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[Xuan Liang](https://orcid.org/0000-0002-1062-4103), [Kazunari Yamaura](https://orcid.org/0000-0003-0390-8244), [Alexei A. Belik](https://orcid.org/0000-0001-9031-2355)

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[Negative Magnetization Phenomena in A-Site Columnar-Ordered Quadruple Perovskites Ce<sub>2</sub>MnM(Mn<sub>2</sub>Sb<sub>2</sub>)O<sub>12</sub> with M = Mn and Zn](https://mdr.nims.go.jp/datasets/9971304d-bf72-4244-b64c-c1a9a7535d34)

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Negative Magnetization Phenomena in A-Site Columnar-Ordered Quadruple Perovskites Ce2MnM(Mn2Sb2)O12 with M = Mn and ZnNegative Magnetization Phenomena in A‑Site Columnar-OrderedQuadruple Perovskites Ce2MnM(Mn2Sb2)O12 with M = Mn and ZnXuan Liang, Kazunari Yamaura, and Alexei A. Belik*Cite This: Inorg. Chem. 2025, 64, 10467−10477 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: A phenomenon of magnetization reversal in response to anapplied magnetic field is very common and forms the basis of magneticmemories. In contrast, the phenomenon of magnetization reversal inresponse to a temperature change is rarer. In this work, we demonstrated apronounced negative magnetization effect (NME) during field-cooledmeasurements in small magnetic fields in members of the A-site columnar-ordered quadruple perovskites, Ce2MnM(Mn2Sb2)O12 with M = Mn andZn, which were prepared by a high-pressure, high-temperature method atabout 6 GPa and about 1600 K. Their crystal structures at roomtemperature were investigated with synchrotron X-ray powder diffractiondata. Both compounds crystallize in space group P42/n (No. 86) with fullrock-salt ordering of Mn and Sb at the B sites. Lattice parameters are a =7.84545(1) and c = 7.95529(2) Å for M = Mn and a = 7.81270(1) and c =7.94100(1) Å for M = Zn. The bond-valence sum analysis and the charge balance suggest that cerium is present in the oxidationstate of +3. They show one magnetic transition at TC = 52 K with the compensation point near 20 K for M = Mn, and at TC = 34 Kwith the compensation point near 29 K for M = Zn. A robust, intrinsic NME was also observed on zero-field-cooled curves whenmeasured in small magnetic fields. The NME could originate from its ferrimagnetic structures.1. INTRODUCTIONThe negative magnetization effect (NME) or phenomenon,also known as magnetization reversal, refers to an uncommonmagnetic behavior in which the magnetization of a materialaligns antiparallel to an applied magnetic field. Specifically,NME describes the crossover of direct-current magnetizationfrom positive to negative under a positive magnetic field astemperature decreases.1−3 This effect deviates from conven-tional magnetism, where magnetization typically aligns with theapplied field and arises due to competing magnetic interactionsthat disrupt conventional ordering. The origins of this behaviorare linked to complex interplays between spin dynamics,magnetic anisotropy, crystal symmetry, and the interactionsamong magnetic ions.4−8Research into NME has garnered considerable interest dueto its potential to reveal new magnetic states and providedeeper insights into the fundamental physics governingmagnetic materials.1−3 Moreover, the dual tunability ofmagnetization by both magnetic fields and temperature offerspromising avenues for future applications in advancedmagnetic storage technologies, spintronic devices, and otherareas where precise control of magnetic states is critical.3,9−11This phenomenon has been observed and studied in variousperovskite materials. In ABO3 perovskites, magnetic inter-actions are primarily dictated by the arrangement of magneticions at the A and B sites, where competition between differentexchange pathways can lead to magnetization reversal.12 Forinstance, in (Tm1−xMnx)MnO3 solid solutions, the orderedTm3+ moments significantly increase at low temperatures,overpowering the saturated magnetic Mn moments at the Bsite. This results in magnetization reversal with a compensationtemperature (Tcomp) of around 15 K in the x = 0.2 and 0.3samples under small magnetic fields.13 Similarly, in rare-earth-based manganite materials such as NdMnO3 andGd0.5Sr0.5MnO3, negative magnetization arises from thenegative exchange interaction between the rare-earth ionsand Mn sublattices.14,15In double perovskites (A2BB′O6), the coexistence of twodistinct magnetic ions at the B and B′ sites introducesadditional complexity to the magnetic interactions.16 Forexample, in A2CoMnO6 double perovskites, where A is a rare-earth element, the competition between ferromagnetic (FM)superexchange interaction of Jahn−Teller (JT)-active Co2+ andJT-inactive Mn4+ and supplementary antiferromagnetic (AFM)interactions arising from the antisite disorder caused by theReceived: February 11, 2025Revised: April 17, 2025Accepted: May 5, 2025Published: May 16, 2025Articlepubs.acs.org/IC© 2025 The Authors. Published byAmerican Chemical Society10467https://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−10477This article is licensed under CC-BY 4.0Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on June 29, 2025 at 23:26:03 (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="Xuan+Liang"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kazunari+Yamaura"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://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.5c00653&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/inocaj/64/21?ref=pdfhttps://pubs.acs.org/toc/inocaj/64/21?ref=pdfhttps://pubs.acs.org/toc/inocaj/64/21?ref=pdfhttps://pubs.acs.org/toc/inocaj/64/21?ref=pdfpubs.acs.org/IC?