# Fileset

[ESI-Gd2CuZn4O12-251223-R.pdf](https://mdr.nims.go.jp/filesets/757185a4-37ac-4236-ae8e-628333fba356/download)

## Creator

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

## Rights

[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

## Other metadata

[Gd2CuZnMn4O12: A-site columnar-ordered perovskite with anisotropic thermal expansion and a gradual charge-order transition](https://mdr.nims.go.jp/datasets/9256295c-c237-4cb7-b633-5abc8ea9844c)

## Fulltext

Supporting Information (Online Material) for Supporting Information (Online Material) for      Gd2CuZnMn4O12: A-site columnar-ordered perovskite with anisotropic thermal expansion and a gradual charge-order transition   Alexei A. Belik*  Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Ibaraki 305-0044, Japan  E-mail: Alexei.Belik@nims.go.jp S1mailto:Alexei.Belik@nims.go.jpTable S1. Selected Bond Lengths (l (Å) < 2.8 Å), Bond Angles (deg), Bond Valence Sums, BVS, and Distortion Parameters of MnO6, ∆, in Gd2CuZnMn4O12 at T = 100 K a  Gd1–O5 ×2 Gd1–O3 ×2 Gd1–O2 ×2 Gd1–O1 ×4 BVS(Gd13+) 2.324(9) 2.400(8) 2.432(9) 2.648(6) 3.37 Gd2–O2 ×2 Gd2–O4 ×2 Gd2–O5 ×2 Gd2–O1 ×4 BVS(Gd23+) 2.361(9) 2.377(9) 2.424(9) 2.659(6) 3.32 Cu–O1 ×4 BVS(Cu2+)  1.958(4) 1.88  Zn–O4 ×2 Zn–O3 ×2 BVS(Zn2+)  1.997(9) 2.003(9) 1.80  Mn1–O2 ×2 Mn1–O3 ×2 Mn1–O1 ×2 BVS(Mn13+) ∆(Mn1–O) Mn1–O1–Mn2 ×2 Mn1–O2–Mn1 Mn1–O3–Mn1 1.890(2) 1.944(3) 2.159(7) 3.30 33.8×10–4 145.16(9) 148.46(9) 138.17(9) Mn2–O5 ×2 Mn2–O1 ×2 Mn2–O4 ×2 BVS(Mn24+) ∆(Mn2–O) Mn2–O4–Mn2 Mn2–O5–Mn2 1.896(2) 1.945(7) 1.964(4) 3.68 2.2×10–4 135.68(9) 146.58(9)  a BVS = ∑ , νi = exp[(R0 − li)/B], N is the coordination number, B = 0.37, R0(Gd3+) = 2.065, R0(Cu2+) = 1.679, R0(Zn2+) = 1.704, R0(Mn4+) = 1.753, and R0(Mn3+) = 1.76. =Nii1ν  S2  4 9 14 19 24295 K, before heating, 200 s295 K, after heating to 800 K, 10 s20.0 21.0 22.0 23.0 24.0 25.02θ  (deg): λ = 0.420186 Å 2θ  (deg): λ = 0.420186 Å 8.8 9.3 9.8*  Figure S1. Fragments of (normalized) experimental synchrotron X-ray powder diffraction patterns of Gd2CuZnMn4O12 at room temperature: the as-synthesized sample (the black curve) and a sample after heating to 800 K in high-temperature synchrotron X-ray powder diffraction experiments (the red curve). The star shows a contribution of the impurity.   S3  7.267.287.307.327.340 100 200 300 400 500 600 700 800Lattice parameters (Å) Temperature (K) aO, Pmmn bO, Pmmn heating Figure S2a. Temperature dependence of the aO and bO lattice parameters of Gd2CuZnMn4O12 between 100 K and 675 K on heating. The fitting at all these temperatures was performed in the Pmmn model.  S41.801.851.901.952.002.052.102.152.202.250 100 200 300 400 500 600 700 800Cu-O1Zn-O3Zn-O41.851.901.952.002.052.102.150 100 200 300 400 500 600 700 800Mn1-O2Mn1-O3Mn1-O1Mn2-O5Mn2-O4Mn2-O1Pmmn model at all temperatures Temperature (K) (b)(c)Bond Lengths (Å) Bond Lengths (Å) Gd2CuZnMn4O12 Mn3+ Mn4+ TCO = 475 K  Figure S2b, 2c. Temperature dependence of (b) the Mn-O bond lengths and (c) the Cu-O and Zn-O bond lengths in Gd2CuZnMn4O12 from 100 K to 675 K. The bond lengths were obtained in the Pmmn model. This figure illustrates that the refinement in the Pmmn model above TCO gave unstable and correlated results giving evidence that the symmetry is higher.   