RESUMEN
The title compound has been synthesized under solvothermal conditions by reacting vanadium(V) oxytriisopropoxide with terephthalic acid in N,N-dimethylformamide. A combination of synchrotron powder diffraction, infrared spectroscopy, scanning and transmission electron microscopy, and thermal and chemical analysis elucidated the chemical, structural and microstructural features of a new 2D layered inorganic-organic framework. Due to the low-crystallinity of the final material, its crystal structure has been solved from synchrotron X-ray powder diffraction data using a direct space global optimization technique and subsequent constraint Rietveld refinement. [V(4)O(4)(OH)(2)(O(2)CC(6)H(4)CO(2))(4)]·DMF crystallizes in the monoclinic system (space group P2/m (No. 10)); cell parameters: a = 20.923(4) Å, b = 5.963(4) Å, c = 20.425(1) Å, ß = 123.70(6)°, V = 2120.1(9) Å(3), Z = 2. The overall structure can be described as an array of parallel 2D layers running along [-101] direction, consisting of two types of vanadium oxidation states and coordination polyhedra: face-shared trigonal prisms (V(4+)) and distorted corner-shared square pyramids (V(5+)). Both configurations form independent parallel chains oriented along the 2-fold symmetry crystallographic b-axis mutually interlinked with terephthalate ligands in a monodentate mode perpendicular to it. The morphology of the compound exhibits long nanofibers, with the growth direction along the layered [-101] axis. The magnetic susceptibility measurements show that the magnetic properties of [V(4)O(4)(OH)(2)(O(2)CC(6)H(4)CO(2))(4)]·DMF can be described by a linear antiferromagnetic chain model, with the isotropic exchange interaction of J = -75 K between the nearest V(4+) neighbours of S = 1/2.
RESUMEN
Layered ZnO microspheric particles were prepared by the thermal decomposition of layered hydrozincite (LZnHC), which was synthesized from zinc nitrate and urea in a water/PEG400 mixture. The influence of the starting reagents, their concentrations, and the amount of PEG in the water/PEG400 mixture on the particle growth was observed. The chemical aspect of the particle growth was proposed in the frame of the partial charge model (PCM), and the formation of [Zn(OH)(2)(OH(2))(4)](0) and [Zn(OH)(HCO(3))(OH(2))(3)](0) was predicted for the solid phase. The assumed growth mechanism, which follows the "nonclassical crystallization" concept of a self-assembling mechanism, was observed in situ by small-angle X-ray scattering (SAXS) and predicts the rapid formation of approximately 6 nm sized building units. The size of these nano building units, stable only in the reaction medium, remains nearly constant during the synthesis, as the concentration of the nano building units increases throughout the reaction. The nano building units connect into leaves of LZnHC with a thickness of 20 nm. These leaves of LZnHC are further agglomerated into porous, microsphere-like particles with sizes up to 4 µm.