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://pubs.acs.org/IC?ref=pdfhttps://pubs.acs.org/IC?ref=pdfhttps://acsopenscience.org/researchers/open-access/https://creativecommons.org/licenses/by/4.0/https://creativecommons.org/licenses/by/4.0/https://creativecommons.org/licenses/by/4.0/interchange of crystallographic positions between Co and Mncan result in spin frustration and the emergence of NME.17,18Quadruple perovskites also present promising candidates forNME due to the inclusion of additional magnetic sites, whichenhances inter-sublattice interactions. Quadruple perovskiteswith the general composition AA′3B4O12 feature a 12-foldcoordinated A site and a square-planar coordinated A′ site,where the A′ site is usually occupied by Cu2+, Fe2+, Mn2+, orMn3+.19−23 Strong interactions between the 3d transitionmetals at the A′ and B sites can lead to simultaneous magneticordering across these cations.19,20 However, to the best of ourknowledge, NME was not observed in AA′3B4O12 perovskites.Quadruple perovskites A2A′A″B4O12 have original columnar-type arrangements of A cations with one column containing Apositions and another column containing alternating A′ and A″positions (the so-called A-site columnar-ordered quadrupleperovskite). The presence of magnetic cations in newarrangements and unusual coordination environments couldlead to complex interactions among magnetic cations locatedin the A′, A″, and B sites resulting in different magnetic groundstates and spin-reorientation transitions.21,22It was recently found that the majority of A2A′A″B4O12perovskites have ferrimagnetic (FIM) structures; however, nosignificant NME was observed.21,23 This outcome wasunexpected, as FIM systems are especially prone to exhibitingNME.3 In FIM systems, magnetic moments of different ionsare aligned in opposite directions, similar to AFM systems, butwith unequal magnitudes.24,25 This imbalance results in netmagnetization. Under certain conditions, such as low temper-atures or specific external magnetic fields, the antiparallelmoments in FIM materials can become dominant, leading to areversal of overall magnetization. This makes FIM materialshighly susceptible to magnetization reversal, as the delicatecompetition between sublattice magnetizations can easily shift,resulting in a crossover from positive to negative magnet-ization.26−28 For example, neutron diffraction measurementsreveal that the origin of negative magnetization in(Tm0.7Mn0.3)MnO3 lies in its FIM structure and the differingtemperature dependences of the sublattice magnetizations.13In this work, we report the observation of the negativemagnetization effect (NME) in A-site columnar-orderedquadruple perovskites, Ce2MnM(Mn2Sb2)O12 (M = Mn,Zn). These compounds crystallize in space group P42/n (No.86) with full Mn and Sb rock-salt ordering at the B sites. Theyundergo one magnetic transition near TC = 52 K for M = Mnand TC = 34 K for M = Zn. During field-cooled measurementsin small magnetic fields, both materials display pronouncedNME, which is also evident in zero-field-cooled curves undersimilar conditions. The observed NME is likely attributable totheir FIM structures, highlighting the influence of complexmagnetic interactions in these materials and the critical role ofmultimoment vector arrangements and anisotropy coupling.2. EXPERIMENTAL SECTIONCe2MnM(Mn2Sb2)O12 samples with M = Mn and Zn were preparedfrom stoichiometric mixtures of CeO2, MnO or ZnO, Mn3O4, andSb2O3 (all 99.9%) at about 6 GPa and about 1600 K for 2 h in Aucapsules by a high-pressure, high-temperature method. After beingannealed at 1600 K, the samples were cooled to room temperature(RT) by turning off the heating current, and the pressure was slowlyreleased. Before use, CeO2 was dried in air at 1270 K for 1 h and theother oxides were dried in air at 390 K for 4 h. No uncommon hazardswere noted.X-ray powder diffraction (XRPD) data were collected on aRIGAKU MiniFlex600 diffractometer using Cu Kα radiation at RT(2θ range of 5−100° with a step of 0.02° and a scan speed of 3°/min). Synchrotron XRPD data were collected on the BL02B2beamline of SPring-8 at RT between 1.95 and 71.25° at a 0.006°interval in 2θ with the wavelength of λ = 0.61974 Å.29 The data from5° (for M = Mn) and 4° (for M = Zn) were used in the refinements,as no experimental reflections were observed below these values. Thesamples were placed into Lindemann glass capillary tubes (innerdiameter: 0.2 mm), which were rotated during measurements. TheRietveld analysis of all XRPD data was performed using the RIETAN-2000 program.30Magnetic measurements were performed on a SQUID magneto-meter (Quantum Design, MPMS3) between 2 and 300 K in anapplied magnetic field of 100 and 10 kOe under both zero-field-cooled (ZFC) and field-cooled on cooling (FCC) conditions.Additional magnetic measurements were also performed between 2and 70 K in different applied fields under ZFC and FCC conditions.The inverse magnetic susceptibilities (χ−1) were fit by the Curie−Weiss equation=T N k T( ) (3 ( ))eff2B1where μeff is the effective magnetic moment, N is Avogadro’s number,kB is Boltzmann’s constant, and Θ is the Curie−Weiss temperature.Figure 1. Fragments of experimental (black circles), calculated (red line), and difference (blue line) synchrotron X-ray powder diffraction patternsof (a) Ce2MnMn(Mn2Sb2)O12 and (b) Ce2MnZn(Mn2Sb2)O12 at T = 295 K. On the panel (a), the tick marks show possible Bragg reflectionpositions of the main perovskite phase (the first black row), CeO2 impurity (the second red row), cubic pyrochlore impurity (the third green row),and La3Mn2Sb3O14-related pyrochlore impurity (the fourth purple row). On the panel (b), the tick marks show possible Bragg reflection positionsof the main perovskite phase (the first black row), CeO2 impurity (the second red row), Na5Co15.5Te6O36-type impurity (the third green row), andLa3Mn2Sb3O14-related pyrochlore impurity (the fourth purple row). (c) Crystal structure of Ce2MnM(Mn2Sb2)O12 with M = Mn and Zn in apolyhedral presentation. The rock-salt-type arrangement of Mn3O6 and SbO6 octahedra is shown on the left. The columnar-type arrangement ofCeO10 polyhedra, Mn1O4 square planar units, and (Mn/Zn)O4 = M2O4 tetrahedra is shown on the right.