Adjustable Magnetic Phase Transition Inducing Unusual Zero Thermal

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Adjustable Magnetic Phase Transition Inducing Unusual Zero Thermal Expansion in Cubic RCo2‑Based Intermetallic Compounds (R = Rare Earth) Jinyu Hu,† Kun Lin,*,† Yili Cao,† Chengyi Yu,† Wenjie Li,† Rongjin Huang,‡ Henry E. Fischer,§ Kenichi Kato,∥ Yuzhu Song,† Jun Chen,† Hongjie Zhang,⊥ and Xianran Xing*,† Inorg. Chem. Downloaded from pubs.acs.org by UNIV OF LOUISIANA AT LAFAYETTE on 04/24/19. For personal use only.

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Beijing Advanced Innovation Center for Materials Genome Engineering, Department of Physical Chemistry, and State Key Laboratory of Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China ‡ Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China § Institut Laue-Langevin (ILL), 71 avenue des Martyrs, CS 20156, 38042 Grenoble Cedex 9, France ∥ RIKEN SPring-8 Center, Hyogo 679-5148, Japan ⊥ State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China S Supporting Information *

key factors that account for the NTE, such as changes in the phonon-related transverse vibration in frameworks of ZrW2O8,9 Ag3[Co(CN)6],10 and ScF3.13 However, most of the these ZTE materials are oxides,14 fluorides,15 or cyanides.16 In comparison, metallic materials, such as Invar alloys,17 have significant advantages and great industry merits because of their superior comprehensive properties like excellent electrical/thermal transport performances and mechanical properties. However, there are only a few metallic materials that exhibit NTE or ZTE behavior.2−4 Besides, the NTE in metallic materials is related to the magnetovolume effect (MVE) and is usually difficult to control because of its phase-transition-like nature, such as those observed in Mn−Co−Ge−In particles18 and LaFe10.6Si2.419 intermetallic compounds. It still remains a big challenge to effectively control the MVE and achieve new ZTE materials with excellent metallic properties. RCo2-based (R = rare earth) intermetallic compounds are a family of well-known metamagnetic20 and magnetocaloric materials.21 These compounds crystallize in a cubic MgCu2type structure at room temperature (Figure 1a). In this structure, the magnetic moments of Co are described as being driven by the molecular field exerted by the localized 4f moments of the R atoms or by an external filed, known as the itinerant-electron metamagnetism.22 These compounds have two different types of magnetic phase transitions at the Curie temperature (TC):23 second order for light R elements (R = Nd, Sm, Gd) and first order for heavy R elements (R = Dy, Ho, Er). Among them, GdCo2 has the highest TC (404 K) with neglectable MVE below TC. On the contrary, the TC values of RCo2 (R = Dy, Ho, Er) are relatively low (137, 89, and 30 K, respectively),23 but these compounds exhibit abrupt volume contraction during the first-order magnetic phase transitions (ΔV/V = −0.31%, −0.33%, and −0.37% for R = Dy, Ho, and Er, respectively).24 In this study, by tuning the magnetic phase transition from first to second order, we tailored the thermal

ABSTRACT: Metallic materials that exhibit negligible thermal expansion or zero thermal expansion (ZTE) have great merit for practical applications, but these materials are rare and their thermal expansions are difficult to control. Here, we successfully tailored the thermal expansion behaviors from strongly but abruptly negative to zero over wide temperature ranges in a series of (Gd,R)(Co,Fe) 2 (R = Dy, Ho, Er) intermetallic compounds by tuning the composition to bring the firstorder magnetic phase transition to second-order. Interestingly, an unusual isotropic ZTE property with a coefficient of thermal expansion of αl = 0.16(0) × 10−6 K−1 was achieved in cubic Gd0.25Dy0.75Co1.93Fe0.07 (GDCF) in the temperature range of 10−275 K. The short-wavelength neutron powder diffraction, synchrotron X-ray diffraction, and magnetic measurement studies evidence that this ZTE behavior was ascribed to the rare-earth-momentdominated spontaneous volume magnetostriction, which can be controlled by an adjustable magnetic phase transition. The present work extends the scope of the ZTE family and provides an effective approach to exploring ZTE materials, such as by adjusting the magnetism or ferroelectricity-related phase transition in the family of functional materials. aterial deformation caused by thermal fluctuation is an essential issue in many engineering applications such as space technology, high precision optical systems, and electronic and biomedical devices.1−4 For the purpose of effectively resisting thermal shock, zero thermal expansion (ZTE) materials, which are neither expansion nor contraction with temperature, emerge as required.5−7 In the past 2 decades, the appearances of negative thermal expansion (NTE) provide a way to tune the material’s coefficient of thermal expansion (CTE) to a desirable level.8−13 The ZTE materials could be feasibly designed and achieved by chemical modification of the