S5  0.060.080.10300 400 500 600 7001st cooling2nd cooling3rd cooling-0.16-0.14-0.12-0.10-0.08300 400 500 600 7001st heating2nd heating3rd heatingHeat flow (W/g) (a) heating Heat flow (W/g) (b) cooling Temperature (K) TCO TCO Gd2CuZnMn4O12, 68.10 mgInstrumental artefact  Figure S3. Differential scanning calorimetry (DSC) curves of a powder sample of Gd2CuZnMn4O12 (68.10 mg) on (a) heating and (b) cooling. Three runs were performed to check the reproducibility. The (full) arrows show the charge-order phase transition temperature determined by high-temperature synchrotron X-ray powder diffraction – no anomalies were detected at this temperature by DSC. The dotted arrow shows anomalies from an instrument observed on nearly all measurements.  S6 -4048120 20 40 60-4048120 20 40 60Magnetization  (µB / f.u.) Magnetization  (µB / f.u.) (a) (b) Magnetic Field (kOe) Gd2CuZnMn4O12, T = 60 KLu2CuZnMn4O12, T = 60 KGd2CuZnMn4O12, T = 5 KLu2CuZnMn4O12, T = 5 K Figure S4. (a) M versus H curves of Gd2CuZnMn4O12 in comparison with those of Lu2CuZnMn4O12 (without magnetic rare-earth elements) at T = 60 K. The curves were quantitatively similar with small differences: Lu2CuZnMn4O12 shows a saturated behavior typical for ferrimagnets while Gd2CuZnMn4O12 shows a small linear increase of M with H (above about 10 kOe), probably due to paramagnetic contribution from the Gd sublattice. We can suggest a similar ferrimagnetic order between the Mn and Cu sublattices in these two compounds. (b) M versus H curves of Gd2CuZnMn4O12 in comparison with those of Lu2CuZnMn4O12 at T = 5 K. The curves were quantitatively different. Lu2CuZnMn4O12 still shows a saturated behavior typical for ferrimagnets while Gd2CuZnMn4O12 shows a different behavior originating from the Gd sublattice contribution.   S7   -10123-3 -2 -1 0 1 2 3 4 52 K5 K7.5 K10 K-10123-3 -2 -1 0 1 2 3 4 512.5 K15 K20 K25 KMagnetization  (µB / f.u.) Magnetization  (µB / f.u.) Magnetic Field (kOe) (a) (b) Gd2CuZnMn4O12  Figure S5a, 5b. M versus H curves of Gd2CuZnMn4O12 in the vicinity of origin at different temperatures. These curves were used for plotting Figure 10 in the main text.  S8   -10123-3 -2 -1 0 1 2 3 4 550 K55 K60 K70 K-10123-3 -2 -1 0 1 2 3 4 530 K35 K40 K45 KMagnetization  (µB / f.u.) Magnetization  (µB / f.u.) Magnetic Field (kOe) (c) (d) Gd2CuZnMn4O12  Figure S5c, 5d. M versus H curves of Gd2CuZnMn4O12 in the vicinity of origin at different temperatures. These curves were used for plotting Figure 10 in the main text.  S9   -15-10-50510152025300 50 100 150 200 250 300 350 400ZFC, 100 OeFCC, 100 Oeχ  (emu×mol−1× Oe−1 ) χ  (emu×mol−1× Oe−1 ) Temperature (K) Temperature (K) Sample 2 -15-10-5051015202530354045500 50 100 150 200 250 300 350 400FCC, 100 Oe, sample 1FCC, 100 Oe, sample 2 Figure S6a. Comparison of magnetic properties of the Gd2CuZnMn4O12 samples prepared at 6GPa and at 1500 K for 2 h in an Au capsule (sample 1) and at 6 GPa and at 1730 K for 2 h in a Pt capsule (sample 2). Negative values on the ZFC curve for sample 2 could be caused by a negative initial trapped field inside a magnetometer (the magnet-reset option did not work during the measurement of sample 2, while the magnet-reset option was applied during the measurement of sample 1 (for the ZFC curve)).  S10    -250-200-150-100-500501000 50 100 150 200 250 300 350 400ZFC, 100 OeFCC, 100 Oe-15-10-5051015-80 -60 -40 -20 0 20 40 60 80sample 1, 5 Ksample 2, 5 KMagnetization  (µB / f.u.) Magnetic Field (kOe) Temperature (K) Sample 2 dχT/dT (emu×mol−1× Oe−1 ) -4-3-2-101234-10 -8 -6 -4 -2 0 2 4 6 8 10 Figure S6b. Comparison of magnetic properties of the Gd2CuZnMn4O12 samples prepared at 6GPa and at 1500 K for 2 h in an Au capsule (sample 1) and at 6 GPa and at 1730 K for 2 h in a Pt capsule (sample 2).   S11 BVS(Cu2+) BVS(Zn2+) BVS(Mn13+) BVS(Mn24+)