A new organically templated monodimensional mixed valence (Fe^II/Fe^III) phosphite: (C₄H₁₂N₂)[Fe^IIFe^III(HPO₃)

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• 作者：Sergio Ferná ; ndez-Armas ; José ; L. Mesa ; José ; L. Pizarro ; Marí ; a I. Arriortua ; Teó ; filo Rojo
• 关键词：A. Microporous materials ; B. Chemical synthesis ; C. Infrared spectroscopy ; C. Mö ; ssbauer spectroscopy ; C. Raman spectroscopy ; D. Crystal structure ; D. Magnetic properties
• 刊名：Materials Research Bulletin
• 出版年：2007
• 期刊代码：60_00255408
• 类别：ms
• 出版时间：22 March 2007
• 卷：42
• 期：3
• 页码：544-552
• 文件大小：602 K

摘要

The organically templated (C₄H₁₂N₂)[Fe^IIFe^III(HPO₃)₂F₃] compound has been synthesized under mild solvothermal conditions. The crystal structure has been determined from X-ray single-crystal diffraction data. The compound crystallizes in the P2₁/n monoclinic space group, with the unit-cell parameters a = 12.935(1), b = 6.4476(7), c = 15.693(2) Å, β = 105.630(9)° and Z = 4. The crystal structure consists of [Fe^IIFe^III(HPO₃)₂F₃]²⁻ chains formed by a central chain built of [Fe(2)O₄F₂] edge-sharing octahedra, and two side chains formed by alternating [Fe(1)O₃F₃] octahedra and [HP(1)O₃] tetrahedra. The piperazinium cations are placed between the chains linked by ionic and hydrogen interactions. The IR and Raman spectra show the existence of two phosphite crystallographically independent. From the diffuse reflectance spectrum the D_q parameter for the iron(II) cations has been calculated (D_q = 820 cm⁻¹). The Mössbauer spectrum in the paramagnetic state shows the simultaneous presence of Fe²⁺ and Fe³⁺. The magnetic measurements indicate the existence of antiferromagnetic interactions.