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Received: February 20, 2019

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DOI: 10.1021/acs.inorgchem.9b00480 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

Co−Ge−In particles18 (αl = 0.68 × 10−6 K−1 at 200−310 K; orthorhombic + hexagonal), LaFe10.6Si2.419 (αl = −0.8 × 10−6 K−1 at 15−150 K; cubic), TbCo1.9Fe0.126 (αl = 0.48 × 10−6 K−1 at 123−307 K; rhombohedral), and Ho2Fe16Cr27 (αl = 0.43 × 10−6 K−1 at 13−330 K; hexagonal), the present GDCF has the advantages of a straight-line-like thermal expansion curve, a wide ZTE window, and structural isotropy, making it a favorable material for both fundamental research and promising application in the cryo equipment. Along with the controllable thermal expansion behavior in (Gd,Dy)(Co,Fe)2 alloys, macroscopic magnetic measurements demonstrate distinct FM/ferrimagnetic (FIM) to paramagnetic (PM) transitions (TC) at 137, 216, and 270 K for DyCo2, Gd0.25Dy0.75Co2, and GDCF, respectively (Figure 2a). It is

Figure 1. (a) Crystal structure of GDCF. (b) Linear thermal expansion (Δl/l0) of GdxDy1−xCo2 and GDCF. The inset refers to Δl/l0 of GdCo2 (x = 1) in the high-temperature zone. Figure 2. (a) M−T curves of GdxDy2−xCo2 and GDCF under H = 500 Oe. The arrows indicate TC. (b) Temperature dependence of a magnetic entropy change (−ΔSM) under H = 0−1 T and the relative ratio of the unit cell volume (V/V300 K) for DyCo2,28 Gd0.25Dy0.75Co2, and GDCF.

expansion behaviors and achieved ZTE in a series of (Gd,R)(Co,Fe)2 (R = Dy, Ho, Er) intermetallic compounds. As shown in Figures 1b and S1a, the GdxDy1−xCo2 (x = 0, 0.15, 0.25, 0.3, 0.35, 0.4, 1) samples exhibit distinctly different linear thermal expansion behaviors. For the parent compound without Gd, a strong but abrupt volume contraction (Δl/l ≈ −0.08%) was observed in a narrow temperature range of 120− 141 K, which is a typical character of the first-order phase transition. Interestingly, with the continually increasing substitution of Gd for Dy, the volume contraction behaviors of GdxDy1−xCo2 solid solutions weaken, and the characteristic of ZTE gradually emerges with its temperature window broadened. Further replacing Dy by Gd raises the CTE and results in normal PTE on GdCo2 (x = 1) with αl = 5.88(0) × 10−6 K−1 (100−404 K). To further optimize the ZTE property, minor Fe was introduced to the Co 16d site, which has been reported to increase the electronic density of states (DOS) at the Fermi level and could enhance the ferromagnetic (FM) exchange interactions.25 Surprisingly, unusual straight-line-like ZTE [αl = 0.61(0) × 10−6 K−1 at 98−270 K] was achieved by the further replacement of 3.5% Fe for Co in Gd0.25Dy0.75Co2, and TC raises by 54 K (Figure S2). Besides, the ZTE property can be maintained in a range of compositions by a synergistic modification of the amounts of Gd and Fe for the present (Gd,Dy)(Co,Fe)2 compounds (Table S1 and Figure S1b), and the above method could also be employed to achieve ZTE in other (Gd,R)(Co,Fe)2 (R = Er, Ho) systems (Figure S1b and Table S1). The temperature dependence of synchrotron X-ray diffraction was utilized to investigate the intrinsic lattice thermal expansion in (Gd,Dy/Er)(Co,Fe)2, which agrees well with the macroscopic measurements (Figures S3 and S4). The CTE of GDCF is much lower than those of normal metallic materials (Figure S5) such as Fe (αl = 12.2(0) × 10−6 K−1), Al (αl = 22.9(0) × 10−6 K−1), and Cu (αl = 16.3(1) × 10−6 K−1). Besides, compared with other ZTE intermetallic compounds, for instance, the Mn−