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−1047710468https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig1&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asFor fitting, we used the FCC data at H = 10 kOe between 200 and295 K. Isothermal magnetization measurements were performedbetween −70 and 70 kOe at different temperatures (5, 10, 20, 30, 40,50, and 60 K). Specific heat was measured on a Quantum DesignPPMS-9T instrument on cooling at magnetic fields of 0 Oe and 90kOe.3. RESULTS AND DISCUSSION3.1. Crystal Structure Determination and Description.The synchrotron XRPD patterns of Ce2MnM(Mn2Sb2)O12samples with M = Mn and Zn are shown in Figure 1a,b (with azoom-in of the low-2θ region in Figure S1). Both samplescrystallize in a tetragonal system with space group P42/n. TheM = Mn sample contained 3.6 wt % CeO2, 0.2 wt % cubic-pyrochlore (space group Fd3̅m, a = 10.2633 Å, which could beSb2O4+x), and 2.9 wt % La3Mn2Sb3O14-type pyrochlore31(space group R3̅m, a = 7.4262 Å and c = 17.6394 Å) impuritieswhile the M = Zn sample contained 4.2 wt % CeO2, 7.9 wt %La3Mn2Sb3O14-type pyrochlore31 (space group R3̅m, a =7.4428 Å and c = 17.6257 Å), and 3.7 wt % Na5Co15.5Te6O36-type32 (space group P63/m, a = 9.6229 Å and c = 9.3509 Å)impurities. The lattice parameters of Ce2MnMn(Mn2Sb2)O12were a = 7.84545(1) Å and c = 7.95529(2) Å, and those ofCe2MnZn(Mn2Sb2)O12 were a = 7.81270(1) Å and c =7.94100(1) Å. The rare-earth stability range (at certainsynthesis conditions) of A-site columnar ordered quadrupleperovskites usually strongly depends on the occupation of theA′, A″, and B sites and is a subject to considerablerestrictions;21,23 for example, R2MnMnMn4O12 is stable for R= Gd−Er, Y,33 R2MnMn(MnTi3)O12 is stable for R = Nd−Gd,34 and NaRMn2Ti4O12 is stable for Sm, Eu, Gd, Dy, Ho,and Y.35 It was found that R2MnMn(Mn2Sb2)O12 are stable forR = La, Pr, Nd, and Sm;36−38 however, R = Ce was omittedfrom the investigation in ref 36. As R2MnZn(Mn2Sb2)O12 hasa different combination of A′, A″, and B cations, we alsopreliminarily investigated the rare-earth stability range ofR2MnZn(Mn2Sb2)O12 and prepared such compounds with R =Nd, Eu, Dy, and Yb. It was found that R2MnZn(Mn2Sb2)O12can be stabilized for R = Nd and Eu (unpublished data) in theA-site columnar-ordered perovskite structure. On the otherhand, samples with R = Dy and Yb crystallized in a double-perovskite structure (space group P21/n) with a statisticaldistribution of R3+, Mn2+, and Zn2+ cations at one A site.Stabilization of Ce3+ (see below for confirmation) in the A siteof quadruple perovskites is uncommon39 because the Ce4+oxidation state is the most stable form in comparison withR2O3 (R = La, Nd, Sm, Eu, Gd, Dy−Lu, and Y) with the R3+oxidation state, and Ce2O3 is easily oxidized.40 We also tried tosynthesize Ce2MnMn(Mn2Sb2)O12 and Ce2MnZn(Mn2Sb2)-O12 at a higher temperature of 1800 K (at 6 GPa in Pt capsulesfor 2 h); however, the samples contained CeO2 and Sb2O4+x (apyrochlore-type structure) as the main phases, suggesting thatthe samples decomposed (Figure S2).Structure parameters of Nd2MnMn(Mn4−xSbx)O1236,38 wereused as the initial model for the crystal structure refinements ofCe2MnM(Mn2Sb2)O12 with M = Mn and Zn. We initiallyassume that all cations were distributed in ideal sites: Ce3+ atthe 10-fold-coordinated A site, Mn2+ at the square-planar A′site (Mn1), and Mn2+/Zn2+ at the tetrahedral A″ site (M2).For the sample Ce2MnZn(Mn2Sb2)O12, Mn2+ cations (23electrons) and Zn2+ cations (28 electrons) differ by 5 electronsor around 20%. This difference is enough to identify them withhigh-quality synchrotron powder X-ray powder diffraction.Refinements of the occupation factors (g) of the Ce site(simultaneously with all atomic displacement parameters (andother parameters), but with fixed g parameters for other sites)gave the following values: g(Ce) = 0.960(2) for M = Mn andg(Ce) = 0.991(2) for M = Zn. Such deviations can be absorbedby reasonable atomic displacement parameters (e.g., B(Ce) =0.693(10) Å2 with g(Ce) = 1 for M = Mn). Nevertheless, weassumed the presence of an antisite disorder when g valuesdeviated from 1 by more than 3%. Therefore, the presence ofMn at the Ce site for M = Mn was assumed in the final model,and we refined the cation distribution with a constraint on thefull site occupation; e.g., g(Ce) + g(Mn) = 1. The occupationfactor of the Ce site was fixed at 1 for M = Zn in the finalmodel. Refined g parameters (simultaneously) for the Sb andMn3 (or M3) sites (under the same conditions as above) wereg(Sb) = 1.001(3) and g(Mn3) = 0.979(4) for M = Mn andg(Sb) = 1.022(3) and g(Mn3) = 1.050(5) for M = Zn.Therefore, the g(Sb) values were fixed at 1 in the final models.Refined g parameters for the Mn1 site (under the sameconditions as above) were g(Mn1) = 0.972(3) for M = Mn andg(Mn1) = 1.018(7) for M = Zn. Therefore, the g(Mn1) valueswere fixed at 1 in the final models. Refined g parameters for theM2 site (under the same conditions as above) were g(Mn2) =0.974(6) for M = Mn and g(Zn2) = 0.922(6) for M = Zn.Based on these values, g(Mn2) was fixed at 1 for M = Mn. Onthe other hand, g(Zn2) and g(Mn3) values for M = Zn couldsuggest some antisite disorder of Zn2+ and Mn2+ between theM2 and Mn3 sites. Therefore, we refined the cationdistribution between these two sites with constraints on thefull site occupation and the total chemical composition. Thefinal crystallographic and structure parameters are presented inTables 1 and 2. We note that when only Mn was assumed atthe M2 site of Ce2MnZn(Mn2Sb2)O12 its refined occupationfactor was 1.144(7).The crystal structure of Ce2MnM(Mn2Sb2)O12 samples withM = Mn and Zn is illustrated in Figure 1c. In this A-sitecolumnar-ordered quadruple perovskite structure with theP42/n space group (No. 86), the Mn (Mn3) and Sb atomseach are located at an octahedral center, and the Mn3/SbO6octahedra are alternately corner-connected in a rock-saltarrangement.41 It has two in-phase and one out-of-phase tiltsof the Mn3/SbO6 octahedra (written a+a+c− in the Glazernotation42) which creates 10 and 4 coordination numbersTable 1. Crystallographic Parameters and StructureRefinement Details of Ce2MnM(Mn2Sb2)O12 with M = Mnand ZnaMMn Zna (Å) 7.84545(1) 7.81270(1)c (Å) 7.95529(2) 7.94100(1)V (Å3) 489.657(1) 484.705(1)molecular weight (g/mol) 935.5048 945.9468Rwp (%) 8.49 9.08Rp (%) 6.42 6.88RI (%) 3.21 3.50RF (%) 1.92 2.23aSynchrotron X-ray powder diffraction (λ = 0.61974 Å). T = 295 K.2θ range used in the refinement: 5−71.25° for M = Mn sample, 4−71.25° for M = Zn sample. Crystal system: tetragonal. Space group:P42/n (No. 86, cell choice 2), Z = 2.