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[Alexei A. Belik](https://orcid.org/0000-0001-9031-2355)

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[Anisotropic Thermal Expansion and a Second-Order Charge Order Transition in the Ferrimagnetic Dy<sub>2</sub>CuZnMn<sub>4</sub>O<sub>12</sub> Perovskite with Triple A-Site Cation Ordering](https://mdr.nims.go.jp/datasets/1026b300-04e9-48b3-b044-036419cdc26d)

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Anisotropic Thermal Expansion and a Second-Order Charge Order Transition in the Ferrimagnetic Dy2CuZnMn4O12 Perovskite with Triple A-Site Cation OrderingAnisotropic Thermal Expansion and a Second-Order Charge OrderTransition in the Ferrimagnetic Dy2CuZnMn4O12 Perovskite withTriple A‑Site Cation OrderingAlexei A. Belik*Cite This: Inorg. Chem. 2023, 62, 20042−20049 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: Dy2CuZnMn4O12 perovskite, belonging to the A-site columnar-orderedquadruple perovskite family with the general composition of A2A′A″B4O12, was prepared bya high-pressure, high-temperature method at 6 GPa and 1500 K. Its crystal structure wasstudied by synchrotron powder X-ray diffraction between 100 and 800 K. The ideal cationdistribution (without antisite disorder) was found to be realized within the sensitivity of thesynchrotron X-ray diffraction method. Between 100 and 400 K, it crystallizes in space groupPmmn (no. 59) and has layered charge ordering of Mn3+ and Mn4+ at the B sites. Above 425 K,it crystallizes in space group P42/nmc (no. 137) with one crystallographic B site and an averageMn3.5+ oxidation state. The charge ordering transition (at TCO = 425 K) appears to be of thesecond order as no anomalies were found on differential scanning calorimetry curves andtemperature dependence of the unit cell volume, and the orthorhombic a and b latticeparameters merge gradually. The compound demonstrates anisotropic thermal expansion withthe c lattice parameter decreasing with increasing temperature above 280 K. A ferrimagnetictransition occurs at TC = 116 K with an additional, gradual rise of magnetic susceptibilities below 45 K, probably due to increases ofthe ordered moments of the Dy sublattices.1. INTRODUCTIONA-site columnar-ordered quadruple perovskite oxides with thegeneral composition of A2A′A″B4O12 are a new playground inthe perovskite science to play with compositional variations andtheir effects on physical properties.1 In comparison with classicalABO3 perovskites with one type of A sites and A-site-orderedquadruple perovskites, AA′3B4O12, with intrinsically two types ofA sites (A with a 12-fold coordination and A′ with a square-planar coordination), A2A′A″B4O12 perovskites have an addi-tional degree of freedom in the presence of the A″ site with atetrahedral coordination (as the first coordination sphere).Therefore, a principally different, new set of cations, which arenot usually located at A sites of perovskites, can be used for theA′′ site, such as Ga3+ and Zn2+.2−5The parent structure of the A2A′A″B4O12 perovskites has P42/nmc symmetry and is formed through large tilts of the a+a+c−type.1 This symmetry is retained in the majority of examples ofsuch perovskites.1,6 The next most commonly observedsymmetry is P42/n, which is produced through full or partialrock-salt-type B-cation orderings, A2A′A″B2B′2O12.1,6 The lesscommon symmetries are P42mc (which is formed through polardistortions in CaMnTi2O6,7 CaMnTi2−xVxO6,8 andNaYMnMn-Ti4O12)9 and Pmmn (which is formed through layered-type B-cation ordering in RMn3O6 (R = Gd to Tm)10,11 andR2CuMnMn4O12 (R = Dy and Y)12 due to partial or full chargeordering of Mn3+ and Mn4+, respectively). The presence ofcharge-ordered structures based on the same element couldsuggest the existence of temperature-driven charge-(dis)orderedtransitions