obvious that the values of TC coincide exactly with the temperature where thermal expansion changes, suggesting that the lattices of (Gd,Dy)(Co,Fe)2 alloys are coupled with magnetic phase transition. To well-illuminate the nature of the magnetic phase transition in (Gd,Dy)(Co,Fe)2, we studied the temperature dependence of a magnetic entropy change (−ΔSM) and the corresponding cell volume change (V/V300 K) at TC. As shown in Figure 2b, DyCo2 displays a sharp peak in −ΔSM accompanied by a sudden shrinkage of the unit cell volume at ∼137 K, indicating a typical first-order magnetic phase transition character.23 With some Dy replaced by Gd for Gd0.25Dy0.75Co2, the peak in −ΔSM broadens and its intensity decreases, accompanied by a minor volume change at ∼216 K, which suggests that the first-order magnetic phase transition is weakened. Furthermore, a rather broad peak in −ΔSM and a smooth evolution in the cell volume happen for GDCF, indicating a typical second-order magnetic phase transition character.28 The second-order magnetic phase transition in GDCF was further confirmed by the positive slopes in the Arrott plots (Figure S6). Apparently, there is a close relationship between the adjustable phase transition and ZTE in (Gd,Dy)(Co,Fe)2. How does the magnetic phase transition tune the thermal expansion in (Gd,Dy)(Co,Fe)2? It is known that the abnormal thermal expansion in magnetic materials was induced by MVE. To extract the contribution from atomic magnetic moment to MVE and give insight into its mechanism, we determined the magnetic structures by a neutron powder diffraction (NPD) experiment. Given the extremely high neutron absorption cross section of Gd, NPD data were recorded with a two-axis B

DOI: 10.1021/acs.inorgchem.9b00480 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

κ indicates that the spontaneous volume magnetostriction ωs is strengthened by spontaneous magnetic ordering. As described in Figure 4a, there exists a satisfactory linear relationship

diffractometer using short-wavelength neutrons (λ = 0.4952) at D4 of ILL29 (Figure 3a).

Figure 4. (a) ωs of GDCF as a function of the square of the Gd/Dy moments. The inset displays the temperature dependence of the magnetic moments of Dy in DyCo235 and Gd/Dy in GDCF. (b) Experimental and calculated thermal expansion of GDCF. Figure 3. (a) NPD patterns of GDCF at 10 and 350 K (b) Contour plots of the NPD profile intensity for GDCF. (c) Temperature dependence of the lattice parameter a of GDCF measured by NPD. The inset shows its crystal and magnetic structure above and below TC. (d) Comparison of the total and partial moments for GDCF. The total magnetic moment for a chemical formula unit Mf.u. (calculated by MGd/Dy − 2MCo/Fe from NPD) agrees well with the macroscopic measurement by a superconducting quantum interference device magnetometer.