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−1047710469https://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_001.pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asaround the three A sites.21 As shown on the right of Figure 1c,the 10-coordinated A-site CeO10 polyhedra are connectedthrough edges and form columns along the c axis. The 4-coordinated A′-site Mn1O4 squares and 4-coordinated A″-siteM2O4 tetrahedra (M2 = Mn/Zn) are separated from eachother but connected with A-site CeO10 polyhedra throughedges and corners, respectively.Table 3 shows the bond lengths, bond angles, bond-valencesum (BVS),43,44 and distortion parameters. The BVS values forthe Ce site (+2.82 and +2.91)44 confirm the +3 oxidation state.There are two quite long Ce−O1 bond lengths (3.004(9) and2.936(15) Å) in the P42/n structure of Ce2MnM(Mn2Sb2)O12samples in agreement with other R2MnMn(Mn2Sb2)O12samples,36−38 but in contrast with the P42/nmc structure ofother related compounds without B-site double ordering.37,38The BVS value of +1.77 for the Mn1 site in the M = Mnsample is consistent with the slightly elongated Mn1−O1 bondlength of 2.117(5) Å (compared with the M = Zn sample, BVS= +1.90, and l(Mn1−O1) = 2.088(6) Å). Reduced BVS valuesfor the square-planar site are often observed in suchperovskites. For the M2 and M3 sites, the BVS values(+1.86 and +2.11 for the M = Mn sample; +1.74 and +1.99 forthe M = Zn sample) also supported the oxidation state +2. TheM2−O2 bond lengths differ noticeably for M = Mn (2.101(5)Å) and M = Zn (2.038(6) Å), reflecting different ionic radii ofMn2+ (rIV = 0.66 Å) and Zn2+ (rIV = 0.60 Å).45 The Zn−Obond lengths in Ce2MnZn(Mn2Sb2)O12 were close, forexample, to those of Dy2MnZn(Mn3Ti)O12 and Dy2MnZn-(Mn2Ti2)O12.46 The BVS values at the Sb site (+5.35 and+5.55) were slightly higher than anticipated, implying that Sb5+cations tend to be overbonded. This conclusion is furthersupported by the relatively short Sb−O bond lengths(1.981(8)−1.987(5) Å for the M = Mn sample and1.960(10)−1.982(10) Å for the M = Zn sample). Interestingly,similar trends in the BVS values of Sb5+ and bond lengths havebeen observed in other A-site columnar-ordered quadrupleperovskites where Sb occupies the B-site.36−38 The resultantcharge distribution is Ce3+2Mn2+M2+(Mn2+2Sb5+2)O12, whileTable 2. Structure Parameters of Ce2MnM(Mn2Sb2)O12 with M = Mn and Zn at 295 K from Synchrotron X-ray PowderDiffraction DataaM Site WP x y z Biso (Å2)Mn Ce 4e 0.25 0.75 0.77610(6) 0.580(11)Mn1-SQ 2b 0.25 0.25 0.75 1.17(9)Mn2-T 2a 0.75 0.75 0.75 0.61(8)Mn3-Oc 4c 0 0.5 0.5 0.65(2)Sb-Oc 4d 0 0 0.5 0.375(9)O1 8g −0.0461(9) 0.5739(9) 0.2345(7) 0.52(11)O2 8g −0.2348(12) −0.0430(7) 0.5831(6) 0.90(12)O3 8g −0.2587(10) 0.0671(6) −0.0319(6) 0.51(9)Zn Ce 4e 0.25 0.75 0.77499(7) 0.647(10)Mn1-SQ 2b 0.25 0.25 0.75 0.63(10)M2-T 2a 0.75 0.75 0.75 1.00(11)M3-Oc 4c 0 0.5 0.5 0.69(3)Sb-Oc 4d 0 0 0.5 0.364(11)O1 8g −0.0532(15) 0.5701(15) 0.2327(9) 1.10(15)O2 8g −0.2291(13) −0.0480(8) 0.5889(8) 0.85(14)O3 8g −0.2591(13) 0.0701(8) −0.0365(8) 1.28(14)aWP is Wyckoff position. For M = Mn sample, g(Ce) = 0.928(3)Ce + 0.072Mn and g(Mn1-SQ) = g(Mn2-T) = g(Mn3-Oc) = g(Sb-Oc) = g(O1) =g(O2) = g(O3) = 1, where g is the occupation factor. For M = Zn sample, g(Ce) = g(Mn1-SQ) = g(Sb-Oc) = g(O1) = g(O2) = g(O3) = 1, g(M2-T) = 0.65(2)Zn + 0.35Mn, and g(M3-Oc) = 0.823Mn + 0.177Zn. Abbreviations: SQ, square-planar (site); T, tetrahedral (site); Oc: octahedral(site).Table 3. Bond Lengths (in Å), Bond Angles (in deg), Bond-Valence Sum (BVS), and Distortion Parameters of MnO6and SbO6 (Δ) in Ce2MnM(Mn2Sb2)O12 with M = Mn andZn at T = 295 K from Synchrotron X-ray Powder DiffractionDataaMMn ZnCe−O1 × 2 2.723(9) 2.775(15)Ce−O1 × 2 3.004(9) 2.936(15)Ce−O2 × 2 2.560(5) 2.572(6)Ce−O3 × 2 2.417(5) 2.359(6)Ce−O3 × 2 2.491(5) 2.508(6)BVS(Ce3+) +2.82 +2.91Mn1−O1 × 4 2.117(5) 2.088(6)Mn1−O2 × 4 3.110(5) 3.124(6)BVS(Mn12+) +1.77 +1.90M2−O2 × 4 2.101(5) 2.038(6)M2−O3 × 4 3.034(5) 3.022(6)BVS(M22+) +1.86 +1.74M3−O1 × 2 2.220(5) 2.232(7)M3−O2 × 2 2.210(9) 2.263(10)M3−O3 × 2 2.112(8) 2.117(11)Δ(M3O6) 5.0×10−4 8.1×10−4BVS(M32+) +2.11 +1.99Sb−O1 × 2 1.987(5) 1.971(7)Sb−O2 × 2 1.986(9) 1.960(10)Sb−O3 × 2 1.981(8) 1.982(10)Δ(SbO6) 1.7×10−6 2.1×10−5BVS(Sb5+) +5.35 +5.55M3−O1−Sb × 2 142.0(4) 141.6(6)M3−O2−Sb × 2 138.4(3) 135.2(4)M3−O3−Sb × 2 146.8(3) 144.7(4)aBVS =∑i=1N νi, νi = exp[(R0 − li)/B], N is the coordination number, liis a bond length, B = 0.37, R0(Ce3+) = 2.121, R0(Mn2+) = 1.79,R0(Zn2+) = 1.704, R0(Sb5+) = 1.942.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−1047710470pubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asCe usually takes the +4 oxidation state in other A-site-orderedquadruple perovskites, such as CeCu3Fe4O12,47 Ce-Cu3Mn4O12,48 and CeCu3Cr4O12.493.2. Magnetic Properties. Figure 2 presents the magneticsusceptibility of Ce2MnM(Mn2Sb2)O12 samples with M = Mnand Zn as a function of temperature at H = 100 and 10 kOeunder ZFC and FCC conditions. In the 100 Oe ZFC and FCCmeasurements, both samples display sharp susceptibilityincreases below TC = 52 K (M = Mn) and TC = 34 K (M =Zn), suggesting a rapid arrangement of FM-like domains alongthe direction of the field, where the TC values (ferrimagneticCurie temperatures) were determined from sharp peaks on theZFC and FCC dχT/dT versus T curves at H = 100 and 10 kOe(Figures S3 and S4). Both 100 Oe ZFC and FCC curves ofCe2MnMn(Mn2Sb2)O12 show a maximum χ value at 47 K(Tχmax), decrease, and then go through a zero point ofmagnetic susceptibility (χ = 0) at Tcomp. Below Tcomp, themagnetizations (judged from the magnetic susceptibilities)remain negative down to the lowest temperature of ∼2 K,showing the NME or magnetization reversal. The 100 Oe ZFCand FCC curves of Ce2MnZn(Mn2Sb2)O12 below Tχmax (∼20K, determined from the 100 Oe ZFC curve) follow totallydifferent paths. The ZFC curve shows a maximum at Tχmax,then decreases and remains negative below ∼13.6 K. On theother hand, the FCC curve increases steadily as thetemperature is decreased and eventually approaches asaturation value at ∼5 K. Notably, no divergence is observedin both samples between the ZFC and FCC curves at 100 Oedown to Tχmax, while the ZFC and FCC curves nearly overlapunder the 10 kOe field. We note that CeO2 and Sb2O4+ximpurities are nonmagnetic, and La3Mn2Sb3O14-type impuritymay be paramagnetic or weakly magnetic. No magnetictransitions were found in La3Mn2Sb3O14, and Nd3Mn2Sb3O14showed a magnetic transition near 2 K.50 Thus, specific heatanomalies in our samples near 2 K (see below) could originatefrom La3Mn2Sb3O14-type impurity (namely, from a phase witha composition close to Ce3Mn2Sb3O14), and similar specificheat anomalies were observed in Nd2MnMn(Mn4−xSbx)O12samples (with x = 1.9 and 2), which also had a similarimpurity.38 Therefore, impurities should have small effects onthe observed magnetic properties.The inverse magnetic susceptibility was fitted by the Curie−Weiss law at temperatures above 200 K. The Curie−Weissparameters were obtained from the Curie−Weiss equation fitdetailed in Experimental Section and concluded in Table 4.The experimentally determined effective magnetic moments(μeff) closely match the theoretically expected values (μcalc).51We note that the inclusion of Ce3+ moments (2.4 μB)51 gave abetter agreement between the calculated and experimentalvalues, thus, giving an indirect support of the oxidation state ofCe. The negative values of the Curie−Weiss temperature (Θ)indicated the dominance of AFM interactions.We emphasize that negative magnetization was alsoobserved on the ZFC curves of Ce2MnMn(Mn2Sb2)O12 andCe2MnZn(Mn2Sb2)O12 measured at 100 Oe (Figure 2). In themajority of cases, negative magnetization on ZFC curves is dueto artifacts caused by two main reasons. The first reason is anegative trapped field inside a magnetometer where a negativetrapped field produces a negative initial magnetization,52,53which sometimes cannot be switched to a positive value by asmall, positive measurement/applied field because of largecoercive fields of a material. The second reason is a sampleinsertion procedure for some models of magnetometers thatare kept at low temperatures as the base temperature (forFigure 2. ZFC (filled symbols) and FCC (empty symbols) dcmagnetic susceptibility (χ = M/H) curves of Ce2MnM(Mn2Sb2)O12with (a) M = Mn and (b) M = Zn measured at 100 Oe (black, circles)and 10 kOe (red, triangles). The black line gives the Curie−Weiss fit(C-W fit) using the FCC χ−1 versus T curves at 10 kOe (the right-hand axis).Table 4. Angles (in deg) Mediating the Main Magnetic Interactions, Ferrimagnetic Curie Temperatures (TC) and Parametersof Curie−Weiss Fits, and M versus H Curves at T = 5 K for Ce2MnM(Mn2Sb2)O12 with M = Mn and Zna⟨Ce−O−MnB⟩M O1 O2 O3 ⟨MnA′−O1−MnB⟩ ⟨MnA″−O2−MnB⟩Mn 83.0(3) 87.1(3) 102.6(3) 103.8(3) 104.7(4)Zn 81.4(4) 85.5(3) 103.6(4) 103.9(4)M TC (K) μeff (μB/fu) μcalc (μB/fu) θ (K) MR (μB/fu) Mextr (μB/fu) HC (kOe)Mn 52 12.71(5) 12.309 −121(3) 0.221 0.15 1.39Zn 34 10.98(2) 10.794 −74.2(11) 0.622 0.67 0.48aCurie−Weiss fits were performed between 200 and 295 K using the FCC χ−1 versus T data at 10 kOe. TC is determined from sharp peaks on the100 Oe FCC dχ/dT versus T curves. MR is the remnant magnetization at T = 5 K. Mextr at T = 5 K is obtained by the extrapolation between 40 and70 kOe to zero field. HC is the coercive field at T = 5 K.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−1047710471https://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig2&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asexample, at 10 or 100 K). In this case, negative magnetizationon ZFC curves was observed even in positive trapped fieldsbecause samples were moved through a magnet belowmagnetic ordering temperatures, and no negative magnet-ization was observed when samples were moved through amagnet at 300 K.54 In our current case, the base temperature ofa magnetometer was 300 K; therefore, samples were movedthrough a magnet at 300 K, which is well above the magneticordering temperatures.To check whether negative magnetization on ZFC curves ofCe2MnMn(Mn2Sb2)O12 and Ce2MnZn(Mn2Sb2)O12 wasintrinsic, we utilized the following procedure. We cooledsamples in applied fields of 10 and −10 Oe (applied after themagnet-reset procedure), which should simulate intentionallylarge positive and negative trapped fields (PTF and NTF),respectively. At the same time, we measured magnetizationdown to 2 K (this is equivalent to the FCC measurements at10 and −10 Oe). As shown in Figure 3, in the paramagneticstates, magnetization of both samples was positive at 10 Oeand negative at −10 Oe, confirming the signs of the “trapped”fields; such FCC curves at 10 and −10 Oe were nearlysymmetrical relative to the temperature axis. Then, ameasurement field of 100 Oe was applied at 2 K, and theZFC curves were measured. The absolute values of magnet-ization did not change much on moving from 10 to 100 Oe(and from −10 to 100 Oe) at 2 K. As a result, magnetizationremained negative when the trapped field was positive (10Oe), and magnetization remained positive when the trappedfield was negative (−10 Oe) due to the presence of negativemagnetization phenomena in both compounds. Therefore, wecan conclude that negative magnetization on ZFC curves inCe2MnMn(Mn2Sb2)O12 and Ce2MnZn(Mn2Sb2)O12 is intrin-sic (assuming that fields should approach zero values from thepositive direction in all ZFC procedures) and originates fromthe existence of NME and finite positive trapped fields inside amagnetometer. It is interesting that magnetization changedsign two times (at 23 and 30 K) in the case of Ce2MnMn-(Mn2Sb2)O12 when the “trapped” field was negative (−10 Oe)because the ZFC M versus T curve (at 100 Oe) followed theFCC M versus T curve (at −10 Oe) up to a certaintemperature (about 25 K); the point where these curves