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Title: Synthesis, structural determination and magnetic properties of layered hybrid organic-inorganic, iron (II) propylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)], and iron (II) octadecylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 17}PO{sub 3})(H{sub 2}O)]

Abstract

Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)] (1) and Fe[(CH{sub 3}(CH{sub 2}){sub 17}PO{sub 3})(H{sub 2}O)] (2) were synthesized by reaction of FeCl{sub 2}.6H{sub 2}O and the relevant phosphonic acid in water in presence of urea and under inert atmosphere. The compounds were characterized by elemental and thermogravimetric analyses, UV-visible and IR spectroscopy. The crystal structure of (1) was determined from X-ray single crystal diffraction studies at room temperature: monoclinic symmetry, space group P2{sub 1}, a=5.707(1)A, b=4.811(1)A, c=11.818(2)A, and {beta}=98.62(3){sup o}. The compound is lamellar and the structure is hybrid, made of alternating inorganic and organic layers along the c direction. The inorganic layers consist of Fe(II) ions octahedrally coordinated by five phosphonate oxygen atoms and one from the water molecule, separated by bi-layers of propyl groups. A preliminary structure characterization of compound (2) suggests a similar layered structure, but with an interlayer spacing of 40.3A. The magnetic properties of the compounds were both studied by a dc and ac SQUID magnetometer. Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)] (1) obeys the Curie-Weiss law at temperatures above 50K (C=3.81cm{sup 3}Kmol{sup -1}, {theta}=-62K), indicating a Fe +II oxidation state, a high-spin d{sup 6} (S=2) electronic configuration and an antiferromagnetic exchange couplings between the near-neighbouringmore » Fe(II) ions. Below T=22K, Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)] exhibits a weak ferromagnetism. The critical temperature of T{sub N}=22K has been determined by ac magnetic susceptibility measurements. Compound (2) shows the same paramagnetic behaviour of the iron (II) propyl derivative. The values of C and {theta} were found to be 3.8cm{sup 3}Kmol{sup -1} and -44K, respectively, thus suggesting the presence of Fe +II ion in the S=2 spin state and antiferromagnetic interactions between Fe(II) ions at low temperatures. Zero-field and field cooled magnetic susceptibility vs. T plots do not overlap below T=30K, suggesting the presence of an ordered magnetic state. The critical temperature, T{sub N}, has been located by the peaks at T{sub N}=26K from the ac susceptibility ({chi}'and {chi}'') vs. T plots. Below T{sub N} hysteresis loops recorded in the temperature region 16<T<26K show an S-shape, while below 15K assume an ellipsoid form. They reveal that compound (2) is a weak ferromagnet. The critical temperature T{sub N} in these layered Fe(II) alkylphosphonates is independent of the distance between the inorganic layers.« less

Authors:
 [1];  [2];  [3];  [4];  [4];  [2]
  1. CNR-Istituto di Struttura della Materia, Sez.2, Via Salaria Km. 29.5, C.P.10, I-00016, Monterotondo Stazione, Rome (Italy). E-mail: Carlo.Bellitto@ism.cnr.it
  2. CNR-Istituto di Struttura della Materia, Sez.2, Via Salaria Km. 29.5, C.P.10, I-00016, Monterotondo Stazione, Rome (Italy)
  3. CNRS-Universite de Nantes, UMR 6502, Institut des Materiaux Jean Rouxel, 2 Rue de la, Houssiniere, BP 32229, 44322 Nantes Cedex 03 (France). E-mail: Philippe.Leone@cnrs-imn.fr
  4. CNRS-Universite de Nantes, UMR 6502, Institut des Materiaux Jean Rouxel, 2 Rue de la, Houssiniere, BP 32229, 44322 Nantes Cedex 03 (France)
Publication Date:
OSTI Identifier:
20784898
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2005.11.016; PII: S0022-4596(05)00541-4; Copyright (c) 2005 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; CRITICAL TEMPERATURE; ELECTRONIC STRUCTURE; FERROMAGNETISM; INFRARED SPECTRA; IRON COMPOUNDS; MAGNETIC SUSCEPTIBILITY; MAGNETOMETERS; MONOCLINIC LATTICES; MONOCRYSTALS; PARAMAGNETISM; PHOSPHONATES; SPACE GROUPS; SQUID DEVICES; SYNTHESIS; TEMPERATURE RANGE 0273-0400 K; THERMAL GRAVIMETRIC ANALYSIS; X-RAY DIFFRACTION

Citation Formats

Bellitto, Carlo, Bauer, Elvira M., Leone, Philippe, Meerschaut, Alain, Guillot-Deudon, Catherine, and Righini, Guido. Synthesis, structural determination and magnetic properties of layered hybrid organic-inorganic, iron (II) propylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)], and iron (II) octadecylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 17}PO{sub 3})(H{sub 2}O)]. United States: N. p., 2006. Web. doi:10.1016/j.jssc.2005.11.016.