between ωs and MGd/Dy2 (κ > 0). On the other hand, among the RCo2 itinerant-electron metamagnetic compounds, significant MVE exists with R = magnetic rare earths such as Tb, Ho, and Er, while YCo2 and LuCo2, which have nonmagnetic rare-earth elements (Y, [Kr]4d15s2; Lu, [Xe]4f145d16s2), are PM without any MVE.24 This suggests that the spontaneous volume magnetostriction of RCo2 stems from the local moment of Gd/Dy. For GDCF, when the spontaneous volume magnetostriction ωs compensates exactly for the nominal thermal contraction ωnm upon cooling (ωs − ωnm = 0, where 10 ≤ T ≤ 275 K), an ideal ZTE alloy was achieved (Figure 4b). In other words, the intriguing ZTE performance of GDCF is induced by a coordination between the thermal contraction from MVE caused by Gd/Dy magnetic moments and the thermal expansion rooting in anharmonicity of the interatomic potential. According to eq 2, the changes of ωs with the temperature can be derived as dωs/dT = 2κC dM(T)/dT. The adjustable phase transition from first to second order slows the reducing rate of the Gd/Dy moments with temperature (dMGd/Dy/dT) and thus controls the thermal expansion in (Gd,Dy)(Co,Fe)2 (Figure 4 Insert). Furthermore, it is worth mentioning that the present ZTE material also exhibits a relatively good metallic character such as favorable electrical conductivity (1.17 × 10−6 Ω m at room temperature) and thermal conductivity (6.26 W m−1 K−1 at room temperature) properties and possesses a peak magneto−1 −1 caloric effect (−ΔSmax K at 0−5 T) near room M = 3.32 J mol temperature (TC = 270 K; Figure S7), suggesting that it may play a potential role in the development of new functional materials for cryo equipment. In summary, an unusual ZTE property was achieved in cubic (Gd,R)(Co,Fe)2 (R = Dy, Ho, Er) intermetallic compounds, which has been realized through transformation from first-order to second-order magnetic phase transition. In the case of GDCF, a straight-line-like ZTE happens over 10−275 K with αl = 0.16(0) × 10−6 K−1 and is isotropic. The ZTE behavior is attributed to the rare-earth-moment-dominated spontaneous volume magnetostriction ωs, which compensates for the nominal thermal contraction exactly below TC. Chemical substitution by Gd and Fe in DyCo2 transforms the magnetic phase transition from the first to second order, which slows the decreasing rate of the Gd/Dy magnetic moments with temperature and thus regulates thermal expansion.

Below TC, the magnetic moments of Gd/Dy and Co/Fe in GDCF are arranged antiparallel and form a FIM structure, while above TC, they are randomly distributed without long-range ordering (Figure 3c, inset). Figure 3c shows the temperature dependence of the lattice parameter a of GDCF in the temperature range of 10−350 K determined by NPD. In addition to the dilatometer and X-ray results, it shows that GDCF displays a ZTE property down to 10 K with αl = 0.16(0) × 10−6 K−1 (10−275 K). Figure 3d shows the magnetic moments of the Gd/Dy and Co/Fe sites plotted as a function of the temperature for the GDCF sample. The magnetic moment of the Co/Fe atoms (1.47 μB at 10 K) is much smaller than that of the Gd/Dy atoms (8.72 μB at 10 K) at all temperatures because of the strong spin−orbit coupling of 4f rare-earth atoms Gd/Dy and the quenched orbital magnetic moments of 3d transition metals Co/Fe.30 In magnetic materials, the spontaneous volume magnetostriction ωs has been used to quantitatively describe the extra volume increase from magnetic contributions. ωs can be obtained by excluding the contribution from phonon vibration according to the well-known Debye−Grüneisen model,31 which was calculated according to the following formula:32 ωexp − ωnm × 100% ωs = ωnm (1) where ωexp is the experimental volume and ωnm is the nominal one calculated based on the Debye−Grüneisen model.3,33 According to the Landau theory, the spontaneous volume magnetostriction could be quantitatively described as ωs = κCM2(T )

(2)

where κ and C represent the compressibility and magnetovolume coupling constant, respectively, and M(T) is the amplitude of the local magnetic moment.34 A positive value of C

DOI: 10.1021/acs.inorgchem.9b00480 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

