Icosahedron [Cl12]12- Templated Gigantic Gd158Co38 Nanocluster with the Largest Ln158 Core for Magnetic Cooling

doi:10.21203/rs.3.rs-699859/v1

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Icosahedron [Cl₁₂]^12- Templated Gigantic Gd₁₅₈Co₃₈ Nanocluster with the Largest Ln₁₅₈ Core for Magnetic Cooling

https://doi.org/10.21203/rs.3.rs-699859/v1

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The synthesis of large nano-sized cluster-molecules is a goal that synthesists and structural scientists have been pursuing, as well as a huge challenge. Herein, the largest 3d-4f metal clusters Cl₁₂@Gd₁₅₈Co₃₈ and Br₁₂@Gd₁₅₈Co₃₈ until now are obtained through the “multi-anions-template” strategy, with a protein-sized metal frame (ca. 4.3 × 3.6 × 3.5 nm³). Different from the mixed distribution of 3d and 4f metals and the hollow structure in the previous giant 3d-4f clusters, for the dense core-shell structure Cl₁₂@Gd₁₅₈Co₃₈ and Br₁₂@Gd₁₅₈Co₃₈, the Ln₁₅₈ core with the highest Ln nuclearity number is induced by icosahedra-shaped templates [Cl₁₂]^12- or [Br₁₂]^12-, while 3d metals (Co) are distributed on its periphery. Their appearances point out a new structure type of non-open giant Ln-based clusters (metal number > 100) and provide an ideal model for studying the multi-level assembly of complex macromolecules. Additionally, Cl₁₂@Gd₁₅₈Co₃₈ shows the largest magnetic entropy change (-∆S_m^max = 46.95 J kg^-1 K^-1 under 2.0 K and ΔH = 7 T) among reported high-nuclearity 3d-4f clusters.

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Synthesis and structural characterization of giant molecules have long been one of the most attractive fields, owing to their fascinating topological structures, complex intramolecular assembly behavior, and numerous physical-chemical properties different from small molecules^1–10. High-nuclearity lanthanide(Ln)-containing clusters are one of the new members of the giant molecular family and has received extensive attention in the past decade associated with charming structures and excellent properties in magnetism, catalysis, and luminescence^11–20.

Ongoing progress in synthetic strategy (such as anion template, mixed-ligand, building blocks strategy, etc.^21–26) has enabled the preparation of giant Ln(4f)-exclusive clusters (such as {Ln₁₀₄}²⁷, {Ln₁₄₀}²⁸) and transition-lanthanide(3d-4f) clusters (such as {La₆₈Ni₉₀}²⁴, {La₇₆Ni₈₈}²⁴, {Gd₇₈Ni₆₄},²⁹ {Ln₉₆Ni₆₄}²³, and {Gd₁₀₂Ni₃₆}³⁰). However, successful preparation and vigorous development of other giant metal clusters (for instance, {Ag₄₉₀}³¹, {Mo₃₆₈}³², {Nd₂₈₈}³³, {Mo₂₄₈}³⁴, and {La₁₀Ni₄₈Sb₁₆W₁₄₀}³⁵ with 214 metal ions) illustrated that the exploration of giant 4f-containing clusters is almost the tip of the iceberg, mainly due to various and complicated coordination modes of lanthanide ions, huge uncertainty in synthesis³⁶.

Compared to 4f-exclusive clusters, it proves that 3d-4f clusters seem to have better synthetic controllability and may have both the advantages of different metals and potential synergistic effects. On the basis of the mentioned above synthetic methods, Kong, Zheng, and Xu et al. fabricated a series of high-nuclearity 3d-4f clusters^21–26. Unfortunately, 3d-4f compounds with more than 100 metal ions were only realized in the Ni-Ln system and featured the similar metal arrangement and open hollow structure types, which were frequently based on the multi-dentate ligand iminodiacetic acid (H₂IDA)^24,37. Recently, Zheng’s group constructed a wheel {Gd₁₀₂Ni₃₆} high-nuclearity cluster without H₂IDA ligand, through utilizing SO₄²⁻-templates and Ni-complexes as protected groups located at the outer vertices of the cluster³⁰. The emergence of this cluster suggests that giant Ni-Ln nano-clusters can also perform the wheel structure, which seems to echo the wheel-shaped {Gd₁₄₀}²⁸. Attempting at assembly 3d and 4f ions into giant clusters featured novel and charming configurations differing from the above two kinds of forms, is promising and challenging.

