7-like Magnetization Plateau of Layered Y2Cu7(TeO3

Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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Structure and 3/7-like Magnetization Plateau of Layered Y2Cu7(TeO3)6Cl6(OH)2 Containing Diamond Chains and Trimers Xiaochen Liu, Zhongwen Ouyang,* Xiaoyu Yue, Xia Jiang, Zhenxing Wang, Junfeng Wang, and Zhengcai Xia Wuhan National High Magnetic Field Center & School of Physics, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China

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S Supporting Information *

ABSTRACT: We have synthesized a new spin-1/2 antiferromagnet, Y2Cu7(TeO3)6Cl6(OH)2, via a traditional hydrothermal method. This compound crystallizes in the triclinic crystal system with space group P1̅. The magnetic ions constitute a two-dimensional layered lattice with a novel topological structure in which the Cu4 clusters make up distorted diamond chains along the a axis and these chains are connected by the Cu3 trimers. The magnetic susceptibility and specific heat measurements show that the compound is antiferromagnetically ordered at TN = 4.1 K. This antiferromagnetic ordering is further supported by electron spin resonance (ESR) data. The magnetization curve presents a fieldinduced metamagnetic transition at 0.2 T, followed by a magnetization plateau within a wide magnetic field range from 7 T to at least 55 T, which corresponds to 3/7 of the saturated magnetization with g = 2.15 obtained from ESR. The possible mechanism for the magnetization plateau is discussed.

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INTRODUCTION Low-dimensional (D) materials have attracted great attention due to the irsimple structure and interesting physical properties.1−5 In particular, Cu-based antiferromagnetic (AFM) compounds with particular lattices such as triangular or kagome lattices exhibit geometrical magnetic frustration and strong quantum spin fluctuations,6−8 giving rise to a great deal of fascinating physical phenomena, such as spin ice, spin liquid, magnetization plateaus, etc.9−14 For instance, the 2D kagome lattice ZnCu3(OH)6Cl2 is not long range magnetically ordered at temperatures down to 50 mK and is regarded as one of the best candidates to achieve a quantum spin liquid.15,16 A diamond chain is the simplest 1D spin frustrated system with exotic magnetic properties: for example, a quantum magnetization plateau.17,18 Through the great efforts of chemists and physicists, several diamond-chain compounds have been synthesized.19−22 There are two representative types of diamond chains: one is composed of a dimer connected via a monomer,19 and the other is formed by tetramers.22 Most of the diamond chains are curtained off by nonmagnetic ions, forming a quasi-1D structure.17 Therefore, to synthesize Cubased compounds containing diamond chains, the choice of nonmagnetic ions or ligands is crucial. Tellurite (TeO3)2− and other similar groups usually display a stereochrmically active lone electron pair which does not participate in the bonding but has a volume similar to that of an oxide and can be regarded as an additional ligand.23−26 The lone electron pair cations are considered to be “chemical scissors” in the crystal structure and have been successfully © XXXX American Chemical Society

applied to obtain low-D magnetic compounds with spin frustration, such as the dimer CuTe2O5,27 tetramers CuSeO328 and Cu4Te5O12Cl4,29 and layered diluted kagome lattice Cu7(OH)6(TeO3)2(SO4)2.30 In order to further reduce the dimensionality of the magnetic structure, the nonmagnetic ions of large ionic radii or high coordination numbers, Y3+ and Sr2+, can be incorporated in the structure: e.g., the buckled kagome Cu3Y(SeO3)2O2Cl31 and dimer SrCu2(TeO3)2Cl232 have been synthesized successfully. Thus, the Cu-based tellurite can be considered as the first choice to investigate the unusual quantum effects of low-D frustrated materials. In this paper, we have successfully synthesized the new 2D layered tellurite Cu-based compound Y2Cu7(TeO3)6Cl6(OH)2 through a traditional hydrothermal method. The 2D structure is constituted by distorted Cu4 diamond chains connected by Cu3 trimers. Since the diamond chains are coupled by magnetic ions, one may see that the compound behaves as a classical spin system. Indeed, the magnetization, specific heat, and ESR measurements show that the compound is antiferromagnetically ordered at TN = 4.1 K. Very interestingly, however, our pulsed high-field magnetization data reveal a field-induced 3/7-like magnetization plateau within a wide range of magnetic fields. Received: February 26, 2019

