TY - JOUR
T1 - Structural characterization of a nanocrystalline inorganic-organic hybrid with fiberlike morphology and one-dimensional antiferromagnetic properties
AU - Djerdj, Igor
AU - Cao, Minhua
AU - Rocquefelte, Xavier
AU - Černý, Radovan
AU - Jagličić, Zvonko
AU - Arčon, Denis
AU - Potǒcnik, Anton
AU - Gozzo, Fabia
AU - Niederberger, Markus
PY - 2009/7/28
Y1 - 2009/7/28
N2 - A new nanocrystalline inorganic-organic hybrid compound, VO(C 6H5COO)2 has been synthesized under solvothermal conditions by reacting vanadium(V) oxytriisopropoxide with benzoic acid in toluene. A detailed investigation of the composition, structure and properties of VO(C6H5COO)2 using chemical and thermal analysis, synchrotron X-ray powder diffraction, electron microscopy techniques including SEM, TEM and SAED, spectroscopy techniques like XPS, EDX and FTIR, SQUID magnetometry and EPR is carefully described. Due to the low-crystallinity of the final material, its crystal structure has been solved from synchrotron X-ray powder diffraction data by combining a direct space global optimization technique and DFT geometry optimization and subsequently refined by the constraint Rietveld method. The compound crystallizes in the monoclinic system with a=20.652(3), b=6.798(1), c=9.954(1)A°, ß=92.145(6)°, space group C2, andZ=4. The inorganic part of the structure can be regarded as staggered V-V-V chains, formed of cornersharing VO6 octahedra, running along the monoclinic b-axis. A strong V-O bond alternation along the chain was evidenced by the DFT geometry optimization. The organic part is based on two crystallographically independent singly ionized benzoate moieties linked to vanadium atoms through a bidentate bridging mode. The morphology of VO(C6H5COO)2 exhibits long nanofibers, which further consist of smaller individual nanofibers aligned in parallel to the growth direction along the b-axis, as expected from the 1D nature of the compound. The magnetic susceptibility and X-band EPR measurements shows that the magnetic properties of VO(C6H5COO) 2 can be described by a S=1/2 linear antiferromagnetic chainmodel with the isotropic interaction between nearest neighbors and an estimated magnetic spin exchange parameter of J=-189K.DFT calculations have also been carried out to simulate the optical response and to estimate the magnetic spin exchange related to VO (C6H5COO)2. Such calculations allowed explaining the yellow-green color of the powder and the one-dimensional character of the magnetic structure.
AB - A new nanocrystalline inorganic-organic hybrid compound, VO(C 6H5COO)2 has been synthesized under solvothermal conditions by reacting vanadium(V) oxytriisopropoxide with benzoic acid in toluene. A detailed investigation of the composition, structure and properties of VO(C6H5COO)2 using chemical and thermal analysis, synchrotron X-ray powder diffraction, electron microscopy techniques including SEM, TEM and SAED, spectroscopy techniques like XPS, EDX and FTIR, SQUID magnetometry and EPR is carefully described. Due to the low-crystallinity of the final material, its crystal structure has been solved from synchrotron X-ray powder diffraction data by combining a direct space global optimization technique and DFT geometry optimization and subsequently refined by the constraint Rietveld method. The compound crystallizes in the monoclinic system with a=20.652(3), b=6.798(1), c=9.954(1)A°, ß=92.145(6)°, space group C2, andZ=4. The inorganic part of the structure can be regarded as staggered V-V-V chains, formed of cornersharing VO6 octahedra, running along the monoclinic b-axis. A strong V-O bond alternation along the chain was evidenced by the DFT geometry optimization. The organic part is based on two crystallographically independent singly ionized benzoate moieties linked to vanadium atoms through a bidentate bridging mode. The morphology of VO(C6H5COO)2 exhibits long nanofibers, which further consist of smaller individual nanofibers aligned in parallel to the growth direction along the b-axis, as expected from the 1D nature of the compound. The magnetic susceptibility and X-band EPR measurements shows that the magnetic properties of VO(C6H5COO) 2 can be described by a S=1/2 linear antiferromagnetic chainmodel with the isotropic interaction between nearest neighbors and an estimated magnetic spin exchange parameter of J=-189K.DFT calculations have also been carried out to simulate the optical response and to estimate the magnetic spin exchange related to VO (C6H5COO)2. Such calculations allowed explaining the yellow-green color of the powder and the one-dimensional character of the magnetic structure.
UR - http://www.scopus.com/inward/record.url?scp=67651092058&partnerID=8YFLogxK
U2 - 10.1021/cm901345h
DO - 10.1021/cm901345h
M3 - Article
AN - SCOPUS:67651092058
SN - 0897-4756
VL - 21
SP - 3356
EP - 3369
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 14
ER -