Relative to the extensive research on the synthesis and properties of Ni-Ln, other high-nuclearity 3d-Ln clusters are less studied, owing to the difficulty of synthesis^38–39. Co ions with the high spin ground state and excellent catalysis have been widely studied^40–44. For instance, {Ln₄₂Co₁₀}, and {Ln₄₅Co₇} possess the outstanding magnetocaloric effect than similar structures of {Ln₄₂Ni₁₀} and {Ln₄₅Ni₇}^5,45. In 2021, a series of {Ln₃₆Co₁₂}⁴⁶ clusters were obtained on the basis of {Ln₃₆Ni₁₂}²² and presented the higher electrocatalytic activity. Meanwhile, {Ln₄₂Co₁₀}⁵, and {Ln₄₅Co₇}⁴⁵, both with 52 metal ions, are so far largest Co-Ln clusters, indicating that the development of Co-Ln materials is far inferior to Ni-Ln. These facts encourage us to explore and synthesize giant Co-Ln clusters, expecting to obtain various structures and diversified excellent properties from the existing ones.

In this work, a fantastic high-nuclearity heterometallic cluster with a 4.3 nm size, [Cl₁₂@Gd₁₅₈Co₃₈(CO₃)₉₀(OAc)₁₈(µ₃-OH)₂₃₆(CH₃NH₂CH₂COO)₆(MIDA)₄₂(H₂O)₈₄]·

Cl₂₄·144(H₂O) and [Br₁₂@Gd₁₅₈Co₃₈(CO₃)₉₀(OAc)₁₈(µ₃-OH)₂₃₆(CH₃NH₂CH₂COO)₆(MIDA)₄₂(H₂O)₇₈(CH₃O)₆]·Cl₁₂·Br₆·94(H₂O) (abbreviated as Cl₁₂@Gd₁₅₈Co₃₈, Br₁₂@Gd₁₅₈Co₃₈, H₂MIDA = N- methyliminodiacetic acid, HOAc = acetic acid), were obtained via icosahedron-like [Cl₁₂]¹²⁻ or [Br₁₂]¹²⁻ anionic templates. According to the metal nuclearity number, alluring Cl₁₂@Gd₁₅₈Co₃₈ and Br₁₂@Gd₁₅₈Co₃₈ clusters both contain the largest number of metal ions (196) in previous 3d-4f compounds, and are more than ca. 4 times of reported largest Co-4f metal clusters^5,45. Another amusing feature of two compounds is the presence of new highest-nuclearity Ln-OH aggregate [Gd₁₅₈(CO₃)₆₆(µ₃-OH)₂₃₆] (Gd₁₅₈). The existence of multiple isotropic anionic templates (12 Cl⁻ or Br⁻) plays a vital role in the formation and stability of the inner Gd₁₅₈. What is more, the inner Gd₁₅₈ is protected by multi-ligands and 38 Co ions to form the captivating Cl₁₂@Gd₁₅₈Co₃₈ and Br₁₂@Gd₁₅₈Co₃₈ clusters. To the best of our knowledge, the emergence of Cl₁₂@Gd₁₅₈Co₃₈ and Br₁₂@Gd₁₅₈Co₃₈ nanoclusters make the structural configurations of 3d-4f cluster family more abundant, which breaks the traditional cavity structure^21–26. Simultaneously, numerous Gd³⁺ ions make Cl₁₂@Gd₁₅₈Co₃₈ and Br₁₂@Gd₁₅₈Co₃₈ clusters display the potential magnetic cooling application with much larger value of -∆S_m^max (46.30 and 46.95 and J kg^− 1 K^− 1 under 2.0 K and ΔH = 7 T) among the identified 3d-4f metal clusters.