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(10) Goodwin, A. L.; Calleja, M.; Conterio, M. J.; Dove, M. T.; Evans, J. S. O.; Keen, D. A.; Peters, L.; Tucker, M. G. Colossal Positive and Negative Thermal Expansion in the Framework Material Ag3[Co(CN)6]. Science 2008, 319, 794−797. (11) Yoon, D.; Son, Y. W.; Cheong, H. Negative thermal expansion coefficient of graphene measured by Raman spectroscopy. Nano Lett. 2011, 11 (8), 3227−3231. (12) Azuma, M.; Chen, W. T.; Seki, H.; Czapski, M.; Olga, S.; Oka, K.; Mizumaki, M.; Watanuki, T.; Ishimatsu, N.; Kawamura, N.; Ishiwata, S.; Tucker, M. G.; Shimakawa, Y.; Attfield, J. P. Colossal negative thermal expansion in BiNiO3 induced by intermetallic charge transfer. Nat. Commun. 2011, 2, 347. (13) Greve, B. K.; Martin, K. L.; Lee, P. L.; Chupas, P. J.; Chapman, K. W.; Wilkinson, A. P. Pronounced Negative Thermal Expansion from a Simple Structure: Cubic ScF3. J. Am. Chem. Soc. 2010, 132 (44), 15496−15498. (14) Chen, J.; Xing, X.; Sun, C.; Hu, P.; Yu, R.; Wang, X.; Li, L. Zero Thermal Expansion in PbTiO3-Based Perovskites. J. Am. Chem. Soc. 2008, 130 (4), 1144−1145. (15) Hu, L.; Chen, J.; Fan, L.; Ren, Y.; Rong, Y.; Pan, Z.; Deng, J.; Yu, R.; Xing, X. Zero thermal expansion and ferromagnetism in cubic Sc1‑xMxF3 (M = Ga, Fe) over a wide temperature range. J. Am. Chem. Soc. 2014, 136 (39), 13566−13569. (16) Phillips, A. E.; Halder, G. J.; Chapman, K. W.; Goodwin, A. L.; Kepert, C. J. Zero Thermal Expansion in a Flexible, Stable Framework Tetramethylammonium Copper(I) Zinc(II) Cyanide. J. Am. Chem. Soc. 2010, 132 (1), 10−11. (17) Guillaume, C. É . Recherches sur les aciers au nickel. J. Phys. Theor. Appl. 1898, 7 (1), 262−274. (18) Shen, F.-R.; Kuang, H.; Hu, F.-X.; Wu, H.; Huang, Q.-Z.; Liang, F.-X.; Qiao, K.-M.; Li, J.; Wang, J.; Liu, Y.; Zhang, L.; He, M.; Zhang, Y.; Zuo, W.-L.; Sun, J.-R.; Shen, B.-G. Ultra-low thermal expansion realized in giant negative thermal expansion materials through self-compensation. APL Mater. 2017, 5 (10), 106102. (19) Wang, W.; Huang, R.; Li, W.; Tan, J.; Zhao, Y.; Li, S.; Huang, C.; Li, L. Zero thermal expansion in NaZn13-type La(Fe,Si)13 compounds. Phys. Chem. Chem. Phys. 2015, 17 (4), 2352−2356. (20) (a) Burzo, E.; Gratz, E.; Pop, V. On the magnetic behaviour of ACo2 (A = Y, Lu, Zr, Sc and Hf) compound. J. Magn. Magn. Mater. 1993, 123 (1−2), 159−164. (b) Duc, N. H.; Goto, T. Itinerant electron metamagnetism of Co sublattice in the lanthanide-cobalt intermetallics. Handbook on the Physics and Chemistry of Rare Earths 1999, 26, 177− 264. (21) de Oliveira, N. A.; von Ranke, P. J.; Tovar Costa, M. V.; Troper, A. Magnetocaloric effect in the intermetallic compounds RCo2 (R = Dy,Ho,Er). Phys. Rev. B: Condens. Matter Mater. Phys. 2002, 66 (9), 094402. (22) Bloch, D.; Lemaire, R. Metallic Alloys and Exchange-Enhanced Paramagnetism. Application to Rare-EarthCobalt Alloys. Phys. Rev. B 1970, 2 (7), 2648−2650. (23) Khmelevskyi, S.; Mohn, P. The order of the magnetic phase transitions in RCo2. J. Phys.: Condens. Matter 2000, 12, 9453−9464. (24) Gratz, E.; Lindbaum, A.; Markosyan, A. S.; Mueller, H.; Sokolov, A. Y. Isotropic and anisotropic magnetoelastic interactions in heavy and light RCo2 Laves phase compounds. J. Phys.: Condens. Matter 1994, 6, 6699−6709. (25) Bentouaf, A.; Mebsout, R.; Rached, H.; Amari, S.; Reshak, A. H.; Aïssa, B. Theoretical investigation of the structural, electronic, magnetic and elastic properties of binary cubic C15-Laves phases TbX2 (X = Co and Fe). J. Alloys Compd. 2016, 689, 885−893. (26) Song, Y.; Chen, J.; Liu, X.; Wang, C.; Zhang, J.; Liu, H.; Zhu, H.; Hu, L.; Lin, K.; Zhang, S.; Xing, X. Zero Thermal Expansion in Magnetic and Metallic Tb(Co,Fe)2 Intermetallic Compounds. J. Am. Chem. Soc. 2018, 140 (2), 602−605. (27) Dan, S.; Mukherjee, S.; Mazumdar, C.; Ranganathan, R. Zero thermal expansion with high Curie temperature in Ho2Fe16Cr alloy. RSC Adv. 2016, 6 (97), 94809−94814.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b00480.