as observed in simple perovskites (e.g., half-dopedR3+0.5A2+0.5MnO3)13 or quadruple perovskites (e.g.,ACu3Fe4O12).14 However, such charge-order transitions havenot been observed so far in A2A′A″B4O12 perovskites.1,10In this work, we prepared a new member of the A-sitecolumnar-ordered quadruple perovskite family with thecomposition of Dy2CuZnMn4O12. In this compound, a newcombination of the A/A′/A″ cations was used (R3+/Cu2+/Zn2+)to achieve the triple A-site cation ordering. This combinationalso gives an average oxidation state of Mn as +3.5�an idealvalue for the realization of possible charge ordering. We indeedfound that Dy2CuZnMn4O12 crystallizes in space group Pmmnat room temperature with 1:1 charge order of Mn3+ and Mn4+ atthe B sites. High-temperature structural studies showed theexistence of a charge-disorder transition above 425 K, which is ofthe second order. We also observed anisotropic thermalexpansion above 280 K and a ferrimagnetic transition belowTC = 116 K.Received: August 15, 2023Revised: October 20, 2023Accepted: November 8, 2023Published: November 27, 2023Articlepubs.acs.org/IC© 2023 American Chemical Society20042https://doi.org/10.1021/acs.inorgchem.3c02835Inorg. Chem. 2023, 62, 20042−20049Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on December 11, 2023 at 10:57:30 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Alexei+A.+Belik"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acs.inorgchem.3c02835&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/inocaj/62/49?ref=pdfhttps://pubs.acs.org/toc/inocaj/62/49?ref=pdfhttps://pubs.acs.org/toc/inocaj/62/49?ref=pdfhttps://pubs.acs.org/toc/inocaj/62/49?ref=pdfpubs.acs.org/IC?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.3c02835?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://pubs.acs.org/IC?ref=pdfhttps://pubs.acs.org/IC?ref=pdf2. EXPERIMENTAL SECTIONDy2CuZnMn4O12 was prepared from a stoichiometric mixture of o-DyMnO3, ZnO (99.9%), CuO (99.9%), andMnO2 (Alfa Aesar, 99.9%)at about 6 GPa and about 1500 K for 2 h in Au capsules. After annealingat 1500 K, the samples were cooled down to room temperature byturning off the heating current, and the pressure was slowly released.Wenote that the oxygen content of a commercial well-crystallized single-phase MnO2 chemical was confirmed by thermal analysis. Single-phaseo-DyMnO3 was prepared from a stoichiometric mixture of Dy2O3(99.9%) and Mn2O3 (99.99%) by annealing in air at 1430 K for 60 hwith several intermediate grindings. After the high-pressure synthesis,the sample was recovered as black powder (Figure S1). Therefore, somemeasurements (such as, specific heat, resistivity, and dielectricconstant), which require dense pellets, could not be performed. Wenote that the melting point of Au at 6 GPa is above 1600 K;15 therefore,Au capsules could be safely used for the synthesis at 1500 K.We did notobserve any reaction between Au and Dy2CuZnMn4O12 or any damageof Au capsules.X-ray powder diffraction (XRPD) data were collected at roomtemperature on a RIGAKU MiniFlex600 diffractometer using Cu Kαradiation (2θ range of 8−100°, a step width of 0.02°, and scan speed of2°/min). Synchrotron XRPD data were collected from 100 to 800 K onbeamline BL02B2 of SPring-8 (the intensity data were taken between2.08° and 78.22° at 0.006° intervals in 2θ using a wavelength of λ =0.619283 Å).16 High statistics data with a measurement time of 100 swere collected at 100, 295, and 600 K; at all other temperatures, themeasurement time was 10 s. The sample was placed into an openLindemann glass capillary tube (inner diameter: 0.2 mm), which wasrotated during measurements. The Rietveld analysis of all XRPD datawas performed using the RIETAN-2000 program.17Magnetic measurements were performed on a SQUID magneto-meter (Quantum Design, MPMS3) between 2 