A

DOI: 10.1021/acs.inorgchem.9b00566 Inorg. Chem. XXXX, XXX, XXX−XXX

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sample was zero field cooled from the paramagnetic (PM) state at 300 K to the desired temperature. Specific heat measurements in zero field from 2 to 30 K were performed with a Quantum Design Physical Property Measurement System (16 T) on an 8.2 mg pellet sample. Pulsed High-Field Magnetization and ESR Measurements. Pulsed high-field magnetization signals were detected via using a pair of coaxial pick-up coils by an induction method in a pulsed magnetic field. The pulsed field was generated by using a long-pulse magnet energized by two 0.8 MJ capacitor banks installed at Wuhan National High Magnetic Field Center, People’s Republic of China, which can achieve a magnetic field up to 55 T with a duration time of 24 ms. The pulsed-field ESR measurements were conducted in a fieldincreasing process from 0 to 30 T with a frequency range of 50−250 GHz using Gunn oscillators and backward wave oscillators as light sources. For the ESR measurements, 1,1-diphenyl-2-picrylhydrazyl (DPPH) with g = 2.0 was used to scale the magnetic field.

EXPERIMENTAL DETAILS

Synthesis. Green single crystals of Y2Cu7(TeO3)6Cl6(OH)2 were prepared via a traditional hydrothermal method. Highly pure (>99.9%) Cu(NO3)2·3H2O, Y(NO3)3·6H2O, TeO2, and NaCl were used as reactants. A mixture of 1.8 mmol of Cu(NO3)2·3H2O (AR, 0.4349 g), 0.6 mmol of Y(NO3)3·6H2O (AR, 0.2298 g), 1.2 mmol of TeO2 (AR, 0.1915 g), NaCl (AR, 0.5 g), and 7 mL of deionized water were sealed in a 28 mL Teflon lined steel autoclave at this work. The stainless steel autoclaves were put into a furnace, heated to 210 °C at a speed of 1 °C/min, and then held at 210 °C for 3 days under autogenous pressure; finally, they were cooled to room temperature at a slow speed of 4 °C/h. After being filtered off and washed with deionized water, pure green sheetlike crystals with very small sizes were obtained. X-ray Crystallographic Studies. X-ray diffraction (XRD) measurements were taken to check the purity of the samples, which is shown in Figure S1 in the Supporting Information. A sheetlike single crystal less than 0.5 mm in length and width was selected and mounted on a glassy fiber for single-crystal XRD measurement. Experimental data were collected at 293 K on an Oxford Diffraction Xcalibur3 CCD diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). The data sets were corrected for Lorentz and polarization factors as well as for absorption via a Multiscan method. The structure was solved completely by direct methods and refined by full-matrix least-squares fitting on F2 by SHELX-97 and Olex2. All non-hydrogen atoms were refined with anisotropic thermal parameters. In addition, the hydrogen atoms were refined with isotropic thermal parameters and located at calculated positions. The final refined structural parameters were verified using the program PLATON. Crystallographic data are displayed in Table 1. The refined atomic positions and important bond lengths and angles are given in Tables S1−S4 in the Supporting Information.