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Sample preparation, experimental methods, data analysis procedures, and relevant physical properties, e.g., electrical/thermal conductivities (PDF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (K.L.). *E-mail: [email protected] (X.X.). ORCID

Kun Lin: 0000-0003-4515-3206 Jun Chen: 0000-0002-7330-8976 Hongjie Zhang: 0000-0001-5433-8611 Xianran Xing: 0000-0003-0704-8886 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grants 21701008, 21231001, and 21590793), National Postdoctoral Program for Innovative Talents (Grant BX201700027), and China Postdoctoral Science Foundation (Grant 2017M620608). The synchrotron radiation experiments were performed at the BL44B2 of the RIKEN SPring-8 Center with the approval of the Japan Synchrotron Radiation Research Institute (Proposals 2018A1210 and 2018B1515).

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REFERENCES

(1) (a) Mohn, P. A century of zero expansion. Nature 1999, 400, 18− 19. (b) Atkinson, A.; Barnett, S.; Gorte, R. J.; Irvine, J. T.; McEvoy, A. J.; Mogensen, M.; Singhal, S. C.; Vohs, J. Advanced anodes for hightemperature fuel cells. Nat. Mater. 2004, 3 (1), 17−27. (c) Barrera, G. D.; Bruno, J. A. O.; Barron, T. H. K.; Allan, N. L. Negative thermal expansion. J. Phys.: Condens. Matter 2005, 17 (4), R217−R252. (2) Evans, J. S. O. Negative thermal expansion materials. J. Chem. Soc., Dalton Trans. 1999, 3317−3326. (3) Chen, J.; Hu, L.; Deng, J.; Xing, X. Negative thermal expansion in functional materials: controllable thermal expansion by chemical modifications. Chem. Soc. Rev. 2015, 44 (11), 3522−3567. (4) Liu, Z.; Gao, Q.; Chen, J.; Deng, J.; Lin, K.; Xing, X. Negative thermal expansion in molecular materials. Chem. Commun. 2018, 54 (41), 5164−5176. (5) Salvador, J. R.; Guo, Fu; Hogan, T.; Kanatzidis, M. G. Zero thermal expansion in YbGaGe due to an electronic valence transition. Nature 2003, 425, 702−705. (6) Margadonna, S.; Prassides, K.; Fitch, A. N. Zero Thermal Expansion in a Prussian Blue Analogue. J. Am. Chem. Soc. 2004, 126 (47), 15390−15391. (7) Song, X.; Sun, Z.; Huang, Q.; Rettenmayr, M.; Liu, X.; Seyring, M.; Li, G.; Rao, G.; Yin, F. Adjustable zero thermal expansion in antiperovskite manganese nitride. Adv. Mater. 2011, 23 (40), 4690− 4694. (8) Takenaka, K.; Takagi, H. Giant negative thermal expansion in Gedoped anti-perovskite manganese nitrides. Appl. Phys. Lett. 2005, 87 (26), 261902. (9) Mary, T. A.; Evans, J. S. O.; Vogt, T.; Sleight, A. W. Negative Thermal Expansion from 0.3 to 1050 K in ZrW2O8. Science 1996, 272 (5258), 90−92. D