and 400 K in appliedfields of 100 Oe and 10 kOe under both zero-field-cooled (ZFC) andfield-cooled on cooling (FCC) conditions. High-temperature data weretaken at 70 kOe from 300 to 470 K. Isothermal magnetizationmeasurements were performed between −70 and 70 kOe at differenttemperatures. A small sample weight of 11.09 mg was used for the dcmagnetic measurements because of a large magnetic moment (1.82emu at 5 K and 70 kOe). Frequency dependent alternating current (ac)susceptibility measurements were performed using a Quantum DesignMPMS3 instrument at a zero static dc field and at different frequencies( f) and different applied oscillating magnetic fields (Hac) from 140 to 2K using a 24.7 mg sample.Differential scanning calorimetry (DSC) curves of a powder samplewere recorded on a Mettler Toledo DSC1 STARe system under a N2flow between 125 and 670 K in an open Al capsule with a heating/cooling rate of 10 K/min. Two DSC runs were performed to check thereproducibility. No DSC anomalies were found between 125 and 670K.3. RESULTS AND DISCUSSIONDy2CuZnMn4O12 was found to be single-phase within thesensitivity of the laboratory XRPD data. All its reflections couldbe indexed in orthorhombic symmetry with a = 7.2599 Å, b =7.2709 Å, and c = 7.7736 Å. Therefore, the Pmmn structuralmodel and the structural parameters of DyMn3O6 (as the initialones)10 were used in the Rietveld analysis of Dy2CuZnMn4O12.Cu2+ (27 electrons) and Zn2+ (28 electrons) cations cannot bedistinguished by (nonresonant) synchrotron XRPD. Therefore,we assumed the distribution of Cu2+ and Zn2+ based on theircoordination preferences: Zn2+ cations have a strong preferencefor tetrahedral sites (among tetrahedral and square-planar ones)while Cu2+ cations have a strong preference for square-planarsites.18 We note that CaZnV2O619 and CaCuFeReO620 wererecently prepared, where Zn2+ and Cu2+ cations are located inboth square-planar (A′) and tetrahedral (A″) sites. However,these compounds were stabilized at much higher pressures of 12and 15.5 GPa, respectively, and they were not stable at 6 GPa.Therefore, we can assume that usual tendencies in the siteTable 1. Structure Parameters of Dy2CuZnMn4O12 at 100 K(the First Line for Each Site) and 295 K (the Second Line forEach Site) from Synchrotron XRPD Dataasite WP x y z Biso (Å2)Dy1 2a 0.25 0.25 0.7785(2) 0.08(2)0.25 0.25 0.7784(2) 0.27(3)Dy2 2a 0.25 0.25 0.2786(2) 0.15(3)0.25 0.25 0.2786(2) 0.40(3)Cu 2b 0.75 0.25 0.7349(4) 0.41(5)0.75 0.25 0.7374(5) 0.61(6)Zn 2b 0.75 0.25 0.2486(4) 0.03(3)0.75 0.25 0.2488(5) 0.30(5)Mn1 4c 0.5 0 0 0.03(5)0.5 0 0 0.11(8)Mn2 4d 0 0.5 0.5 0.10(5)0 0.5 0.5 0.26(8)O1 8g 0.4402(7) −0.0599(7) 0.2624(10) 0.61(8)0.4389(8) −0.0589(8) 0.2610(11) 1.02(9)O2 4f 0.0634(10) 0.25 0.0336(13) 0.19(12)0.0623(10) 0.25 0.0344(13) 0.08(11)O3 4e 0.25 0.5396(11) 0.9105(11) 0.18(13)0.25 0.5380(11) 0.9083(12) 0.30(14)O4 4f 0.5391(12) 0.25 0.4231(13) 0.61(16)0.5389(11) 0.25 0.4238(13) 0.71(16)O5 4e 0.25 0.4330(10) 0.5386(13) 0.06(11)0.25 0.4353(10) 0.5405(13) 0.25(13)aSource: Synchrotron powder X-ray diffraction (λ = 0.61928 Å); usedd-space range: from 0.4916 to 7.1 Å. Crystal system: orthorhombic;space group Pmmn (no. 59, origin choice 2); Z = 2. Molecular weight:865.6708 g/mol. The occupation factors (g) of all the sites are unity(g = 1). WP: Wyckoff position. No detectable impurities. 100 K: a =7.25134(2) Å, b = 7.25958(2) Å, c = 7.76916(1) Å, and V =408.9820(14) Å3; Rwp = 7.02%, Rp = 5.15%, RB = 2.86%, and RF =1.41%; ρcal = 7.030 g/cm3. 