A New Layered Inorganic−Organic Hybrid Manganese(II) Phosphite:  (C₂H₁₀N₂)[Mn₃(HPO₃)₄]. Hydrothermal Synthesis, Crystal Structure, and Spectroscopic and Magnetic Properties

Abstract

A new manganese(II) phosphite templated by ethylenediamine has been prepared by hydrothermal synthesis and characterized by X-ray diffraction data and spectroscopic techniques. A study of the evolution of the synthetic process suggests the presence of a manganese(II) phosphite as intermediate in the first steps of the reaction. The (C 2 H 10 N 2 )-[Mn 3 (HPO 3 ) 4 ] compound crystallizes in the triclinic space group P-1 with a ) 5.459 and Z ) 1. The compound exhibits a layered structure along the c axis with the ethylenediammonium cations located between the sheets. Within the layers the face-sharing MnO 6 octahedra give rise to trimeric entities which are interconnected by HPO 3 tetrahedra. Studies of luminescence and diffuse reflectance spectroscopies have been carried out. The values of the Dq ) 875 cm -1 and Racah parameters, B ) 660 and C ) 3160 cm -1 , have been calculated. The ESR spectra at different temperatures show isotropic signals with a g value of 2.01, which remains unchanged with variation in temperature. The thermal evolution of both the intensity and the line width of the ESR signals shows an increase from room temperature to 4.2 K. From the magnetic measurements the presence of antiferromagnetic interactions in the compound can be observed. The high-temperature magnetic data have been fitted to a model for linear isolated trimers of Mn(II) with a J exchange parameter of -17 K. At temperatures lower than ca. 80 K a long magnetic order, propagated via phosphite anions along the sheets, is established.

Two Novel Transition‐Metal Phosphite Compounds with 4‐, 6‐ and 12‐Membered Rings: Hydrothermal Syntheses, Crystal Structures and Magnetic Properties of Na2[M(HPO3)2] (M = Fe, Co)

“…[31] In this context, it becomes possible to understand the experimental results obtained when the syntheses of the title compounds were performed. Since the protons of the phosphorous acid are easily removed under alkaline conditions, the phosphorus atom is suitable for simultaneously binding to three M II atoms to form the polyhedral network of alternating MO 6 6 (M = Zn, Co, Ni). All the above observations indicate that the pH of the solution indeed plays a crucial role in the reactive process and mainly determines the stability ranges of the various compounds.…”

“…[2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] Besides, in the past few years, considerable efforts have been devoted to exploratory work on the possibilities of incorporating the phosphorus atom as a pseudo-pyramidal HPO 3 2-hydrogen phosphite group into extended structures and these studies have yielded a structurally diverse range of transition-metal phosphites, e.g. (VO)(HPO 3 )(H 2 O) 5 with isolated single chains, [18] ZnCa(HPO 3 ) 2 (H 2 O) 2 , [19] Fe(HPO 3 H) 3 , [20] M(HPO 3 )(H 2 O) (M = Co, Ni) [21] and (NH 4 ) 2 Zn 5 (HPO 3 ) 6 (H 2 O) 4 [22] with layered structures as well as NaM(H 2 PO 3 ) 3 (H 2 O) (M = Mn, Co), [23] [Zn 2 (H 2 O) 4 ]-(HPO 3 ) 2 (H 2 O), [24] Na 2 Zn 3 (HPO 3 ) 4 [24] and M 11 (HPO 3 ) 8 -(OH) 6 (M = Co, Ni, Zn) [25] with 3D structures. A few examples of inorganic-organic hybrid phosphites with transition-cated.…”

3D supermolecular cobalt phosphite with luminescent and magnetic property

“…Since the first zinc phosphite was reported by the Abraham Clearfield' group in 1990 [3], much work has been focused on the incorporation of pseudo-pyramidal phosphite units [HPO 3 ] 2 − in the framework instead of tetrahedral phosphate groups [HPO 4 ] 3 − , which may reduce the connection of M-O-P, so as to generate more open interrupted frameworks [4][5][6][7][8][9][10]. The transitional metal element cobalt, with unique activity of reaction and various coordination modes of tetrahedron, bi-pyramid, and octahedron, has been conducive to phosphite microporous compounds with novel structure [11][12][13][14]. Furthermore, this kind of material might exhibit potential magnetic and catalytic properties.…”

Hydrothermal synthesis and structural characterization of the first indium phosphite In2(HPO3)3(H2O)

“…The incorporations of pseudo pyramidal hydrogen phosphite group [HPO 3 ] 2À into desired structures create rich structural and compositional diversity. Up to now, some organically templated metal phosphite were reported in vanadium phosphite [3], chromium phosphite [4], manganese phosphite [5], iron phosphite…”