Bellitto, Carlo, Bauer, Elvira M., Leone, Philippe, Meerschaut, Alain, Guillot-Deudon, Catherine, & Righini, Guido. Synthesis, structural determination and magnetic properties of layered hybrid organic-inorganic, iron (II) propylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)], and iron (II) octadecylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 17}PO{sub 3})(H{sub 2}O)]. United States. doi:10.1016/j.jssc.2005.11.016.
Bellitto, Carlo, Bauer, Elvira M., Leone, Philippe, Meerschaut, Alain, Guillot-Deudon, Catherine, and Righini, Guido. Wed . "Synthesis, structural determination and magnetic properties of layered hybrid organic-inorganic, iron (II) propylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)], and iron (II) octadecylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 17}PO{sub 3})(H{sub 2}O)]". United States. doi:10.1016/j.jssc.2005.11.016.
@article{osti_20784898,
title = {Synthesis, structural determination and magnetic properties of layered hybrid organic-inorganic, iron (II) propylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)], and iron (II) octadecylphosphonate, Fe[(CH{sub 3}(CH{sub 2}){sub 17}PO{sub 3})(H{sub 2}O)]},
author = {Bellitto, Carlo and Bauer, Elvira M. and Leone, Philippe and Meerschaut, Alain and Guillot-Deudon, Catherine and Righini, Guido},
abstractNote = {Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)] (1) and Fe[(CH{sub 3}(CH{sub 2}){sub 17}PO{sub 3})(H{sub 2}O)] (2) were synthesized by reaction of FeCl{sub 2}.6H{sub 2}O and the relevant phosphonic acid in water in presence of urea and under inert atmosphere. The compounds were characterized by elemental and thermogravimetric analyses, UV-visible and IR spectroscopy. The crystal structure of (1) was determined from X-ray single crystal diffraction studies at room temperature: monoclinic symmetry, space group P2{sub 1}, a=5.707(1)A, b=4.811(1)A, c=11.818(2)A, and {beta}=98.62(3){sup o}. The compound is lamellar and the structure is hybrid, made of alternating inorganic and organic layers along the c direction. The inorganic layers consist of Fe(II) ions octahedrally coordinated by five phosphonate oxygen atoms and one from the water molecule, separated by bi-layers of propyl groups. A preliminary structure characterization of compound (2) suggests a similar layered structure, but with an interlayer spacing of 40.3A. The magnetic properties of the compounds were both studied by a dc and ac SQUID magnetometer. Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)] (1) obeys the Curie-Weiss law at temperatures above 50K (C=3.81cm{sup 3}Kmol{sup -1}, {theta}=-62K), indicating a Fe +II oxidation state, a high-spin d{sup 6} (S=2) electronic configuration and an antiferromagnetic exchange couplings between the near-neighbouring Fe(II) ions. Below T=22K, Fe[(CH{sub 3}(CH{sub 2}){sub 2}PO{sub 3})(H{sub 2}O)] exhibits a weak ferromagnetism. The critical temperature of T{sub N}=22K has been determined by ac magnetic susceptibility measurements. Compound (2) shows the same paramagnetic behaviour of the iron (II) propyl derivative. The values of C and {theta} were found to be 3.8cm{sup 3}Kmol{sup -1} and -44K, respectively, thus suggesting the presence of Fe +II ion in the S=2 spin state and antiferromagnetic interactions between Fe(II) ions at low temperatures. Zero-field and field cooled magnetic susceptibility vs. T plots do not overlap below T=30K, suggesting the presence of an ordered magnetic state. The critical temperature, T{sub N}, has been located by the peaks at T{sub N}=26K from the ac susceptibility ({chi}'and {chi}'') vs. T plots. Below T{sub N} hysteresis loops recorded in the temperature region 16<T<26K show an S-shape, while below 15K assume an ellipsoid form. They reveal that compound (2) is a weak ferromagnet. The critical temperature T{sub N} in these layered Fe(II) alkylphosphonates is independent of the distance between the inorganic layers.},