295 K: a = 7.25988(2) Å, b = 7.27087(2)Å, c = 7.77362(2) Å, and V = 410.3355(19) Å3; Rwp = 7.26%, Rp =5.33%, RB = 3.22%, and RF = 1.66%; ρcal = 7.006 g/cm3.Table 2. Selected Bond Lengths (l (Å) < 2.8 Å), Bond Angles(deg), Bond Valence Sums, BVS, and Distortion Parametersof MnO6, Δ, in Dy2CuZnMn4O12 at 295 KaDy1−O5 × 2 2.288(9) Dy2−O2 × 2 2.337(9)Dy1−O3 × 2 2.325(8) Dy2−O4 × 2 2.382(9)Dy1−O2 × 2 2.412(9) Dy2−O5 × 2 2.441(9)Dy1−O1 × 4 2.669(7) Dy2−O1 × 4 2.635(7)BVS(Dy13+) +3.38 BVS(Dy23+) +3.13Cu−O1 × 4 1.952(4) Zn−O3 × 2 1.967(9)BVS(Cu2+) +1.91 Zn−O4 × 2 2.050(9)BVS(Zn2+) +1.77Mn1−O2 × 2 1.892(2) Mn2−O5 × 2 1.901(2)Mn1−O3 × 2 1.969(3) Mn2−O4 × 2 1.932(3)Mn1−O1 × 2 2.120(8) Mn2−O1 × 2 1.958(8)BVS(Mn13+) +3.29 BVS(Mn24+) +3.72Δ(Mn1−O) 22.6 × 10−4 Δ(Mn2−O) 1.4 × 10−4Mn1−O1−Mn2 × 2 144.73(9) Mn2−O4−Mn2 140.32(9)Mn1−O2−Mn1 147.75(9) Mn2−O5−Mn2 145.35(9)Mn1−O3−Mn1 134.33(9)aBVS = ∑i=1N νi, νi = exp[(R0 − li)/B], N is the coordination number, B= 0.37, R0(Dy3+) = 2.036, R0(Cu2+) = 1.679, R0(Zn2+) = 1.704,R0(Mn4+) = 1.753, and R0(Mn3+) = 1.76.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.3c02835Inorg. Chem. 2023, 62, 20042−2004920043https://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.3c02835/suppl_file/ic3c02835_si_001.pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.3c02835?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-aspreferences for Cu2+ and Zn2+ cations are realized inDy2CuZnMn4O12 prepared at 6 GPa.Small antisite disorders are often realized in A2A′A″B4O12perovskites with A = rare earths, A′ = Mn, and A″ = Mn. Suchantisite disorders could be observed with synchrotron XRPDdata as small (but detectable) deviations of occupation factorsfrom unity (for ideal cation distribution models).3−5,11However, during the structural analysis of Dy2CuZnMn4O12,all cation occupation factors converged to values close to unity.We report here the occupation factors at 600 K as the symmetryat 600 K is higher (see below) and the number of refinedstructural parameters is smaller. The following values wereobtained (when all other structural and nonstructuralparameters were refined simultaneously including atomicdisplacement parameters): g(Dy) = 0.985(2), g(Cu) =0.482(3) (for a disordered model with the ideal g = 0.5), andg(Zn) = 0.995(6) with fixed g(Mn) = 1 and g(Cu) = 0.487(3),g(Zn) = 1.014(6), and g(Mn) = 1.018(2) with fixed g(Dy) = 1.We also note that whenMnwas located at the tetrahedral A″ site(or the square-planar A′ site), its occupation factor was refinedto be 1.265(7) (or 0.600(3) for the A′ site), that is, significantlylarger than unity (or 0.5). Therefore, we concluded that the idealcation distributions are realized in Dy2CuZnMn4O12 within thesensitivity of synchrotron XRPD data.Refined structural parameters, primary bond lengths, andbond valence sums (BVS)21 of Dy2CuZnMn4O12 at 100 and 295K are summarized in Tables 1 and 2 and Table S1. Experimental,calculated, and difference synchrotron XRPD patterns ofDy2CuZnMn4O12 at 295 K are shown in Figure 1. The crystalstructure of Dy2CuZnMn4O12 at 295 K is presented in Figure 2a.The Pmmn structural model was used to obtain the latticeparameters between 100 and 450 K (Figure 3). At 425 and 450Figure 1. Experimental (black crosses), calculated (red line), and difference (blue line at the bottom) synchrotron powder X-ray diffraction patterns ofDy2CuZnMn4O12 atT = 295K between 6 and 60°. The tickmarks show possible Bragg reflection positions. The inset shows similar curves atT = 600 Kbetween 6 and 26°.Figure 2. Crystal structures of Dy2CuZnMn4O12 at (a) T = 295 K in the charge-ordered state and (b) T = 600 K in the charge-disordered state.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.3c02835Inorg. Chem. 2023, 62, 20042−2004920044https://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.3c02835/suppl_file/ic3c02835_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig2&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.3c02835?