Structure analysis. Single-crystal X-ray diffraction (SCXRD) demonstrates that the structure of Cl₁₂@Gd₁₅₈Co₃₈ is similatr to Br₁₂@Gd₁₅₈Co₃₈, here only Cl₁₂@Gd₁₅₈Co₃₈ as example to be discussed in detail. Cl₁₂@Gd₁₅₈Co₃₈ crystallizes in the trigonal crystal system, R-3 space group. The cationic core of Cl₁₂@Gd₁₅₈Co₃₈ constitutes of six Cl₁₂@Gd₂₇Co₇(CO₃)₁₅(OAc)₄(µ₃-OH)₄₀(CH₃NH₂CH₂COO)(MIDA)₇(H₂O)₁₄ (Cl₁₂@Gd₂₇Co₇, in which Gd4, Co4, and O29 are distributed in the C₃ axis) building units (Fig. 1a, 1b). Cl₁₂@Gd₂₇Co₇ is made up of one highly symmetrical cationic unit Gd₂₆Co₅(CO₃)₁₅(OAc)₃(µ₃-OH)₄₀(MIDA)₇(H₂O)₁₄ (Gd₂₆Co₅) and two Cl⁻ anionic templates, one Gd, two Co ions, one OAc⁻, and one CH₃NH₂CH₂COO⁻ ligand (decomposition of H₂MIDA, Fig. S14, Scheme S2). In addition, Gd₂₆Co₅ (Fig. 1c) can be regarded as three different motifs: type I, formulated as Gd₅Co₂(MIDA)₂(OAc)(CO₃)₃(µ₃-OH)₄ (Gd₅Co₂), is distributed in the top of Gd₂₆Co₅; type II, formulated as Gd₁₆(MIDA)₂(CO₃)₉(µ₃-OH)₂₂ (Gd₁₆), is distributed in the middle of Gd₂₆Co₅; type III, formulated as Gd₅Co₃(MIDA)₃(OAc)(CO₃)₂(µ₃-OH)₄ (Gd₅Co₃), is distributed in the bottom of Gd₂₆Co₅. Besides, two Gd₇(MIDA)(CO₃)₃(µ₃-OH)₁₁ (Gd₇, Fig. 1e) is connected by two Gd(CO₃) to form Gd₁₆. Based on four CO₃²⁻ and four µ₃-OH⁻ groups, Gd₅Co₂, Gd₁₆, and Gd₅Co₃ motifs are joined together to form Gd₂₆Co₅. Cl₁₂@Gd₁₅₈Co₃₈ has a 3-fold symmetric (C₃) axis and an inversion center (Fig. S11-12). Three asymmetric building units Cl₁₂@Gd₂₇Co₇ obtained by rotation are connected together alternately via CO₃²⁻ and µ₃-OH⁻ anions to form a trimer Gd₇₉Co₁₉(CO₃)₄₅(OAc)₁₂(µ₃-OH)₁₂₀(CH₃NH₂CH₂COO)₃(MIDA)₂₁ (Gd₇₉Co₁₉). Two trimers Gd₇₉Co₁₉ obtained by inversion are further joined into Gd₁₅₈Co₃₈.

It is worth noting that a large series of CO₃²⁻ anions as important templates and linkers among metal ions, deriving from the decomposition of organic ligands, exhibit a rich variety of coordination modes (Fig. S3), reflecting the complexity of the nanocluster structure, and the adaptability of the anion templates. Meanwhile, the main ligand MIDA²⁻ also shows unusual and diverse coordination modes (Fig. S4). For example, high chemical affinity of N atom from organic ligands tends to coordinate with 3d ions³⁸, but N atoms in this work are also linked with 4f ions.

Interestingly, in Cl₂@Gd₂₇Co₇, two crystallographically independent halide ions (Cl1 and Cl2) are found in the center of similar two Gd-CO₃-OH cages [(Gd₁₆(CO₃)₆(µ₃-OH)₇, Fig. 2a, 2c], hydrogen-bonded to 7 µ₃-OH⁻ groups, respectively (Fig. 2d, 2f, distance of Cl···O: from 3.219 Å to 3.419 Å, angle of Cl-H-O: from 155.15° to 176.16°)²². Additionally, six Cl1 and six Cl2 ions obtained by rotainversion form one icosahedron [Cl₁₂]¹²⁻ cage (Cl₁₂, distance of Cl···Cl: from 7.216 Å to 8.445 Å, Fig. 2e, 3b). The 12 Gd-CO₃-OH cages templated by Cl⁻ ions form the main structure [Gd₁₁₆(CO₃)₆₆(µ₃-OH)₈₄] (Fig. 2b) of Ln-core [Gd₁₅₈(CO₃)₆₆(µ₃-OH)₂₃₆] by sharing 4f metals or anions (CO₃²⁻ and OH⁻). Although Cl⁻ ions as the templates in metal clusters have been obtained (such as {Gd₃₆Ni₁₂}²² templated by 2 Cl⁻; {Gd₈Cr₄}⁴⁷ templated by one Cl⁻ and one ClO₄⁻), this 3d-4f nanocluster with more than ten Cl⁻ templates (Cl₁₂ with one icosahedron pattern) is firstly reported, and it has important guiding significance for the prediction and construction of high-nuclearity 4f-containing nanoclusters.