doi = {10.1016/j.jssc.2005.11.016},
journal = {Journal of Solid State Chemistry},
number = 2,
volume = 179,
place = {United States},
year = {Wed Feb 15 00:00:00 EST 2006},
month = {Wed Feb 15 00:00:00 EST 2006}
}
  • Co[(CH{sub 3}PO{sub 3})(H{sub 2}O)] (1) and Co[(C{sub 2}H{sub 5}PO{sub 3})(H{sub 2}O)] (2) were prepared by the hydrothermal method and isolated as blue-violet platelet crystals. They were characterized by X-ray diffraction, FT-IR, TGA-DSC techniques and their magnetic properties studied by a dc-SQUID magnetometer. Compound (1) shows an hybrid layered structure, made of alternating inorganic and organic layers along the a-direction of the unit cell. The inorganic layers contain Co(II) ions six-coordinated by five phosphonate oxygen atoms and one from the water molecule. These layers are separated by bi-layers of methyl groups and van der Waals contacts are established between them. Inmore » compound (2), the layered hybrid structure is rather similar to that described for compound (1), but the alternation of the inorganic and organic layers is along the b-direction of the unit cell. The magnetic behavior of (1) and (2) as function of temperature and magnetic field was studied. The compounds obey the Curie-Weiss law at temperatures above 100K, the Curie C, and Weiss {theta} constants for the methyl derivative being C=3.36cm{sup 3}Kmol{sup -1} and {theta}=-53K and for the ethyl derivative C=3.62cm{sup 3}Kmol{sup -1} and {theta}=-75K, respectively. The observed magnetic moments for Co atom at room temperature (i.e. {mu}{sub eff}=5.18 and 5.38 BM, respectively) are higher than those expected for a spin-only value for high spin Co(II) (S=3/2), revealing a substantial orbital contribution to the magnetic moment. The negative values of {theta} are an indication of the presence of antiferromagnetic exchange couplings between the near-neighbors Co(II) ions, within the layers. [Co(C{sub n}H{sub 2n+1}PO{sub 3})(H{sub 2}O)] (n=1,2) are 2D Ising antiferromagnets at low temperatures.« less
  • Fe(II)C{sub 2}H{sub 5}PO{sub 3}{center_dot}H{sub 2}O has been prepared via prolonged reaction between iron oxychloride and ethylphosphonic acid in acetone, in a sealed tube. The lamellar structure is very similar to that of previously reported divalent metal phosphonates M(II)(RPO{sub 3}){center_dot}H{sub 2}O (M = Mg, Mn, Ni, Zn). The compound shows sign of 2D antiferromagnetic correlations above the Neel temperature T{sub N} = 24K and a weak ferromagnetic behavior is observed below T{sub N}. The authors also report on the preparation methods and the crystal structures of two new anhydrous copper phosphonates {alpha}-Cu(II)(C{sub 2}H{sub 5}PO{sub 3}), and {beta}-Cu(II)(CH{sub 3}PO{sub 3}) which exhibitsmore » an original tubular three-dimensional structure. The reactivity of bulky phosphonic acids is also described, with the case of Co(II)(t-C{sub 4}H{sub 9}PO{sub 3}){center_dot}H{sub 2}O.« less
  • The first microporous solids incorporating two octahedrally coordinated transition elements, the phosphates (TMA)[sub 2](NH[sub 4])[sub 2][Fe[sub 2]Mo[sub 12]O[sub 30](H[sub 2]PO[sub 4])[sub 6](HOP[sub 4])[sub 2]][center dot]11H[sub 2]O (1) and (TMA)[sub 2]Na[sub 4][Fe[sub 3]Mo[sub 12]O[sub 30](H[sub x]PO[sub 4])[sub 8]][center dot]16H[sub 2]O (2) (TMA = (CH[sub 3])[sub 4]N[sup +]), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction and water absorption isotherms. Phosphate 1 is prepared in 94% yield from Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (NH[sub 4])[sub 2]HPO[sub 4], (TMA)OH, H[sub 3]PO[sub 4], and H[sub 2]O in a mole ratio of 