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RESULTS AND DISCUSSION The room-temperature single-crystal XRD analysis shows that Y2Cu7(TeO3)6Cl6(OH)2 crystallizes in the triclinic crystal system with space group P1̅. The unit-cell parameters are a = 7.3673(1) Å, b = 8.7412(1) Å, c = 10.8256(1) Å, α = 88.621(1)°, β = 77.735(1)°, and γ = 74.675(1)°. The coordination environments of Cu, Y, and Te atoms are shown in Schemes S1−S3 in the Supporting Information. The Y atoms are coordinated by eight oxygen atoms composing a distorted YO8 polyhedron with Y−O bonds ranging in length from 2.281(5) to 2.487(5) Å. The Te atoms have three independent crystallographic sites. The Te1 sites are surrounded by three oxygen atoms, forming TeO3 trigonal pyramids with Te−O bond lengths ranging from 1.867(5) to 1.932(5) Å. The Te2 and Te3 sites are also surrounded by three oxygen atoms with Te−O bonds of 1.882(5)−1.909(5) and 1.869(5)−2.427(5) Å, respectively. The Cu atoms have four independent crystallographic sites. The Cu1 sites are coordinated by five oxygen atoms and one chlorine atom, forming a Cu1O5Cl (Cu1 ions) octahedral pyramid with Cu− O bonds of 1.907(6)−2.303(6) Å and a Cu−Cl bond of 2.921(3) Å. The Cu2 sites are surrounded by two oxygen atoms and two chlorine atoms, composing a Cu2O2Cl2 (Cu2 ions) square with Cu−O bond of 1.967(5) Å and Cu−Cl bond of 2.237(2) Å. The Cu3 sites are coordinated by four oxygen atoms and two chlorine atoms, making up a Cu3O4Cl2 (Cu3 ions) octahedral pyramid with Cu−O bonds of 1.914(4)− 2.397(5) Å and Cu−Cl bonds of 2.400(2) and 2.912(3) Å. The Cu4 sites are coordinated by three oxygen atoms and one chlorine atom, forming a Cu4O3Cl square (Cu4 ions) with Cu−O bond lengths ranging from 1.895(6) to 1.962(5) Å and one chlorine atom with Cu−Cl bond of 2.2859(19) Å. Figure 1 shows the crystal structure for Y2Cu7(TeO3)6Cl6(OH)2 viewed along the a axis and (011) plane, respectively. The two Cu4 ion squares and one Cu2 ion square are connected by the corner-sharing oxygen atom of a OH− group, composing a Cu3O6Cl4 cluster (Cu3 trimer). The Cu1 and Cu3 ions are connected to each other by edge-sharing oxygen atoms of TeO3 groups forming a Cu4O12Cl4 cluster (Cu4 cluster) with a parallelogram. As shown in Figure 1b, the Cu4 clusters constitute distorted diamond chains along the a axis. These diamond chains are connected by the Cu3 trimers, through the corner-sharing chlorine atom, stretching among the (011) plane and forming a 2D corrugated sheet with vacancies. These 2D layers stretch in the space by YO8 and make up a 3D framework of the magnetic unit of Y2Cu7(TeO3)6Cl6(OH)2. By removal of the nonmagnetic

Table 1. Crystallographic Data and Structural Refinements for Y2Cu7(TeO3)6Cl6(OH)2 formula formula wt T, K λ, Å space group a, Å b, Å c, Å α, deg β, deg γ, deg V, Å3 Z density, g cm−3 μ, mm −1 GOF on F2 R1, wR2 (I ≥ 2σ(I))a R1, wR2 (all data)

Y2Cu7(TeO3)6Cl6(OH)2 1922.92 293(2) 0.71073 P1̅ 7.3724(5) 8.7660(10) 10.8334(11) 88.532(9) 77.663(8) 74.563(9) 658.92(12) 1 4.846 17.079 1.038 0.0300, 0.0782 0.0317, 0.0800

R1 = ∑||Fo| − |Fc||/∑|Fo|; wR2 = {∑w[(Fo)2 − (Fc)2]2/ ∑w[(Fo)2]2}1/2.

a

Magnetization and Specific Heat Measurements. The magnetization measurements of Y2Cu7(TeO3)6Cl6(OH)2 were conducted by using a superconducting quantum interference device (SQUID) magnetometer. A powdered sample was bundled with preservative film and put into a sample holder that was suspended in the bottom of a plastic drinking straw. The temperature-dependent magnetization (M) and magnetic susceptibility (χ) measurements were conducted between 2 and 300 K at different fields. The fielddependent isothermal magnetization measurements were preformed from 0 to 7 T at different temperatures. Before each measurement, the B

DOI: 10.1021/acs.inorgchem.9b00566 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 2. Topological arrangement of Cu2+ ions viewed along the (011) plane. The four independent crystallographic sites of Cu2+ ions are marked as Cu1, Cu2, Cu3, and Cu4.

Table 2. Cu−Cu Distances (Å) and Corresponding Cu−O− Cu and Cu−Cl−Cu Angles (deg) in Y2Cu7(TeO3)6Cl6(OH)2 angle (deg) ∠Cu3−O4−Cu1 ∠Cu1−O1−Cu3 ∠Cu3−O1−Cu3 ∠Cu3−Cl−Cu4 ∠Cu4−O9−Cu2

distance (Å) 96.65(19) 99.9(3) 97.1(3) 90.76(9) 110.6(3)

Cu1···Cu3 Cu3···Cu1 Cu3···Cu3 Cu3···Cu4 Cu2···Cu4 Cu1···Cu1

2.9737(13) 3.3664(13) 3.2860(19) 3.7256(13) 3.2291(10) 3.087(3)

Figure 1. 2D layer structure of Y2Cu7(TeO3)6Cl6(OH)2 viewed along (a) the a axis and (b) the (011) plane, in which the Cu3 trimers and Cu4 clusters are blue, the Te atoms are dark yellow, Y atoms are dark cyan, Cl atoms are light green, O atoms are red, and H atoms are pink.