For the sake to facilitate the illustration and comprehending of the complex metal skeleton, Cl₁₂@Gd₁₅₈Co₃₈ can be disassembled into three components (Fig. S15): (i) six Gd(MIDA)₂(CO₃)(µ₃-OH)₂ groups, exhibiting a near-octahedral geometry; (ii) six Co(MIDA)₃ groups, showing a hexagonal arrangement; (iii) one Cl₁₂@Gd₁₅₂Co₃₂(CO₃)₂₄(µ₃-OH)₁₁₆ group (Cl₁₂@Gd₁₅₂Co₃₂), revealing a typical core-shell structure and modular features. From the inside to outside, Cl₁₂@Gd₁₅₂Co₃₂ (Fig. 3 and S16) is treated as Gd₂₀@Cl₁₂@Gd₄₈Co₃₂@(Gd)₁₂@(Gd₁₂)₆, and presents one dodecahedron Ln-core of 20 Gd³⁺ ions [Gd₂₀(CO₃)₁₂] (Gd₂₀, Fig. 3a), one icosahedron of 12 Cl⁻ ions (Cl₁₂, Fig. 3b), one truncated-cube-like cage of Gd₁₃₂Co₃₂ (Fig. 3i). Gd₁₃₂Co₃₂ comprised of eight propeller-like heterometallic building blocks [Gd₆Co₄(µ₃-OH)₉] (Gd₆Co₄, Fig. 3e) as truncated-cubic vertices forming main metal framework [Gd₄₈Co₃₂(µ₃-OH)₄₄] (Gd₄₈Co₃₂, Fig. 3d), 12 Gd(µ₃-OH)₃ groups (Gd, Fig. 3f) as edges, six saddle-shaped motifs ([Gd₁₂(CO₃)₂(µ₃-OH)₆], Gd₁₂, Fig. 3g) as faces. So, Gd₁₃₂Co₃₂ can be viewed as (Gd₆Co₄)₈@(Gd)₁₂@(Gd₁₂)₆. Here are 10 Co³⁺ and 28 Co²⁺ ions in final products, determined by XPS (Fig. S33) and charge balance.

Althrough the metal structures of Br₁₂@Gd₁₅₈Co₃₈ and Cl₁₂@Gd₁₅₈Co₃₈ are very similar, ther are some difference between two compound: (i) six CH₃O ligands and 30 anions (12 Cl⁻ and 18 Br⁻) are exisisted in Br₁₂@Gd₁₅₈Co₃₈ to balace the charge balance; (ii) but 36 anions (30 Cl⁻) are exisisted in Cl₁₂@Gd₁₅₈Co_38.