DOI: 10.1021/acs.inorgchem.9b00480 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry (28) Wang, D.; Liu, H.; Tang, S.; Yang, S.; Huang, S.; Du, Y. Magnetic properties and magnetocaloric effects in (GdxDy1−x) Co2 compounds. Phys. Lett. A 2002, 297 (3−4), 247−252. (29) (a) Fischer, H. E.; Cuello, G. J.; Palleau, P.; Feltin, D.; Barnes, A. C.; Badyal, Y. S.; Simonson, J. M. D4c: A very high precision diffractometer for disordered materials. Appl. Phys. A: Mater. Sci. Process. 2002, 74 (0), s160−s162. (b) Lin, K.; Fischer, H. E.; Hu, J. Revealing the magnetic structure of Gd0.35Dy0.65(Co,Fe)2 with unusual zero thermal expansion property; Institut Laue-Langevin, 2018; DOI: 10.5291/ILL-DATA.DIR-164. (30) (a) Nesbitt, E. A.; Williams, H. J.; Wernick, J. H.; Sherwood, R. C. Magnetic Moments of Intermetallic Compounds of Transition and Rare-Earth Elements. J. Appl. Phys. 1962, 33 (5), 1674−1678. (b) Guirado-Lopez, R. A.; Dorantes-Davila, J.; Pastor, G. M. Orbital magnetism in transition-metal clusters: from Hund’s rules to bulk quenching. Phys. Rev. Lett. 2003, 90 (22), 226402. (31) Lu, X.; Selleby, M.; Sundman, B. Theoretical modeling of molar volume and thermal expansion. Acta Mater. 2005, 53 (8), 2259−2272. (32) (a) Chen, J.; Wang, F.; Huang, Q.; Hu, L.; Song, X.; Deng, J.; Yu, R.; Xing, X. Effectively control negative thermal expansion of singlephase ferroelectrics of PbTiO3-(Bi,La)FeO3 over a giant range. Sci. Rep. 2013, 3, 2458. (b) Pan, Z.; Chen, J.; Jiang, X.; Hu, L.; Yu, R.; Yamamoto, H.; Ogata, T.; Hattori, Y.; Guo, F.; Fan, X.; Li, Y.; Li, G.; Gu, H.; Ren, Y.; Lin, Z.; Azuma, M.; Xing, X. Colossal Volume Contraction in Strong Polar Perovskites of Pb(Ti,V)O3. J. Am. Chem. Soc. 2017, 139 (42), 14865−14868. (33) Dabrowski, B.; Avdeev, M.; Chmaissem, O.; Kolesnik, S.; Klamut, P. W.; Maxwell, M.; Jorgensen, J. D. Freezing of octahedral tilts below the Curie temperature in SrRu1−vO3 perovskites. Phys. Rev. B: Condens. Matter Mater. Phys. 2005, 71 (10), 104411. (34) (a) Moriya, T.; Usami, K. Magneto-volume effect and invar phenomena in ferromagnetic metals. Solid State Commun. 1980, 34 (2), 95−99. Fujita, A.; Fukamichi, K.; Wang, J. T.; Kawazoe, Y. Large magnetovolume effects and band structure of itinerant-electron metamagnetic La(FexSi1−x)13 compounds. Phys. Rev. B: Condens. Matter Mater. Phys. 2003, 68 (10), 104431. (35) Burzo, E.; Vlaic, P.; Kozlenko, D. P.; Kichanov, S. E.; Rutkauskas, A. V.; Savenko, B. N. Crystal structure and magnetic behaviour of DyCo2 compound at high pressures. J. Alloys Compd. 2017, 724, 1184− 1191.

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DOI: 10.1021/acs.inorgchem.9b00480 Inorg. Chem. XXXX, XXX, XXX−XXX