areseparated could be related to temperature dependence ofcoercive fields. For example, these curves start to separateabove about 7 K in Ce2MnZn(Mn2Sb2)O12. Therefore, ZFCcurves of the M = Zn sample (obtained under negative trappedfields) do not show negative values, and the “compensation”temperature (about 13 K) on ZFC curves of the M = Znsample (obtained under positive trapped fields) does notmatch with the compensation temperature of the FCC curves.To further explore the NME in Ce2MnMn(Mn2Sb2)O12 andCe2MnZn(Mn2Sb2)O12, FCC magnetic susceptibility measure-ments were performed under various applied magnetic fields.As shown in Figure 4a, the magnetic susceptibility ofCe2MnMn(Mn2Sb2)O12 exhibits a consistent trend acrossdifferent fields: a rapid increase below TC, reaching a peak atTχmax (47 K), followed by a decrease. NME is observed at lowtemperatures when H ≤ 600 Oe, with Tcomp shifting to lowervalues as the field increases (inset of Figure 4a) and areduction in the NME component. For H ≥ 800 Oe, onlyFigure 3. Magnetization (M versus T) curves of Ce2MnM(Mn2Sb2)-O12 with (a) M = Mn and (b) M = Zn measured at differentconditions and fields. PTF indicates a positive trapped field, and NTFrepresents a negative trapped field.Figure 4. FCC dc magnetic susceptibility (χ = M/H) curves ofCe2MnM(Mn2Sb2)O12 with (a) M = Mn and (b) M = Zn measuredat different fields. The inset in (a) shows the plot of the compensationtemperature (Tcomp) as a function of the applied magnetic field. Theinset in (b) shows a zoomed-in region near the Curie temperature(TC).Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−1047710472https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig4&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-aspositive magnetization is observed, and the susceptibilityshows a slight increase at ∼23 K. Furthermore, the maximumvalues of the FCC curves above Tcomp increase as the fielddecreases. As will be further discussed below, the NME inCe2MnMn(Mn2Sb2)O12 likely arises from FM ordering ofMn2+ at the A′ and A″ sites and an AFM arrangement of Mn2+at the B site.34,36 These competing magnetic interactions giverise to complex temperature-dependent magnetization behav-ior. In contrast, Ce2MnZn(Mn2Sb2)O12 shows NME only at asignificantly lower field range (H ≤ 20 Oe), with Tcompdecreasing from 29.6 K at H = 10 Oe to 28.5 K at H = 20Oe) (Figure 4b). Below TC, the magnetic susceptibility rapidlypeaks at Tχmax = 32.6 K, followed by either a continuousincrease (H ≥ 40 Oe) or a decrease (H ≤ 20 Oe). Thesuppressed NME in Ce2MnZn(Mn2Sb2)O12 can be attributedto the presence of nonmagnetic Zn2+ ions, which do notparticipate in magnetic exchange interactions.Isothermal magnetization curves (M versus H) at differenttemperatures are presented in Figure 5, with the correspondingparameters being summarized in Table 4. The presence ofhysteresis substantiates the presence of FM components inmagnetic ordering. At 5 K, both samples exhibit an incompletewasp-waisted shape with low remnant magnetization (MR) andcoercive fields (HC), attributed to the coexistence ofcompeting FM and AFM interactions.55 The unsaturatedbehavior of both samples under high magnetic fields indicatesthat AFM coupling is the dominant factor influencing theirmagnetic properties. The extrapolated magnetization (Mextr)determined via linear extrapolation is quite small, reflecting thepresence of strong magnetic competition and complex latticecoupling. As the temperature increases, the hysteresis loopnarrows and HC decreases (see insets of Figure 5 and FiguresS5 and S6). Notably, a slight increase inMR is observed around40 K of Ce2MnMn(Mn2Sb2)O12, which corresponds to ananomaly in the 10 kOe ZFC and FCC curves (Figure 2a).The specific heat (Cp) measurements at H = 0 and 90 kOefor Ce2MnMn(Mn2Sb2)O12 and Ce2MnZn(Mn2Sb2)O12 arepresented in Figure 6a. Pronounced anomalies are observed attheir respective TC values, confirming the presence of long-range magnetic ordering. These anomalies reflect an increasein magnetic entropy as the system transitions from an orderedstate to a disordered state. Interestingly, while the magnetictransition in Ce2MnMn(Mn2Sb2)O12 is suppressed under afield of 90 kOe, the transition in Ce2MnZn(Mn2Sb2)O12remains relatively unchanged. This difference may be due tothe substitution of Mn by Zn, which reduces the number ofmagnetic ions and potentially weakens the AFM coupling,leading to a reduced response of the magnetic order to externalfields in Ce2MnZn(Mn2Sb2)O12. There is evidence of theappearance of the second magnetic transition near 40 K inCe2MnMn(Mn2Sb2)O12 at 90 kOe (Figure 6a). In magneticinsulators, the Cp capacity is predominantly governed by latticevibrations at higher temperatures and magnetic excitations atlower temperatures. To isolate the magnetic contribution fromthe total Cp, the lattice contribution (Clattice) was estimatedusing the experimentally measured Cp of Nd2ZnZn(Zn2Sb2)-O12, a compound with the same structure and paramagneticbehavior down to 2 K (unpublished data) (Figures S7 and S8).This paramagnetic material features nonmagnetic cationsoccupying the A′, A″, and B sites. The magnetic part of theheat capacity is calculated by subtracting the lattice part, Cmag =Cp − Clattice (the left axis of Figure 6b). The magnetic entropyFigure 5. M versus H curves of Ce2MnM(Mn2Sb2)O12 with (a) M =Mn and (b) M = Zn at different temperatures. Each inset shows azoomed-in region near zero field.Figure 6. (a) Specific heat data of Ce2MnM(Mn2Sb2)O12 with M =Mn and Zn plotted as Cp/T versus T. Measurements were performedon cooling at H = 0 and 90 kOe. (b) Temperature dependences of themagnetic contribution to the heat capacity (Cmag) and the magneticentropy (Smag) of Ce2MnM(Mn2Sb2)O12 with M = Mn and Zn at H =0 Oe.