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asK, the orthorhombic aO and bO lattice parameters alreadymerged, suggesting a phase transition to a tetragonal structure.The orthorhombic splitting of reflections also disappeared(Figure 4). Therefore, at 450 K and above, we used the P42/nmcmodel3 to obtain temperature dependence of the latticeparameters. The refined structural parameters and bond lengthsat 600 K are summarized in Tables 3 and 4, and the fittingpatterns are shown in the inset of Figure 1. The crystal structureof Dy2CuZnMn4O12 at 600 K is given in Figure 2b. We note thatthe Cu site could be split from the 2a site (with g = 1) to the 4csite (with g = 0.5) in the P42/nmc model.In the Pmmn model, there are two independent sites for the Bcations, Mn1 (4c) and Mn2 (4d). The Mn1 and Mn2 sites havedifferent BVS parameters of +3.29 and +3.72. More importantly,the Mn1 and Mn2 sites have very different octahedral distortionparameters of 22.6 × 10−4 and 1.4 × 10−4, respectively. Thesetwo facts give evidence that the Mn1 site should be occupied byMn3+ cations resulting in a strong Jahn−Teller distortion of theMn1O6 octahedron. The Mn2 site should be occupied by Mn4+cations without strong Jahn−Teller distortions of the Mn2O6octahedron. We note that BVS parameters for Mn3+ at B sites ofperovskites (for example, in RMnO3 with strong Jahn−Tellerdistortions whereMn definitely has an oxidation state of +3)22,23are often higher than expected (for example, +3.15 to +3.25). At600 K in the P42/nmc model, there is one crystallographic sitefor the B cations. The BVS value of +3.47 was close to theexpected average value of +3.5, and the octahedral distortionparameter had an intermediate value of 7.6 × 10−4, reflecting thestatistical presence of 50% of Mn3+ cations. Therefore, weconclude that a charge-order (CO) structure is realized belowTCO = 425 K. Figure 5 shows temperature dependence of theMn−O, Cu−O, and Zn−O bond lengths. The Mn1−O1 bondshows a tendency for a gradual decrease with increasingtemperature, and the Mn2−O1 and Mn−O1 bonds show atendency for a gradual increase. Other bonds were nearlytemperature independent within the sensitivity of the structuralanalysis based on synchrotron powder X-ray diffraction.No DSC anomalies were detected near TCO = 425 K (FigureS2 of the Supporting Information). The temperature depend-ence of the unit cell volume (Figure 3b) shows no anomaliesbetween 100 and 800 K. The orthorhombic aO and bO latticeparameters merge gradually when approaching TCO = 425 K. Allof these observations suggest that the structural phase transitionat TCO = 425 K is of the second order.The orthorhombic aO and bO lattice parameters andtetragonal aT lattice parameter monotonically increase withtemperature from 100 to 800 K (Figure 3). On the other hand,the orthorhombic cO lattice parameter slightly increases from100 to 280 K and then decreases from 280 to 800 K (as cT above425 K). Therefore, Dy2CuZnMn4O12 demonstrates anisotropicthermal expansion above 280 K. As shown in Figure 5, nodetectable anomalies were observed on temperature depend-ence of the bond lengths. Therefore, the origin of the anisotropicthermal expansion is not clear at the moment. Neutrondiffraction studies, which can locate oxygen atoms moreaccurately, will be needed to understand the structural evolutionof Dy2CuZnMn4O12 with temperature more precisely.Temperature-driven structural phase transitions inA2A′A″B4O12 perovskites have only been discovered so far inCaMnTi2O67 and CaMnTi2−xVxO68 during a ferroelectric-paraelectric phase transition (P42mc ⇔ P42/nmc). Thediscovery of a charge-order transition in Dy2CuZnMn4O12(Pmmn ⇔ P42/nmc) could suggest the existence of suchtemperature-driven transitions in other A2A′A″B4O12 perov-skites that crystallize in space group Pmmn at room temperature(e.g., RMn3O610,11 and R2CuMnMn4O12).12 High-temperatureDSC experiments were performed in the case of RMn3O6,10 butno anomalies were detected. Therefore, it was concluded thatRMn3O6 does