Magnetic properties. The large presence of metal ions inspires us to investigate the magnetic properties of Br₁₂@Gd₁₅₈Co₃₈ and Cl₁₂@Gd₁₅₈Co₃₈. The plot of temperature-dependent magnetic susceptibility (χ_MT-T) was studied under 1.0 kOe direct current (dc) field with the scope of 1.8–300 K (Fig. S38, S39). The χ_MT values under the room temperature were 1380.75 (Cl₁₂@Gd₁₅₈Co₃₈) and 1384.91 (Br₁₂@Gd₁₅₈Co₃₈) cm³ K mol^− 1, which is bigger than the theoretical value of 1296.75 cm³ K mol^− 1 for 158 uncorrelated Gd³⁺ (S = 7 /2, g = 2) and 28 high-spin Co²⁺ (S = 3/2, g = 2)⁴⁵. The difference between the theoretical and test values is put down to the remarkable orbital contributions of the high-spin Co²⁺ ions⁵. As the temperature goes down, the value of χ_MT gradually decreases and achieves 726.25 (Cl₁₂@Gd₁₅₈Co₃₈) and 696.30 (Br₁₂@Gd₁₅₈Co₃₈) cm³ K mol^− 1 at 1.8 K. This behavior is mainly ascribed to the depopulation of Kramers excited state levels of octahedral coordination environment for Co²⁺ ion because the magnetic interaction between 3d and 4f or 4f and 4f ions. Based on the Curie-Weiss Law, fitting the plot of χ_M⁻¹ versus T shows parameters, [C = 1415 cm³ K mol^− 1 and θ = −6.04 K (Cl₁₂@Gd₁₅₈Co₃₈); C = 1462.60 cm³ K mol^− 1 and θ = −3.20 K (Br₁₂@Gd₁₅₈Co₃₈)], for the sum contribution of orbital of Co²⁺ ion and the coupling between metal ions (Fig. S40, S41). The field-dependent magnetization (M-H) of Cl₁₂@Gd₁₅₈Co₃₈ was performed in the range of 1.8–20 K at 0–7 T (Fig. S42, S43). The curves of M vs H represent a steady rise in magnetization and attain 1045.29 Nµ_B (Cl₁₂@Gd₁₅₈Co₃₈) and 1058.57 Nµ_B (Br₁₂@Gd₁₅₈Co₃₈) Nµ_B at 7 T at 1.8 K, which are slightly lesser than the expected value 1190 Nµ_B for 158 uncorrelated Gd³⁺ (S = 7/2, g = 2) and 28 high-spin Co²⁺ (S = 3/2, g = 2)⁴⁵. It also results from the orbital effect of Co²⁺, which gives an effective spin S_eff = 1/2 and the magnetization is usually ~ 2.1 Nµ_B per Co²⁺ ion⁴⁸.A large class of Gd³⁺ ions in Cl₁₂@Gd₁₅₈Co₃₈ and Br₁₂@Gd₁₅₈Co₃₈ urge us to explore its magnetocaloric effect. The calculated magnetic entropy changes ∆S_m were evaluated via using the Maxwell relation (∆S_m(T) = ∫[∂M(T, H)/∂T ]_H dH)²⁹. As shown in Fig. 4, S44, the values of -∆S_m^max are 46.95 (Cl₁₂@Gd₁₅₈Co₃₈) and 46.30 (Br₁₂@Gd₁₅₈Co₃₈) J kg^− 1 K^− 1 at 2.0 K at 7 T. The values are smaller than their theoretical values (64.33 and 62.32 J kg^− 1 K^− 1) by applying the formula of -∆S_m = nRln(2S + 1), which are attributable to the presence of possible antiferromagnetic interaction³⁰. Nevertheless, their values were much larger than known 3d-4f cluster complexes (Table S6). And the value of Cl₁₂@Gd₁₅₈Co₃₈ is the largest at present. In low magnetic field, Br₁₂@Gd₁₅₈Co₃₈ and Cl₁₂@Gd₁₅₈Co₃₈ also show prominent magnetocaloric effect with -∆S_m = 20.13, 20.81 J kg^− 1 K^− 1 at 2.0 K and 2 T, respectively (Table S7)⁴⁹.

In summarize, two charming and giant 3d-4f nanoclusters (ca. 4.3 × 3.6 × 3.5 nm³) have been successfully synthesized using “[Cl₁₂]¹²⁻ or [Br₁₂]¹²⁻ templates” in the presence of multidentate organic ligand (H₂MIDA). 4f metal core (Gd₁₅₈) is protected by 38 Co ions and small ligands to form Br₁₂@Gd₁₅₈Co₃₈ and Cl₁₂@Gd₁₅₈Co₃₈, which both contain 196 metal ions to be the largest 3d-4f cluster until now. In addition, abundant Gd³⁺ ions make Cl₁₂@Gd₁₅₈Co₃₈ and Br₁₂@Gd₁₅₈Co₃₈ show potential magnetic cooling materials with -∆S_m^max = 46.95 and 46.30 J kg^− 1 K^− 1, at 2 K for ΔH = 7 T, which are much larger than known 3d-4f clusters. This work not only overcomes the traditional cavity structure, but also provides one entertaining assumption of high-nuclearity 3d-4f metal frameworks. Next, we will try our best to prepare more 3d-4f molecular magnetocaloric materials through anion-template method.