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−1047710473https://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig6&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-as(Smag) was subsequently determined by integrating Cmag/T(the right axis of Figure 6b). The expected magnetic entropyfor the Mn2+ moment is Smag = Rln(2J + 1) = Rln6 ≈ 14.89 JK−1 mol−1, where R = 8.314 J K−1 mol−1 is the universal gasconstant. The Smag for both samples gradually increases at lowtemperatures, nearing saturation around 100 K. At T = 100 K,Smag for Ce2MnMn(Mn2Sb2)O12 is 51.2 J K−1 mol−1, while thatfor Ce2MnZn(Mn2Sb2)O12 is 40.5 J K−1 mol−1. These valuesare slightly lower than the expected Boltzmann entropyestimated from the Mn content (4Rln6 and 3Rln6, Figure 6)due to difficulties in the precise estimation of the latticecontribution. The difference between the two is consistentwith the reduction in Smag due to the substitution of Mn by Znat the A″ site, which reduces the number of magnetic momentscontributing to the total entropy.3.3. Discussion. The NME observed in Ce2MnM-(Mn2Sb2)O12 (M = Mn, Zn) represents a remarkablephenomenon arising from the intricate interplay betweenmagnetic sublattices and the crystal structure. Such a systembelongs to one of the five known NME mechanisms,3specifically those involving antiparallel ordering between two(or more) FM sublattices associated with distinct crystallo-graphic sites. This discussion first addresses the mechanism ofNME in Ce2MnMn(Mn2Sb2)O12 and then illustrates howsubstituting Mn2+ with nonmagnetic Zn2+ at the A″ site affectsNME in Ce2MnZn(Mn2Sb2)O12. The type and relativestrength of magnetic interactions in both materials are criticallydetermined by the geometry of the M−O−M superexchangepathways, with the corresponding angles summarized in Table4. In Ce2MnMn(Mn2Sb2)O12, the rock-salt ordering of B siteMn2+ and Sb5+ cations necessitates the involvement of super-superexchange MnB−O−Sb−O−MnB pathways; furthermore,the octahedral geometry of B site Mn2+ minimizes interactionswith neighboring B sites. The square-planar coordination ofthe A′ site Mn2+ and the tetrahedral coordination of the A″ siteMn2+ prevent direct magnetic interactions between equivalentA′ and A″ sites. Consequently, the magnetic behavior ofCe2MnMn(Mn2Sb2)O12 is dominated by two key AFMsuperexchange pathways: MnA′−O−MnB and MnA″−O−MnB.The respective superexchange bond angles support moderateAFM coupling, consistent with the Goodenough −Kanamori−Anderson (GKA) rules.56 A′ and A″ site Mn2+ moments alignparallel to each other but antiparallel to B site Mn2+ moments,creating a FIM lattice.36,55 The AFM coupling mechanism hasbeen experimentally confirmed in related compounds throughneutron powder diffraction (NPD) studies, includingR2MnMn(Mn2Sb2)O12 with R = La, Pr, and Nd.36,55The schematic illustration of the spin configurations inCe2MnMn(Mn2Sb2)O12 is presented in Figure 7, and thetemperature-dependent magnetic behavior exhibits fourdistinct regimes. (i) T > TC: Above TC, thermal agitationdominates, leading to paramagnetic behavior without long-range magnetic ordering. (ii) Tχmax < T < TC: As the systemcools below TC, magnetic ordering develops. The A′ and A″site Mn2+ moments (MMnA′,A″) grow rapidly due to strongexchange interactions, while B site Mn2+ moments (MMnB)increase more slowly due to dilution of the whole B sublattice.The sublattice moments align along the easy axis, which isdictated by magnetic anisotropy. Net magnetization (Mnet)remains positive but small due to the imbalance betweensublattices. At Tχmax, magnetic susceptibility peaks, reflectingthe system’s heightened responsiveness to external fields. Thenear invariance of Tχmax across different fields (Figure 4a)suggests that local AFM coupling and thermal agitation, ratherthan external fields, govern this characteristic temperature. (iii)Tcomp < T < Tχmax: As the temperature decreases further, MMnBgrows significantly faster than MMnA′,A″. The 4-fold coordina-tion of both A′ and A″ sites imposes strong local anisotropiesthat hinder rapid magnetic reorientation, enabling MMnB todominate. This imbalance causes Mnet to decrease, reachingzero at Tcomp as opposing sublattice moments cancel out(MMnA′,A″ = MMnB). (iv) T < Tcomp: Below Tcomp, MMnBdominates, leading to negative Mnet. Strong AFM couplingbetween the B and A′/A″ sites suppresses further alignmentwith external fields. This transition aligns with Neél theory,57underscoring the roles of sublattice interactions and anisotropyin determining magnetic behavior.The influence of external magnetic fields on the NME isevident across these regimes. At low measurement magneticfields (below coercive fields), one sublattice overcomesanother sublattice in each domain, and the magnetic fieldcannot switch magnetization in domains, resulting in a smoothM versus T (or χ versus T) curves across Tcomp. On the otherhand, an apparent broad maximum appears in larger magneticfields (Figure 2a). For example, the observed maximum on the10 kOe ZFC and FCC curves of Ce2MnMn(Mn2Sb2)O12 is atypical feature of FIM materials with NME.13,58 A low-temperature minimum is also observed very close to Tcomp(when the measurement field is not too high). The origin ofthis behavior lies again in the NME, when the magnetic field ishigh enough (above coercive fields) to switch magnetization indomains to the opposite direction at Tcomp because states withnegative magnetization relative to the direction of a magneticfield are energetically unfavorable. One sublattice continues toovercome another sublattice or the absolute values ofFigure 7. Schematic illustration of the spin configurations in Ce2MnMn(Mn2Sb2)O12. NME denotes the negative magnetization effect.Inorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−1047710474https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?fig=fig7&ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asmagnetization continue to increase below Tcomp at anymagnetic field.Similar behavior of χ versus T curves was observed inMnLaMnSbO6,36,55 when measured at 1 kOe, with a broadmaximum below TC = 48 K and a sharp upturn below 9 K.This is a typical feature of FIM materials with NME.13,58Therefore, MnLaMnSbO6 could also exhibit NME below 9 Kat lower magnetic fields, and the ordered moments of Mn2+ atA′, A″, and B sites could be different in