晶格参数为a = 6.3758(5) Å，b = 6.8840(5) Å，c = 9.0254(5) Å，α = 69.010(2)°，β = 85.197(2)°，γ = 79.452(2)°，V = 363.53(5) ų，Z = 1。MIL - 61的结构由X射线粉末衍射图谱从头确定。MIL - 61结晶于Pnma（编号62）正交空间群，晶格参数为a = 14.8860(1) Å，b = 6.9164(1) Å，c = 10.6669(2) Å，V = 1098.23(3) ų，Z = 4。两种结构都包含相同的无机结构单元，该单元由V(III)O(4)(OH)(2)八面体的反式链组成。MIL - 60和MIL - 61的三维框架由这些链通过有机分子连接而成，从而界定了包封水分子的通道或笼。给出了这两个相的磁行为：MIL - 60是顺磁性的，而MIL - 61在T(N) = 55(5) K以下呈现反铁磁有序。