not show charge-order transitions up to 873 K.Our current results give evidence that such transitions could notbe detected by DSC, and direct high-temperature structuralstudies are needed to discover such transitions.FCC magnetic susceptibilities showed sharp rises below TC =116 K in a small applied magnetic field of 100 Oe, suggesting thedevelopment of a strong ferromagnetic (FM) component(Figure 6) with additional, gradual rises below about 45 K.The additional anomalies could bemore clearly seen on the ZFCcurve and on the differential dχT/dT versus T curves (FigureS3). At H = 100 Oe, a difference between the ZFC and FCC χversus T curves was observed below TC. At H = 10 kOe, almostFigure 3. (a) Temperature dependence of the aO, bO, and aT latticeparameters of Dy2CuZnMn4O12 between 100 and 800 K. (b)Temperature dependence of the cO and cT lattice parameters (theleft-hand axis) and the unit-cell volume (the right-hand axis) ofDy2CuZnMn4O12. Errors are smaller than the symbol sizes. αV is thevolumetric coefficient of thermal expansion calculated between T = 450K and T = 775 K. O, orthorhombic; T, tetragonal.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.3c02835Inorg. Chem. 2023, 62, 20042−2004920045https://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.3c02835/suppl_file/ic3c02835_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.3c02835/suppl_file/ic3c02835_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.3c02835/suppl_file/ic3c02835_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig3&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.3c02835?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asno difference was detected between the ZFC and FCC χ versusT curves. The χ−1 versus T curves followed the Curie−Weisslaw, and a fit by the law between 300 and 400 K gave a positiveCurie−Weiss temperature, θ = +125 K, indicating predom-inantly FM interactions between magnetic ions. The calculatedeffective magnetic moment (μcalc) is 17.485μB (for thecalculation we used 10.6μB for Dy3+, 4.899μB for Mn3+,3.873μB for Mn4+, and 1.732μB for Cu2+ and an equation μcalc2= 2 μDy2 + 2 μMn(III)2 + 2 μMn(IV)2 + μCu2). The experimentaleffective magnetic moment was about 9% smaller (μeff =15.99μB). While the origin of this reduction is not clear at themoment, the same tendency was observed for all other membersFigure 4.Temperature dependence of the synchrotron X-ray powder diffraction patterns of Dy2CuZnMn4O12 from 100 to 450 K (between 6 and 30°).The inset shows details near the 040O, 400O, and 400T reflections to emphasize the disappearance of the orthorhombic (O) distortion. T, tetragonal.Table 3. Structure Parameters of Dy2CuZnMn4O12 at 600 K from Synchrotron X-ray Powder Diffraction Dataaatom WP g x y z Biso (Å2)Dy 4d 1 0.25 0.25 0.22151(5) 0.788(8)Cu 4c 0.5 0.75 0.25 0.7642(8) 1.04(7)Zn 2b 1 0.75 0.25 0.25 0.83(5)Mn 8e 1 0 0 0 0.500(10)O1 8g 1 0.25 0.0629(5) −0.0362(5) 0.68(7)O2 8g 1 0.25 0.5393(5) 0.5849(5) 1.08(9)O3 8f 1 0.4395(4) −x 0.25 1.51(9)ag is the occupation factor. Source: Synchrotron powder X-ray diffraction (λ = 0.61928 Å); used d-space range: from 0.4916 to 7.1 Å. Crystalsystem: tetragonal; space group: P42/nmc (no. 137, origin choice 2); Z = 2. Molecular weight: 865.6708 g/mol. a = 7.30342(1) Å, c = 7.75007(2)Å, and V = 413.3886(12) Å3; Rwp = 7.26%, Rp = 5.40%, RB = 4.78%, and RF = 3.97%; ρcal = 6.955 g/cm3.Table 4. Bond Lengths (in Å; Below 2.8 Å), Bond Angles (indeg), Bond-Valence Sum (BVS), and Distortion Parametersof MnO6 (Δ) in Dy2CuZnMn4O12 at 600 KaDy−O1 × 2 2.323(4) Mn−O1 × 2 1.904(1)Dy−O2 × 2 2.363(4) Mn−O2 × 2 1.962(2)Dy−O1 × 2 2.420(4) Mn−O3 × 2 2.036(1)Dy−O3 × 4 2.666(1) Δ(MnO6) 7.6 × 10−4BVS(Dy3+) +3.19 BVS(Mn3+) +3.47Cu−O3 × 4 1.960(4) Mn−O1−Mn × 2 147.15(6)BVS(Cu2+) +1.87 Mn−O2−Mn × 2 137.08(6)Zn−O2 × 4 2.002(4) Mn−O3−Mn × 2 144.25(6)BVS(Zn2+) +1.79Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.3c02835Inorg. Chem. 2023, 62, 20042−2004920046https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig4&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.3c02835?