MIO₃F (M = Co and Ni): Magnetic Iodate Fluorides with Zigzag Chains

Abstract

The iodate anion group has been widely used for design and synthesis of functional materials including nonlinear optical materials but rarely for magnetic materials. Particularly, none of magnetic iodate fluorides has been reported yet. In this work, first, two novel magnetic iodate fluorides MIO3F (M = Co 1 and Ni 2) have been synthesized by a hydrothermal method and characterized by magnetic susceptibility, magnetization, and heat capacity measurements as well as thermogravimetry, Fourier transform infrared spectroscopy (FT-IR), and ultraviolet–visible–near-infrared (UV–vis–NIR) spectroscopy. Compounds 1 and 2 are isostructural and crystallize in the monoclinic space group P21/n with alternating M2+–F2–M2+–O2–M2+ zigzag spin chains along the b axis, which are further separated by triangular IO3 groups in the ab plane. Magnetic susceptibilities suggest that 1 exhibits an antiferromagnetic long-range order (LRO) at 16.5 K, confirmed by heat capacity results with released entropy consistent with the theoretical value for a pseudo-spin of 1/2 for Co2+ at low temperatures. Meanwhile, 2 displays a broad maximum around 10.5 K for low dimensional magnetism followed by a sharp peak at 5.7 K indicating the occurrence of an LRO transition, in good agreement with the heat capacity measurement. Field-dependent magnetizations show an obvious spin-flop transition around 4.5 T and a magnetic hysteresis loop between 4.5 and 7 T for 1, but only a slight slope change could be observed around 2.3 T for 2. Thermal stability, FT-IR, and UV–vis–NIR spectroscopy of 1 and 2 are also reported.

KMB4O6F3 (M = Co, Fe): two-dimensional magnetic fluorooxoborates with triangular lattices directed by triangular BO3 units

“…97 Moreover, the broad absorption peaks at around 3411 cm −1 and 2922 cm −1 may be from water molecules on the surface of samples absorbed in air. 25,98,99 UV-vis-NIR diffuse reflectance spectra…”

“…1c), 16 and Shastry-Sutherland lattices; 17 and 3D systems of cube tile lattices, 18 pyrochlore (or breathing pyrochlore) lattices, 19 diamond lattices, 20 hyper-Kagomé lattices, 21 and hyper-honeycomb lattices, 22 have been theoretically proposed. Meanwhile, experimentally, a number of magnetic compounds with their corresponding spin lattices have been realized and investigated, for example, zigzag chains of SrCuO 2 , 23 BaTb 2 O 4 , 24 MIO 3 F (M = Co and Ni), 25 and MnWO 4 ; 26 diamond chains of Cu 3 (CO 3 ) 2 (OH) 2 , 27 K 3 Cu 3 AlO 2 (SO 4 ) 4 , 28 and Cu 2 FePO 4 F 4 (H 2 O) 4 ; 29 spin ladders of ACu 2 O 3 (A = Sr, Ca) 30,31 Fig. 1 Common magnetic spin frustrated lattices of the (a) triangular lattice, (b) Kagomé lattice, and (c) honeycomb lattice; (d) triangular BBU of the BO 3 group; and (e) directed coordination for specific magnetic lattices by the use of the triangular BO 3 group with magnetic ions.…”

“…1c), 16 and Shastry–Sutherland lattices; 17 and 3D systems of cube tile lattices, 18 pyrochlore (or breathing pyrochlore) lattices, 19 diamond lattices, 20 hyper-Kagomé lattices, 21 and hyper-honeycomb lattices, 22 have been theoretically proposed. Meanwhile, experimentally, a number of magnetic compounds with their corresponding spin lattices have been realized and investigated, for example, zigzag chains of SrCuO 2 , 23 BaTb 2 O 4 , 24 MIO 3 F (M = Co and Ni), 25 and MnWO 4 ; 26 diamond chains of Cu 3 (CO 3 ) 2 (OH) 2 , 27 K 3 Cu 3 AlO 2 (SO 4 ) 4 , 28 and Cu 2 FePO 4 F 4 (H 2 O) 4 ; 29 spin ladders of ACu 2 O 3 (A = Sr, Ca) 30,31 and Sr 2 Cu 3 O 5 ; 32 triangular lattices of YbMgGaO 4 33,34 and NaYbS 2 ; 35,36 Kagomé lattices of ZnCu 3 (OH) 6 Cl 2 37,38 and Cu 3 V 2 O 7 (OH) 2 ·2H 2 O; 39,40 square lattices of Li 2 VOAO 4 (A = Si, Ge) 41 and VOMoO 4 ; 42 honeycomb lattices of A 2 IrO 3 (A = Na, Li, Cu), 43,44 α-RuCl 3 , 45 and NaIrO 3 ; 46 Shastry–Sutherland lattices of SrCu 2 (BO 3 ) 2 47 and (CuCl)LaNb 2 O 7 ; 48 the cube lattice of CsFe 3 (SeO 3 ) 2 F 6 ; 49 pyrochlore lattices of RE 2 Ti 2 O 7 (RE = Yb, Dy, Ho), 50 Lu 2 Mo 2 O 7 and Lu 2 Mo 2 O 5 N 2 ; 51 the diamond lattice of NiRh 2 O 4 ; 52 the hyper-Kagomé lattice of Na 4 Ir 3 O 8 ; 53 and the hype-honeycomb lattice of β-Li 2 IrO 3 . 54…”

Extended Honeycomb Metal Chloride with Tunable Antiferromagnetic Correlations

“…19−22 Introducing transition metals into perovskite structures represents a promising approach for altering optoelectronic properties and introducing cooperative magnetism. 23,24 Regarding the A 3 M 2 X 9 family, it can be categorized into two distinct types: the zero-dimensional (0D) dimer structure (P6 3 /mmc) and the two-dimensional (2D) (111)-ordered layered structure (P3̅ m1). 25−27 Among these, the 0D dimer structure incorporating transition metals is an interesting platform for the bilayer triangular lattice (BLTL) antiferromagnets.…”

“…Several lead-free metal-halide perovskites have emerged as promising candidates, including vacancy-ordered double perovskite (A 2 MX 6 , e.g., A = Cs + , K + ; M = Sn 4+ and Te 4+ ; X = halide ions), , double perovskite (A 2 M I M III X 6 , e.g., A = Cs + , Rb + ; M I = Ag + and Na + ; M III = Bi 3+ , Sb 3+ , and In 3+ ; X = halide ions), − and vacancy-ordered triple perovskite (A 3 M 2 X 9 , e.g., A = K + , Cs + ; M = Bi 3+ and Sb 3+ ; X = halide ions). − However, most of the current research is focused on nonmagnetic systems. In comparison to the extensively studied optoelectronic properties, the investigation of magnetic properties remains relatively limited. − Introducing transition metals into perovskite structures represents a promising approach for altering optoelectronic properties and introducing cooperative magnetism. , …”