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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}
}