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asof the R2CuZnMn4O12 (for example, μcalc = 9.00μB versus μeff =8.29μB for R = Lu) and R2CuGaMn4O12 series.3Temperature dependence of magnetic susceptibilities ofDy2CuZnMn4O12 was qualitatively similar to that of the parentDy2MnMnMn4O12 (= DyMn3O6).10 But the absolute values ofmagnetic susceptibilities were about 10 times larger inDy2CuZnMn4O12 at both H = 100 Oe and 10 kOe. This factsuggests that the ordered moments in Dy2CuZnMn4O12 weremuch larger than those of Dy2MnMnMn4O12. Recent neutrondiffraction studies found that the ordered moments weresignificantly reduced (in comparison with the expected fullmoments) in an isostructural compound Y2MnMnMn4O12 dueto competing exchange interactions, and there was acompetition between antiferromagnetic and ferrimagneticground states.24 The magnetic frustration could be reducedthrough the introduction of nonmagnetic Zn2+ cations into theA″ site in Dy2CuZnMn4O12 and through the full charge orderingof Mn3+ and Mn4+, resulting in larger ordered magneticmoments. The gradual rise of magnetic susceptibilities below45 K could be caused by the gradual increase of the orderedmoments of the Dy3+ sublattices, but it was difficult (from theavailable data) to determine at what temperature the Dy3+sublattices start to order.On the other hand, temperature dependence of magneticsusceptibilities of Dy2CuZnMn4O12 was different from that ofDy2CuMnMn4O12 at small magnetic fields and at temperaturesbelow about 40 K.12 In Dy2CuMnMn4O12, magnetic suscepti-bilities decreased at low temperatures. This fact suggestsdifferent magnetic structures for these two compounds. Themagnetic susceptibility behavior of Dy2CuMnMn4O12 wasconsistent with the determined magnetic structure, where theDy1 and Dy2 sublattices order antiferromagnetically relative toeach other but with different magnitudes, and the resultinguncompensated moment on the Dy sublattices aligns anti-ferromagnetically relative to the FM Mn sublattices.12Isothermal magnetization measurements (Figure 7) showed abehavior typical for soft ferrimagnets with a coercive field,HC, ofabout 200 Oe at T = 5 K and a large saturation magnetization,MS, of about 25.6μB (at T = 5 K and H = 70 kOe). The nearsaturation value was already observed from about H = 20 kOe.This saturation value is smaller than the full magnetization of35μB expected for a full FM alignment (using the maximumvalue of 10 μB for Dy3+). On the other hand, Dy3+ cations have anoticeable single-ion anisotropy; therefore, the full moment ofDy3+ cannot be reached in powder samples. Magnetic structuresof related compounds, Dy2CuMnMn4O12 and Y2CuGaMn4O12,were investigated by neutron diffraction. It was found that the B-site Mn sublattices are ordered ferromagnetically but withreduced magnetic moments (2.2μB per Mn in Y2CuGaMn4O12and 2.5μB per Mn4+ and 3.3μB per Mn3+ in Dy2CuMnMn4O12).Considering uncertainties in ordered moments on the Dy andMn sublattices, the maximum contribution of 1μB from the Cusublattice of Dy2CuZnMn4O12 can be neglected in thediscussion below.MS was about 9.5μB (at T = 5 K) in a related compoundwithout magnetic rare-earth cations, Lu2CuZnMn4O12 (theinset of Figure 7), given an average moment of 2.4μB per Mn,which is close to the experimentally determined values in therelated compounds. Assuming a similar magnetic structure withsimilar ordered moments at the B sublattices inDy2CuZnMn4O12 and Lu2CuZnMn4O12, the difference in theMS values could be attributed to the Dy3+ sublattices. Thedifference was about 16μB, which was