Li_1.43[Fe^II_4.43Fe^III_0.57(HPO₃)₆]·1.5H₂O: A Phosphite Oxoanion-Based Compound with Lithium Exchange Capability and Spin-Glass Magnetic Behavior

Abstract

The title compound is hydrothermally synthesized from an aqueous mixture of FeCl3, H3PO4, and LiOH (autoclave, pH 3.0, 170 °C, 5 d).

Re-entrant spin glass and stepped magnetization in mixed-valence SrFe3(PO4)3

“…Single crystal RbNa 3 Fe 7 (PO 4 ) 6 shows fielddependent magnetization jumps, where the metamagnetism could be attribute to the combinations of the geometry frustration of magnetic lattice, short Fe(II)yFe(II) distance and uniaxial magnetic properties of trigonal bipyramidal Fe(II) [14]. Similar fielddependent magnetization step reported so far can be attributed to quantum tunneling magnetization, avalanches, spin rearrangements, or domain-wall depinning [15]. The presence of PO 4 groups is also important since their corners are generally shared by several metallic cations.…”

Phosphite as Polyanion-Based Cathode for Li-Ion Battery: Synthesis, Structure, and Electrochemistry of LiFe(HPO3)2

“…The P−O distances are in the range 1.511(2)−1.539(2) Å and the P−H bond length is 1.29(4) Å (constrained), all corroborating well with the reported values for P−O and P−H distances in many reported metal phosphites. 22,29,30 The Li atom is located in the special position, 8d, and is coordinated by 31 for Fe1 (BVS = 3.09) and P1 (BVS = 3.97, disregarding hydrogen) confirms the oxidation states Fe and P as 3+. It is to be noted that the proof of oxidation state of +3 for P in phosphite group from BVS value is indirect because of the lack of reliable bond valence parameters for pure P(III)−O bonds.…”

“…As the temperature increases from 450 to 800°C, a considerable mass gain can be observed, which can be assigned to the oxidation of P(III) to P(V) to form a phosphate or pyrophosphate as a result of oxygen impurity in the N 2 purge gas, similar to other phosphite based materials reported in the literature. 22,33 Figure 5 depicts the FT-IR spectrum of LiFe(HPO 3 ) 2 . The spectrum is composed of the signature sharp P−H stretching mode at 2450 cm −1 and the P−O stretching modes prevailing in the region 900−1100 cm −1 overlapping with the bending vibrations of P−H bond.…”

“…The spectrum is composed of the signature sharp P−H stretching mode at 2450 cm −1 and the P−O stretching modes prevailing in the region 900−1100 cm −1 overlapping with the bending vibrations of P−H bond. 22 The low frequency part of the spectrum shows moderate absorption peaks assigned to the bending modes of P−O bonds. The absence of strong absorption peaks in the 3200−3500 cm −1 region indicates …”

Ax(H3O)2−xMn5(HPO3)6 (A = Li, Na, K and NH4): open-framework manganese(ii) phosphites templated by mixed cationic species

“…Intralayer pathways characteristics could frustrate the magnetic exchange system, giving rise to a complex magnetic behaviour probably related to an incommensurate magnetic structure. 28 it seems that the nature and the unique oxidation state, +2, of the manganese atoms in A x (H 3 O) 2-x Mn 5 (HPO 3 ) 6 suppresses the randomness in the magnetic interactions observed in the isostructural compound, eliminating the spin-glass state. Finally, the compounds exhibit 95 and the "UPV/EHU" (UFI11/15), which we gratefully acknowledge.…”