Material and Instrumentation. All materials were of merchant origin and were used firsthand. The Perkin-Elmer 2400 elemental analyzer was used to perform Elemental analyses (EA; C, H and N). Under room temperature enviromrnt, powder X-ray diffraction (PXRD) was documented (collected in the range of 3 − 50°.) on a Bruker D8X diffractometer furnished with monochromatized Cu-K_α under λ = 1.5418 Å radiation. Infrared spectra (IR) was recorded (from 4000 to 400 cm^− 1) by pressed KBr pellets with a Nicolet Impact 410 FTIR spectrometer. TGA (thermogravimetric analysis and differential scanning calorimeter measurement) was recorded among 25 to 900°C in a flowing nitrogen environment with a heating degree of 10 K·min^− 1 via the NETZSCH STA409 thermogravimetric analyzer. The ZSX Primus II was used to analuze the X-ray fluorescence (XRF) spectrometry. The Hitachi S-4800 scanning electron microscope was carried out to analyze the SEM images and energy dispersive spectrometer (EDS), with a stimulative voltage of 20 kV. The direct current magnetic data (temperature of 1.8–300 K), and the magnetisation isothermal measurements (field with 0–7 T) were obtained on MPMS-XL7 SQUID magnetometer. Experimental susceptibilities were revisional for the diamagnetism estimated Pascal's tables and for products holder by antecedently calibration. The KRATOS AXIS SUPRA™ spectrometer, outfitted with a monochromatized Al Kα source, wsa used to record X-ray photoelectron spectroscopy (XPS). The charge effect was trued via using the binding energy of C1s (284.8 eV) to weaken the sample charging influence.

Synthesis of Cl ₁₂ @Gd ₁₅₈ Co ₃₈. The mixture of GdCl₃·6H₂O (0.185 g, 0.5 mmol), Co(OAc)₂·6H₂O (0.120 g, 0.5 mmol), N-Methyliminodiacetic acid (H₂MIDA; 0.077 g, 0.5 mmol), imidazole (0.068 g, 1 mmol) were melted in deionized water (4 mL), ethanol (5 mL), methanol (1 mL), which was stirred with 2 hours under about 25 ℃. Finally, the mixture was heated 72 h with 160°C. Octahedron-like pink crystals were collected by filtration and washed by deionized water (61.33 % based on Gd). Elemental analyses for C₃₅₄H₁₁₂₄Gd₁₅₈Co₃₈N₄₈O₉₅₀Cl₃₆, calculated (%): C, 8.56; H, 2.26; N, 1.35; found (%): C, 8.62 H, 2.23; N, 1.28.

Synthesis of Br ₁₂ @Gd ₁₅₈ Co ₃₈. The mixture of Gd(NO₃)₃·6H₂O (0.223 g, 0.5 mmol), Co(OAc)₂·6H₂O (0.120 g, 0.5 mmol), KBr (0.119 g, 1mmol), N-Methyliminodiacetic acid (H₂MIDA; 0.077 g, 0.5 mmol), imidazole (0.068 g, 1 mmol) were melted in deionized water (4 mL), ethanol (5 mL), methanol (1 mL), which was stirred with 2 hours under about 25 ℃ and the pH was adjusted to 4.5 with HCl (1 M). Finally, the mixture was heated 72 h with 160°C. Octahedron-like pink crystals were collected by filtration and washed by deionized water (61.33 % based on Gd). Elemental analyses for C₃₆₀H₁₀₃₀Br₁₈Cl₁₂Co₃₈Gd₁₅₈N₄₈O₉₀₀, calculated (%): C, 8.75; H, 2.09; N, 1.36; found (%): C, 8.69; H, 2.12; N, 1.45.

Data availability. Data supporting the findings of this manuscript are available from the corresponding authors upon reasonable request. The X-ray crystallographic coordinates for structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition number CCDC: 2090809 (Cl₁₂@Gd₁₅₈Co₃₈), 2090810 (Br₁₂@Gd₁₅₈Co₃₈).

Acknowledgments

This work was supported by the National Key R&D Program of China (2018YFA0306004), the Natural Science Foundation of China (21571103 and 21973038), Jiangsu Province (BK20191359), the Joint Fund for Regional Innovation and De-velopment (U20A2073).

Author contributions

Y.X. conceived and designed the experiments. N.F.L., J.W., J.L.W., conducted the synthesis and characterization. X.M.L., N.F.L. drew pictures in the manuscript. X.M.L., N.F.L., Y.S., Y.X., H.M., analyzed the experimental results. X.M.L., N.F.L., Y. S., Y. Xu co-wrote the manuscript.

Additional information

Supplementary information is available in the online version of the paper. Reprints and permissions information is available online at www.nature.com/reprints. Correspondence and requests for materials should be addressed to Y. Xu.

Competing financial interests

The authors declare no competing financial interests.

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Icosahedron [Cl₁₂]^12- Templated Gigantic Gd₁₅₈Co₃₈ Nanocluster with the Largest Ln₁₅₈ Core for Magnetic Cooling

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