ions Y3+, TeO32−, Cl−, and OH−, the topological structure formed by Cu2+ ions builds a 2D spin−lattice in the layer shown in Figure 2. The Cu−Cu distances (Å) and corresponding Cu−O−Cu and Cu−Cl−Cu bond angles (deg) in Y2Cu7(TeO3)6Cl6(OH)2 are displayed in Table 2. Figure 3 shows the M(T) curves measured at different magnetic fields. The low-field curves exhibit a cusp around TN = 4.1 K due to the onset of AFM ordering (see the inset). Below this temperature, the M(T) curves show an upturn which is suppressed with increasing magnetic field. This feature can be ascribed to a small amount of extrinsic PM impurities or defects in the sample, referred to as a Curie tail.33 Interestingly, above 0.2 T, the upturn and the cusp associated with TN disappear gradually. Meanwhile, the M(T) curve presents a large magnetization. These are indicative of the presence of a field-induced magnetic transition at low temperature. Figure 4 shows the 1/χ(T) curves measured at fields below 1 T. All of the curves are not linear at the high-temperature PM state except for the 1 T data. The 1/χ(T) data are magnetic field dependent and do not follow the Curie−Weiss law. At low field, the value of χ(T) is larger (or 1/χ(T) is small),

Figure 3. M(T) curves measured at different magnetic fields. The inset shows the curves at low temperatures and low fields.

whereas at high field χ(T) is small (or 1/χ(T) is large). This suggests that there is a ferromagnetic impurity in the PM matrix. At low field, the contribution of this ferromagnetic component to the susceptibility is dominant, but it is well suppressed at high magnetic field. As a result, the low-field nonlinear 1/χ(T) curve becomes linear at high field. The AFM transition is further supported by the specific heat data in Figure 5, which shows a λ-like peak at 4.1 K. The inset shows the magnetic contribution Cmag obtained by subtracting the phonon contribution, which can be described as Cbg= aT3 + bT5 + cT7 with a = 8.63241 × 10−4 J/K−4 (mol Cu2+)−1, b = −6.23267 × 10−7 J/K−6 (mol Cu2+)−1, and c = 2.03192 × 10−10 J/K−8 (mol Cu2+)−1. The entropy change is derived by C

DOI: 10.1021/acs.inorgchem.9b00566 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

accompanied by an enhancement in intensity. Below TN, another peak appears at lower field due to the onset of AFM order. Figure 7 shows the M(H) curves measured at 2 K. The curve displays an anomaly at Hc = 0.2 T (see also the inset), which

Figure 4. 1/χ(T) curves measured at fields below 1 T.

Figure 7. M(H) curves measured with SQUID at 2, 3, 4, 5, and 7 K. The inset shows the data from 0 to 1 T. The red squares stand for the 2 K data taken from the field-dependent M(T) curves in Figure 3.

corresponds to a field-induced magnetic transition from the AFM state to a new magnetic state with a sizable magnetization. Figure 7 also shows the 2 K data taken from the fielddependent M(T) curves in Figure 3. As expected, these data match well with the M(H) curve measured at 2 K. Thus, both the M(T) and M(H) curves support the occurrence of the field-induced magnetic transition. At 5 K (>TN), this transition disappears and the magnetization curve presents a PM-like behavior. To examine if the magnetization will reach saturation, highfield magnetization was measured at 2 K using a pulsed magnetic field up to 55 T. Figure 8 shows the M(H) curve

Figure 5. Temperature-dependent specific heat at zero field. The red line is the phonon contribution. The inset shows the magnetic contribution Cmag and the temperature-dependent entropy S.

integrating Cmag/T from 2 to 30 K, which gives ΔS = 1.71 J K−1 (mol Cu2+)−1, close to 29.7% of S = R ln(2S + 1) calculated from the Cu2+ system, where R is the gas constant. This indicates that long-range magnetic ordering at TN causes the loss of a part of the magnetic entropy. To further investigate the magnetism of Y2Cu7(TeO3)6Cl6(OH)2, we performed high-field ESR measurements. Figure 6 shows the temperature-dependent ESR spectra measured at 60 GHz. At 25 K, a weak electron PM resonance (EPR) peak is observed and the g factor is derived to be g = 2.15, a typical value for Cu2+. As the temperature decreases, the resonance peak shifts gradually to lower field

