Two Dawson-Templated Three-Dimensional Metal−Organic Frameworks Based on Oxalate-Bridged Binuclear Cobalt(II)/Nickel(II) SBUs and Bpy Linkers

Abstract

The Dawson anion P 2W 18O 62 (6-) has been used as a noncoordinating polyoxoanion template for the construction of two metal-organic frameworks, namely, [M 2(bpy) 3(H 2O) 2(ox)][P 2W 18O 62]2(H 2-bpy). nH 2O (M = Co(II), n = 3 ( 1); M = Ni(II), n = 2 ( 2)) (bpy = 4,4'-bipyridine; ox = C 2O 4 (2-)). Single-crystal X-ray analysis reveals that both of the structures exhibit 3D host frameworks constructed from the oxalate-bridged binuclear superoctahedron secondary building units (SBUs) and bpy linkers and the voids of which are occupied by Dawson anions, guest bpy, and water molecules. Magnetic studies reveal that there are antiferromagnetic exchange interactions among the transition-metal centers in compounds 1 and 2. Furthermore, a compound 1-modified carbon paste electrode ( 1-CPE) displays good electrocatalytic activity toward the reduction of nitrite.

1D Chain Crystal Structure of Copper(II) Oxalate Containing a 4,4'-Bipyridine and 1,10-Phenanthroline Ligands: [Cu2(ox)(4,4'-bpy)(phen)2](NO3)2

“…For example, 4,4'-bipyridine (4,4'-bpy) is an excellent ligand and a number of one-, twoand three-dimensional infinite metal-4,4'-bpy frameworks have been generated. [7][8][9][10] Multi-carboxylates as important flexible spacer ligands have also been used to form metal-organic frameworks (MOF), due to their conformational and coordination versatility. [11][12][13] We have been pursuing synthetic strategies for the preparation of non-interpenetrating open frameworks with variable cavities or channels, in which rod-like rigid spacers such as 4,4'-bpy and related species are chosen as building blocks.…”

Carbon paste electrodes in the new millennium

“…[171,176]), scanning tunneling microscopy and atomic force microscopy (STM, AFM [42,177]) microscopic elemental analysis (MEA [176]), thermogravimetry (TG [157,159]), UV/ VIS- [177], IR-, FT/IR-, and Raman spectroscopy [155,171,180], XPS-and XRF-spectroscopy [159,177], XR-diffraction [155,159], or H 1 -NMR, C 13 -NMR, and Si 29 -NMR [155,171]. With respect to electrochemical characte-risations, the most frequent is cyclic voltammetry (CV [158,160,176]), including configuration with the rotated disc electrode (RDE [159]), followed by voltammetry in the DPV or SWV mode [154,177], respectively, or occasionally by chronoamperometry (CA), coulometry (COU [158]), and potentiometry (POT [153]). …”

Synthesis and 1D Chain Crystal Structure of Zinc(II) Terephthalate Complex: [Zn(tp)(py)(H2O)]n

“…7,8 4,4'-Bipyridine (4,4'-bpy) is also an excellent ligand and a number of one-, two-and three-dimensional infinite metal-4,4'-bpy frameworks have been generated. [9][10][11][12] Although many interesting examples including the ligand combination of terephthalate and 4,4'-bipyridine have been reported, [13][14][15] the development of synthetic routes to systems containing two or more different bridging ligands is much less well explored, and it is generally not yet possible to predict either the composition or structure of the product, much work is required for the rational design and synthesis.…”