5:1:1:2:7:16:150 at 200[degrees]C for 64 h, while 2 is synthesizedmore » in 62% yield by the reaction of Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (TMA)OH, H[sub 3]PO[sub 4] and H[sub 2]O in a mole ratio of 5:1:1:8:18:250 at 200[degrees]C for 3 days. Orange crystals of 1 are rhombohedral. Both structures are based on Fe[Mo[sub 6]O[sub 15](H[sub x]PO[sub 4])[sub 2]] units which are connected via their phosphate groups to additional Fe[sup 3+] ions to give three-dimensional frameworks. Both compounds display structures that can be rationalized on the basis of regions of hydrophobic and hydrophilic interactions. The interconnected voids and channels in the ferric molybdenum phosphate frameworks are filled with a mixture of charged-compensating cations and water of solvation. Reversible water absorption isotherms indicate that both compounds are microporous with internal void volumes of about 15 and 25 vol % for 1 and 2, respectively. 23 refs., 10 figs., 3 tabs.« less
  • The synthesis, crystal structure and physical properties of the new series {alpha}{sub 1} and {alpha}{sub 2} of radical salts made with bis (ethylenedithio) tetrathiafulvalene (BEDT-TTF or ET) and Keggin polyoxoanions are reported. The structure of the {alpha}{sub 1}-ET{sub 8}[XW{sub 12}O{sub 40}] (X=Co{sup II}, Cu{sup II}, 2(H{sup +}) and Fe{sup III}) series consists of alternating layers of the organic donor and the Keggin polyoxometalates. The organic layers contain three crystallographically independent molecules that form two different parallel stacks alternating in the [101] direction. The structure of the {alpha}{sub 2}-ET{sub 8}[XW{sub 12}O{sub 40}] (X=Co{sup II}, Cu{sup II}, 2(H{sup +}), Fe{sup III} andmore » B{sup III}) series is similar to that of the {alpha}{sub 1} phase but the organic layers contain only two crystallographically independent molecules. In both {alpha} phases the Keggin polyanions form closed packed pseudohexagonal layers. Both crystal structures suggest the presence of two types of differently charged stacks: a dimerized one with almost neutral ET molecules, and an eclipsed one formed by almost ionized ET molecules. This inhomogeneous charge distribution is confirmed by Raman spectroscopy. Conductivity measurements show that all compounds are semiconductors, in agreement with the band structure EHT calculations. Magnetic measurements indicate the presence of antiferromagnetic interactions in the organic sublattice with the presence of a strong Curie tail and confirm the electronic distribution in the two kinds of stacks. ESR spectra of the salts with dimagnetic anions complete these results and for the radical salts with paramagnetic anions indicate that both sublattices coexist but do not interact significantly.« less
  • A new 3D-layered inorganic-organic hybrid [D/L-C{sub 6}H{sub 13}O{sub 2}N-H]{sub 3}[(PO{sub 4})W{sub 12}O{sub 36}].4.5H{sub 2}O (1), as racemic material in the solid phase, has been synthesized and fully characterized by elemental microanalysis, single crystal X-ray diffraction, and infrared, Raman, and proton nuclear magnetic resonance spectroscopes. The most unique structural feature of 1 is its three-dimensional inorganic infinite tunnel-like framework that results in weak van der Waals interactions along the a-axis. A weak interlayer interaction between the titled layers provides a desirable condition to explore its potential as a host in a host-guest complex. The racemization has been observed in the crystalmore » structure with the centric space group (P2{sub 1}/c). The latter consists of {alpha}-[(PO{sub 4})W{sub 12}O{sub 36}]{sup 3-}and [D/L-C{sub 6}H{sub 13}O{sub 2}N-H]{sup +} moieties with water molecules linked together by a complex network of hydrogen bond interactions.« less