Figure 8. High-field magnetization M(H) curves measured at 2 K calibrated with the SQUID data. The black dashed line indicates the calculated curve from exact diagonalization of the Hamiltonian for an isolated Cu7 cluster.

calibrated with SQUID data. The H-decreasing curve nearly follows the H-increasing curve. The magnetization increases rapidly at low fields. Above 7 T, the magnetization increases slowly with a small slope. Extrapolating the linear part of the curve to zero field gives rise to 0.41 μB/Cu2+, which is far from the magnetic saturation. Note that this value is close to 0.46 μB/Cu2+, i.e., 3/7 of the saturation magnetization Ms with g = 2.15 obtained from the ESR spectra (Figure 6). Thus, a field-

Figure 6. Temperature-dependent ESR spectra measured at 60 GHz from 2 to 25 K. The DPPH resonance line is shown as a field marker. D

DOI: 10.1021/acs.inorgchem.9b00566 Inorg. Chem. XXXX, XXX, XXX−XXX

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induced 3/7 magnetization plateau above 7 T is well established by our high-field magnetization data. We now qualitatively discuss the origin of the 3/7 magnetization plateau. First, the occurrence of a plateau can have a quantum origin. Within the framework of an isolated Cu7 cluster composed of a Cu4 cluster and a Cu3 trimer with AFM interactions J1 and J2 (see Figure 2), one can indeed obtain a wide 3/7 plateau up to 55 T by diagonalizing the Hamiltonian H = −∑Ji,jSi·Sj + ∑gμBSiz·H with g = 2.15, J1/kB = −77 K, and J2/kB = −0.3 K. Obviously, such a Hamiltonian model is too simplified because only the interactions within Cu4 and Cu3 clusters are considered. As seen from the Cu−Cu bond lengths and Cu−O/Cl−Cu bond angles (Table 2), the complicated intercluster interactions cannot be ignored, which leads to AFM ordering at 4.1 K. With the intercluster couplings in a 2D layered lattice, it is not clear whether the wide 3/7 magnetization plateau survives. Second, the magnetization plateau can have a classical origin. Usually in a classical picture, the magnetization increases linearly with magnetic field up to magnetic saturation by tilting the spins along the field direction. However, the tittle compound Y2Cu7(TeO3)6Cl6(OH)2 contains four nonequivalent Cu sites. Under an external magnetic field, it is possible that Cu ions from some crystallographic sites are spin polarized and those from the other sites are not. This would allow for a classical plateau phase. To explore the exact origin of the 3/7 magnetization plateau, neutron diffraction experiments are desired to determine the magnetic structure and spin magnetic moments of Cu ions.

AUTHOR INFORMATION

Corresponding Author

*E-mail for Z.O.: [email protected]. ORCID

Xiaochen Liu: 0000-0001-5802-7781 Xiaoyu Yue: 0000-0003-0673-9810 Zhenxing Wang: 0000-0003-2199-4684 Zhengcai Xia: 0000-0002-0534-2830 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grant Nos. 11874023 and 11574098) and by the Fundamental Research Funds for the Central Universities (Grant No. 2019kfyXKJC008). Z.X. is grateful for support from the National Key Research and Development Program of China (Grant No. 2016YFA0401003) and the Natural Science Foundation of China (Grant No. 11674115).

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REFERENCES

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CONCLUSIONS In summary, we have successfully synthesized the new 2D layered tellurite antiferromagnet Y2Cu7(TeO3)6Cl6(OH)2 that crystallizes in the triclinic crystal system with space group P1̅. The 2D layered lattice is composed of Cu3 trimers and Cu4 clusters forming a diamond chain along the a axis. The layers are curtained off from each other by the YO8 polyhedrons. The compound is ordered at TN = 4.1 K on the basis of the magnetization, specific heat, and ESR data. The M(H) curve at 2 K exhibits a field-induced magnetic transition at 0.2 T. Interestingly, the high-field M(H) curve reveals a well-defined magnetization plateau within a field range of 7−55 T. The plateau magnetization is derived to be 0.41 μB/Cu2+. This value is nearly 3/7 of the saturated value (g = 2.15), suggesting the presence of a 3/7 magnetization plateau.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b00566. Simulated and experimental powder XRD patterns, atomic coordination environments, and the final refined atomic positions and structural parameters for Y2Cu7(TeO3)6Cl6(OH)2 (PDF) Accession Codes

CCDC 1893507 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. E

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Inorganic Chemistry

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DOI: 10.1021/acs.inorgchem.9b00566 Inorg. Chem. XXXX, XXX, XXX−XXX