contrast to theassumptions of refs 36 and 55. Sm3+ cations usually show no orweak ordered magnetic moments in perovskite oxides,59 andMnSmMnSbO6 also demonstrated a broad maximum on its χversus T curves (at 1 kOe).36 On the other hand,MnRMnSbO6 compounds from the same series withdetectable R3+ ordered moments (R = Pr and Nd)36,55 showedno (direct or indirect) signs of NME. Therefore, we canassume that Ce3+ cations in Ce2MnMn(Mn2Sb2)O12 shouldhave no or very weak ordered magnetic moments in order toshow NME, as this effect appears to be a competition ofordered moments of Mn at the A′, A″, and B sites. We notethat NME was observed in Sm2MnMn(Mn2Ti2)O12.59However, another sample34 with the same composition didnot show NME, suggesting that small variations in cationdistributions could play a major role in the appearance ofNME.Substituting Mn2+ at the A″ site with nonmagnetic Zn2+ inCe2MnZn(Mn2Sb2)O12 significantly affects its magneticproperties. Zn substitution eliminates the A″−O−B AFMpathway, reducing the overall AFM coupling. This weakenssublattice competition, leading to higher remnant magnet-ization and diminished NME, as observed in Ce2MnZn-(Mn2Sb2)O12. Moreover, the TC and Tcomp temperatures arecloser in Ce2MnZn(Mn2Sb2)O12 than in Ce2MnMn(Mn2Sb2)-O12. This proximity suggests that just below TC, a largermoment is induced on the A′ site than on the B sites.However, as there are no magnetic cations at the A″ site inCe2MnZn(Mn2Sb2)O12, the MMnB (from two Mn2+ cations)quickly overtakes the MMnA′ (from one Mn2+ cation), resultingin Tcomp being very close to TC. On the other hand, inCe2MnMn(Mn2Sb2)O12, the presence of magnetic Mn2+cations at both the A′ and A″ sites leads to a more competitiveinteraction with the two Mn2+ cations at the B sites within theFIM structure. This competition allows MMnB to surpassMMnA′,A″ at a much lower temperature, resulting in a morepronounced separation between TC and Tcomp. These findingshighlight the critical role of cation composition and siteoccupancy in dictating the magnetic behavior and NME ofthese complex perovskite-like oxides. We note that broadmaxima were also observed in Ce2MnZn(Mn2Sb2)O12 betweenTC and Tcomp on χ versus T curves when measured at magneticfields above 40 Oe (the inset of Figure 4b) in agreement withthe general tendency discussed in the above paragraph.However, because TC and Tcomp are very close to each other,the maxima are very small.4. CONCLUSIONSIn conclusion, this study presents the observation of thepronounced negative magnetization effect (NME) in A-sitecolumnar-ordered quadruple perovskites, specificallyCe2MnM(Mn2Sb2)O12 (M = Mn and Zn). These compoundscrystallize in the P42/n (No. 86) space group, demonstratingthe complete rock-salt ordering of Mn and Sb at the B sites.The bond-valence sum analysis and charge balance confirmthat cerium exists in the +3 oxidation state. The compoundsexhibit distinct magnetic transitions at TC = 52 K for M = Mnand TC = 34 K for M = Zn. Field-cooled measurements undersmall magnetic fields reveal pronounced NME, which is furthercorroborated by zero-field-cooled curves under similarconditions. The observed NME is likely a consequence ofthe ferrimagnetic structures inherent to these materials. Thesefindings underscore the critical influence of complex magneticinteractions and anisotropy coupling in governing their uniquemagnetic properties.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653.Magnified figures for Rietveld refinements, laboratoryXRPD patterns of the samples prepared at differentconditions, differential magnetic susceptibility curves,coercive fields as a function of temperature, and specificheat and magnetic entropy change as a function oftemperature (PDF)Crystallographic parameters of main and impurityphases (PDF)Crystallographic parameters of main and impurityphases (PDF)■ AUTHOR INFORMATIONCorresponding AuthorAlexei A. Belik − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; orcid.org/0000-0001-9031-2355;Email: Alexei.Belik@nims.go.jpAuthorsXuan Liang − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; Graduate School of Chemical Sciences andEngineering, Hokkaido University, Sapporo, Hokkaido 060-0810, JapanKazunari Yamaura − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; Graduate School of Chemical Sciences andEngineering, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan; orcid.org/0000-0003-0390-8244Complete contact information is available at:https://pubs.acs.org/10.1021/acs.inorgchem.5c00653NotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSThis work was partially supported by a Grant-in-Aid forScientific Research (No. JP25K01657) from the Japan Societyfor the Promotion of Science. Synchrotron radiation experi-ments were conducted at the powder diffraction beamlineBL02B2 at SPring-8 with the permission from the JapanSynchrotron Radiation Research Institute (Proposal Number:2023B1676). We thank Dr. S. Kobayashi for his help atBL02B2 of SPring-8. MANA is supported by the WorldInorganic Chemistry pubs.acs.org/IC Articlehttps://doi.org/10.1021/acs.inorgchem.5c00653Inorg. Chem. 2025, 64, 10467−1047710475https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?goto=supporting-infohttps://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_002.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.5c00653/suppl_file/ic5c00653_si_003.pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Alexei+A.+Belik"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0001-9031-2355mailto:Alexei.Belik@nims.go.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Xuan+Liang"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kazunari+Yamaura"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-0390-8244https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00653?ref=pdfpubs.acs.org/IC?ref=pdfhttps://doi.org/10.1021/acs.inorgchem.5c00653?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asPremier International Research Center Initiative (WPI),MEXT, Japan.■ REFERENCES(1) Ren, Y.; Palstra, T. 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