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Title: Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds

Abstract

The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the V atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close tomore » 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.« less

Authors:
 [1];  [2]; ;  [3];  [4];  [2];  [5];
  1. Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN San Miguel de Tucumán (Argentina)
  2. Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional, México (Mexico)
  3. CEQUINOR (CONICET-UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 and 115, 1900, La Plata (Argentina)
  4. INFIQC – CONICET, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Haya de la Torre esq, Medina Allende, Ciudad Universitaria, X5000HUA Córdoba (Argentina)
  5. INQUINOA-UNT-CONICET, Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN San Miguel de Tucumán (Argentina)
Publication Date:
OSTI Identifier:
22584156
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 239; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIFERROMAGNETISM; CRYSTALS; CYANIDES; HYDRATES; HYDROGEN; INTERACTIONS; LAYERS; LIGANDS; MAGNETIC PROPERTIES; MAGNETIZATION; NITRIC OXIDE; ORTHORHOMBIC LATTICES; PARAMAGNETISM; POWDERS; SOLIDS; SPACE GROUPS; TRANSITION ELEMENTS; WATER; X RADIATION; X-RAY DIFFRACTION

Citation Formats

Gil, D.M., Osiry, H., Pomiro, F., Varetti, E.L., Carbonio, R.E., Alejandro, R.R., Ben Altabef, A., and and others. Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.04.025.
Gil, D.M., Osiry, H., Pomiro, F., Varetti, E.L., Carbonio, R.E., Alejandro, R.R., Ben Altabef, A., & and others. Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds. United States. doi:10.1016/J.JSSC.2016.04.025.
Gil, D.M., Osiry, H., Pomiro, F., Varetti, E.L., Carbonio, R.E., Alejandro, R.R., Ben Altabef, A., and and others. 2016. "Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds". United States. doi:10.1016/J.JSSC.2016.04.025.
@article{osti_22584156,
title = {Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds},
author = {Gil, D.M. and Osiry, H. and Pomiro, F. and Varetti, E.L. and Carbonio, R.E. and Alejandro, R.R. and Ben Altabef, A. and and others},
abstractNote = {The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the V atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close to 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.},
doi = {10.1016/J.JSSC.2016.04.025},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 239,
place = {United States},
year = 2016,
month = 7
}
  • A topology and symmetry analysis of structures of the Sr-vanadyl-vanadate family Sr{sub 2}VO(VO{sub 4}){sub 2} with a quasi-one-dimensional spin system, which is responsible for magnetic properties, is performed. Based on the known structure with space group I2/a, structures belonging to its subgroups with ordered vanadyl bonds in octahedra containing the magnetic V{sup +4} ion are derived. Structures with a polar orientation of vanadyl bonds in chains of octahedra correspond to space groups P2{sub 1}/c, P2/c, and Pc, and structures with a nonpolar orientation of vanadyl bonds correspond to space groups P2/a, P2, and P2/n. Variants of disordering of vanadyl bondsmore » over two directions, namely, along the b and a axes, are considered for all structures. The predicted structures can be used for the diagnostics of phases obtained in this family and as initial information necessary for studies of magnetic properties of crystals.« less
  • The vanadyl(IV) hydrogen phosphate hemihydrate, VOHPO[sub 4][center dot]0.5H[sub 2]O, is a pyrolytic precursor of the vanadyl(IV) pyrophosphate phase, (VO)[sub 2]P[sub 2]O[sub 7], generally believed to be the active phase in the selective oxidation of n-butane into maleic anhydride. Pyrolytic transformation into the pyrophosphate phase occurs with conservation of a morphology of the material. VOHPO[sub 4][center dot]0.5H[sub 2]O is a layered hydrogen phosphate, where -POH groups form interlayer hydrogen bonds with the water molecules shared by two face-linked vanadyl octahedra. The structure of the hemihydrate is similar to that of [alpha]-zirconium hydrogen phosphate ([alpha]-ZrP), where hydrogen bonds are within the samemore » layer and -POH groups are also pointed into the interlayer space. In contrast to [alpha]-ZrP, where extensive data exist, intercalation chemistry of the layered vanadyl(IV) hydrogen phosphate hemihydrate at present is a terra incognita. This paper reports the results of the first systematic study of VOHPO[sub 4][center dot]0.5H[sub 2]O intercalation with aliphatic amines as a new route to novel vanadyl(IV) phosphate phases. N-Alkylamines have been commonly known as excellent intercalation agents for testing the intracrystalline reactivity of layered oxides. Intercalated alkylamines may also facilitate introduction of thermostable guest molecules, or [open quotes]pillars[close quotes], by ion exchange producing microporous materials which can modify catalytic and sorptive properties. 9 refs., 6 figs., 2 tabs.« less
  • Sodium nitroprusside (NP) is a potent vasodilator that also inhibits platelet aggregation. To test the hypothesis that NP causes both of these effects by altering the balance between prostacyclin (PGI2) produced by endothelial cells and thromboxane A2 (TXA2) produced by platelets, we incubated each of these cell types with NP for 5 minutes and assayed the PGI2 and TXA2 produced. NP at pharmacologically achieved doses (0.01--30 micrograms/ml) inhibited platelet aggregation and resultant TXA2 synthesis in a dose- and time-dependent manner (p less than 0.001). The inhibition was not dependent on cAMP production, external calcium concentration, or suppression of TXA2 synthesis.more » NP did not alter the production of PGI2 by cultured human endothelial cells as measured by radioimmunoassay for 6-Keto-PGF1 alpha, the stable hydrolysis product of PGI2. However, supernates of NP-treated endothelial cells containing low, noninhibitory concentrations of NP unexpectedly inhibited platelet aggregation. This inhibition of platelet aggregation was due to synergy between PGI2 (0.1--3 nM) and NP (p interaction less than 0.03). The synergistic inhibition by NP and PGI2 of platelet aggregation and TXA2 synthesis in vivo may explain some of the beneficial actions of NP in the treatment of hypertension and congestive heart failure.« less
  • No abstract prepared.
  • For a series of alanine-based peptides having 1--3 amino acid residues as spacers, the chromophore, pyrenesulfonyl (Pyr), has been attached at the N-terminus and an electron donor, dimethyl-1,4-benzenediamine (DMPD), covalently bound at the C-terminus. Evidence for an intramolecular charge-transfer interaction involving the electron donor and acceptor groups has been obtained from absorption spectra. Intramolecular electron transfer involving the end groups, Pyr (electron acceptor) and DMPD (electron donor) has been confirmed by ultrafast pump-probe methods. The radical-ion pair states that are generated on Ti/sapphire laser excitation at 400 nm decay in the picosecond to nanosecond time domain and generally show multiexponentialmore » decay kinetics. These rates of charge recombination are among the fastest yet observed involving electron transfer between terminal groups for peptide oligomers. The falloff of rate constants for ion pair recombination is irregular in terms of the through-bond distance that separates Pyr and DMPD groups for the various peptide links; i.e., back electron transfer remains fast for the tripeptide, Pyr-Ala-Ala-Ala-DMPD, despite an average through-bond distance between photoactive groups that reaches 18 {angstrom}. Molecular modeling studies show that the peptides are free to adopt conformations in essentially random fashion, without showing evidence for long range ordering of the peptide chain.« less