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首页> 外文期刊>Acta crystallographica. Section C, Structural chemistry. >Three novel topologically different metal-organic frameworks built from 3-nitro-4-(pyridin-4-yl)-benzoic acid
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Three novel topologically different metal-organic frameworks built from 3-nitro-4-(pyridin-4-yl)-benzoic acid

机译:三个新型拓扑上不同的金属 - 有机框架,由3硝基-4-(吡啶-4-基) - 苯甲酸构成

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The design and synthesis of metal-organic frameworks (MOFs) have attracted much interest due to the intriguing diversity of their architectures and topologies. However, building MOFs with different topological structures from the same ligand is still a challenge. Using 3-nitro-4-(pyridin-4-yl)benzoic acid (HL) as a new ligand, three novel MOFs, namely poly[[(N,N-dimethylformamide-kappa O)bis[mu(2)-3-nitro-4-(pyridin-4-yl)benzoato-mu O-3,O':N]cadmium(II)] N,N-dimethylformamide monosolvate methanol monosolvate], {[Cd(C12H7N2O4)(2)(C3H7NO)]center dot C3H7NO center dot CH3OH}(n), (1), poly[[(mu(2)-acetato-kappa O-2:O')[mu(3)-3-nitro-4-(pyridin-4-yl)benzoato-kappa O-3:O':N]bis[mu(3)-3-nitro-4-(pyridin-4-yl)benzoato-kappa O-4,O':O':N]dicadmium(II)] N,N-dimethylacetamide disolvate monohydrate], {[C(d)2(C12H7N2O4)(3)(CH3CO2)]center dot 2C(4)H(9)NO center dot H2O}(n), (2), and catena-poly[[[diaquanickel(II)]-bis[mu(2)-3-nitro-4-(pyridin-4-yl)benzoato-kappa O-2:N]] N,N-dimethylacetamide disolvate], {[Ni(C12H7N2O4)(2)(H2O)(2)]center dot 2C(4)H(9)NO}(n), (3), have been prepared. Single-crystal structure analysis shows that the CdII atom in MOF (1) has a distorted pentagonal bipyramidal [CdN(2)O5] coordination geometry. The [CdN2O5] units as 4-connected nodes are interconnected by L- ligands to form a fourfold interpenetrating three-dimensional (3D) framework with a dia topology. In MOF (2), there are two crystallographically different CdII ions showing a distorted pentagonal bipyramidal [CdNO6] and a distorted octahedral [CdN2O4] coordination geometry, respectively. Two CdII ions are connected by three carboxylate groups to form a binuclear [Cd-2(COO)(3)] cluster. Each binuclear cluster as a 6-connected node is further linked by acetate groups and L- ligands to produce a non-interpenetrating 3D framework with a pcu topology. MOF (3) contains two crystallographically distinct NiII ions on special positions. Each NiII ion adopts an elongated octahedral [NiN2O4] geometry. Each NiII ion as a 4-connected node is linked by L- ligands to generate a two-dimensional network with an sql topology, which is further stabilized by two types of intermolecular OW-HW center dot center dot center dot O hydrogen bonds to form a 3D supramolecular framework. MOFs (1)-(3) were also characterized by powder X-ray diffraction, IR spectroscopy and thermogravimetic analysis. Furthermore, the solid-state photoluminescence of HL and MOFs (1) and (2) have been investigated. The photoluminescence of MOFs (1) and (2) are enhanced and red-shifted with respect to free HL. The gas adsorption investigation of MOF (2) indicates a good separation selectivity (71) of CO2/N-2 at 273 K (i.e. the amount of CO2 adsorption is 71 times higher than N-2 at the same pressure).
机译:由于其架构和拓扑的有趣多样性,金属 - 有机框架(MOF)的设计和合成引起了很多兴趣。然而,建立具有来自同一配体的不同拓扑结构的MOF仍然是一个挑战。使用3-硝基-4-(吡啶-4-基)苯甲酸(HL)作为新配体,三种新的MOF,即聚[[(n,N-二甲基甲酰胺-Kappa O)双[亩(2)-3 -NITRO-4-(吡啶-4-基)Benzoato-MU O-3,O':N]镉(II)] N,N-二甲基甲酰胺单溶化物甲醇单溶酸盐],{[CD(C12H7N2O4)(2)(C3H7NO )]中心点C3H7NO中心点CH 3 OH}(N),(1),聚[[(mu(2) - 乙酸酯-Kappa O-2:O')[mu(3)-3-硝基-4-(吡啶-4-yl)Benzoato-Kappa O-3:O':N] Bis [Mu(3)-3-硝基-4-(Pyridin-4-Y1)Benzoato-Kappa O-4,O':O': n]二亚溴铵(II)] N,N-二甲基乙酰胺脱落一水合物],{[C(D)2(C12H7N2O4)(3)(3)(CH 3 CO 2)]中心点2C(4)H(9)NO中心点H2O}(n ),(2)和Catena-poly [[蜜蛋白(II)] - BIS [mu(2)-3-硝基-4-(吡啶-4-基)苯并κ-κ0-2:n]] n] ,N-二甲基乙酰胺脱落液],{[Ni(C12H7N2O4)(2)(2)(2)(2)(2)H(9)H(9)NO}(N),(3)已制备。单晶结构分析表明,MOF(1)中的CDII原子具有扭曲的五角形双吡酰胺[CDN(2)O5]配位几何形状。作为4连接节点的[CDN2O5]单元由L-配体互连,以形成具有DIA拓扑的四倍互连的三维(3D)框架。在MOF(2)中,有两个结晶不同的CDII离子,显示出扭曲的五边形双吡酰胺[CDNO6]和扭曲的八面体[CDN2O4]配位几何形状。两个Cdii离子通过三个羧酸盐基团连接,形成Binuclear [Cd-2(CoO)(3)]簇。每个Binuclear集群作为6连接的节点进一步被醋酸基团和L-配体连接,以产生具有PCU拓扑的非互穿的3D框架。 MOF(3)在特殊位置含有两个晶形上不同的NIII离子。每个NiII离子采用细长的八面体[Nin2O4]几何形状。作为4连接的节点的每个NiII离子由L-配体连接,以产生具有SQL拓扑的二维网络,其通过两种类型的分子OW-HW中心点中心点中心点O氢键来形成的平SQL拓扑。一个3D超分子框架。 MOF(1) - (3)的特征还以粉末X射线衍射,红外光谱和热标重分析为特征。此外,已经研究了HL和MOF(1)和(2)的固态光致发光。 MOF(1)和(2)的光致发光得到增强和相对于游离HL的转移。 MOF(2)的气体吸附研究表明,在273k(即,CO 2吸附量在相同压力下的N-2高71倍的CO 2 / N-2的良好分离选择性(71)。

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