significantly larger thanthe maximum Dy3+ ordered moment. This fact suggests thatboth Dy3+ sublattices (Dy1 and Dy2) give FM contributions tothe magnetic structure with an average value of 8μB. Therefore,M versus H curves of Dy2CuZnMn4O12 (and comparison withthe related compounds) suggest that the Mn1 and Mn2sublattices are ordered ferromagnetically and the Dy1 andDy2 sublattices are ordered ferromagnetically relative to eachother and to the Mn sublattices.4. CONCLUSIONSIn conclusion, we prepared a new member of the A-sitecolumnar-ordered quadruple perovskites, Dy2CuZnMn4O12,which crystallizes in the charge-order structure at roomtemperature with Pmmn symmetry. Using direct high-temper-Figure 5.Temperature dependence of (a) theMn−Obond lengths and(b) the Cu−O and Zn−O bond lengths in Dy2CuZnMn4O12.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.3c02835Inorg. Chem. 2023, 62, 20042−2004920047https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig5&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.3c02835?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asature structural studies, we could detect a charge-disordertransition above 425 K, while other methods could not detectsuch a transition. Triple A-site cation ordering was realizedthrough a new combination of the A/A′/A″ cations (Dy3+/Cu2+/Zn2+). Dy2CuZnMn4O12 exhibits a ferrimagnetic tran-Figure 6. Left-hand axis presents ZFC (filled symbols) and FCC (empty symbols) dc magnetic susceptibility (χ = M/H) curves of Dy2CuZnMn4O12measured at 100 Oe and 10 kOe (multiplied by 10). Right-hand axis shows the FCC χ−1 versus T curves at 10 kOe with the Curie−Weiss fit (blackline). Parameters of the fit are shown on the figure.Figure 7. M versus H curves of Dy2CuZnMn4O12 at 5, 25, 60, and 100 K (f.u.: formula unit). The left-hand inset compares M versus H curves ofDy2CuZnMn4O12 and Lu2CuZnMn4O12 at 5 K. The right-hand inset compares M versus H curves of Dy2CuZnMn4O12 and Dy2MnMnMn4O1210 at 5K. MS is the magnetization value at H = 70 kOe and T = 5 K.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.3c02835Inorg. Chem. 2023, 62, 20042−2004920048https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835?fig=fig7&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.3c02835?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-assition below 116 K with a large saturation magnetization andinvolvement of the Dy3+ sublattices at low temperatures.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02835.Bond distances of Dy2CuZnMn4O12 at 100 K, DSCcurves, details of M vs H curves, M vs T curves, anddifferential magnetic susceptibility curves, ac magneticsusceptibility curves, and a photograph of the as-synthesized powder (PDF)■ AUTHOR INFORMATIONCorresponding AuthorAlexei A. Belik − Research Center for MaterialsNanoarchitectonics (MANA), National Institute for MaterialsScience (NIMS), Tsukuba, Ibaraki 305-0044, Japan;orcid.org/0000-0001-9031-2355; Email: Alexei.Belik@nims.go.jpComplete contact information is available at:https://pubs.acs.org/10.1021/acs.inorgchem.3c02835NotesThe author declares no competing financial interest.■ ACKNOWLEDGMENTSThe synchrotron radiation experiments were performed atSPring-8 with the approval of Japan Synchrotron RadiationResearch Institute (proposal numbers: 2023A1496 and2023A2361). We thank Dr. S. Kobayashi for his help atBL02B2 of SPring-8.■ REFERENCES(1) Belik, A. A. Rise of A-site Columnar-Ordered A2A′A″B4O12Quadruple Perovskites with Intrinsic Triple Order. Dalton Trans.2018, 47, 3209−3217.(2) Liu, R.; Khalyavin, D. D.; Tsunoda, N.; Kumagai, Y.; Oba, F.;Katsuya, Y.; Tanaka, M.; Yamaura, K.; Belik, A. A. Spin-Glass MagneticProperties of A-Site Columnar-Ordered Quadruple PerovskitesY2MnGa(Mn4−xGax)O12 with 0 ≤ x ≤ 3. 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