Nättinen Kalle I, Rissanen Kari
Department of Chemistry, University of Jyväskylä, P.O. Box 35, FIN-40351 Jyväskylä, Finland.
Inorg Chem. 2003 Aug 25;42(17):5126-34. doi: 10.1021/ic034246r.
Single-crystal X-ray crystallography was used to determine the structures of four metallo-organic frameworks (MOFs). A dendritic tetradentate ligand (tetrakis(isonicotinoxymethyl)methane, TINM) was used with first-row transition-metal elements copper, nickel, and cobalt to synthesize MOFs with a PtS interpenetration, due to both planar and tetrahedral junctions being present in the framework. Two different polymeric complexes, 1 and 2, were obtained from similar starting materials, TINM and Cu(NO(3))(2).3H(2)O, but different solvents. The use of dichloromethane in addition to methanol and water promoted the coordination of nitrate ions to the copper. With only methanol and water used as solvent, the copper atom was coordinated to water molecules instead. Compound 1 has pores going through the structure in two dimensions, along crystallographic axes a and c with diameters of the pores (the diameters correspond to the minimum distances between van der Waals surfaces of opposing walls defined by projection along channel axis) approximately 1.0 x 3.1 and 2.5 x 3.7 A, respectively. Compound 2 has channels along all crystallographic axes. The dimensions of the channels are 3.2 x 3.7, 3.7 x 5.0, and 2.8 x 4.1 A, respectively. The structures of 3 and 4 entrap a large guest ligand molecule in the framework. The guest ligand is uncoordinated, although the pattern that the entrapped guests form brings the two arms of any two guests within close range. The lack of 3-fold penetration is due to only two arms being close to each other and also the fact that there is no space for an additional set of metal centers.
采用单晶X射线晶体学方法测定了四种金属有机框架（MOF）的结构。使用树枝状四齿配体（四（异烟酰氧基甲基）甲烷，TINM）与第一排过渡金属元素铜、镍和钴合成具有PtS互穿结构的MOF，这是因为框架中同时存在平面和四面体连接。从相似的起始原料TINM和Cu(NO₃)₂·3H₂O出发，但使用不同的溶剂，得到了两种不同的聚合物配合物1和2。除甲醇和水外，使用二氯甲烷促进了硝酸根离子与铜的配位。仅使用甲醇和水作为溶剂时，铜原子则与水分子配位。化合物1在二维方向上有贯穿结构的孔，沿着晶体学轴a和c，孔的直径（直径对应于沿通道轴投影定义的相对壁的范德华表面之间的最小距离）分别约为1.0×3.1 Å和2.5×3.7 Å。化合物2在所有晶体学轴方向上都有通道。通道尺寸分别为3.2×3.7 Å、3.7×5.0 Å和2.8×4.1 Å。配合物3和4的结构在框架中捕获了一个大的客体配体分子。客体配体未配位，尽管被捕获的客体形成的模式使任意两个客体的两条臂靠近。缺乏三重贯穿是由于只有两条臂彼此靠近，并且没有空间容纳额外的一组金属中心。
