A Four‐Shell, Nesting Doll‐like 3d–4f Cluster Containing 108 Metal Ions

Abstract

High-nuclearity metal complexes are a unique class of molecules. [1][2][3][4][5][6] Often in the nanoscopic size regime, they display fascinating structural diversity and possess properties that are potentially useful for developing novel catalysts, [1] materials for adsorption and storage, [2] molecular electronics, [3] optics, [4] and magnetism. [5,6] Particular interest in this field has been directed towards heterometallic complexes that feature both d-and f-block elements, and the distinct coordination behaviors of different metal ions have been observed in a large number of stunningly beautiful complexes. [7][8][9][10][11][12][13][14][15][16][17] The unique arrangement of the multiple metal centers within the complex framework, coupled with their inherently disparate electronic structures, often leads to attractive properties, of which novel magnetic phenomena such as single-molecule [14,15] and single-chain magnetism [16,17] are arguably the most notable. Our own efforts along this line of research have resulted in a number of giant 3d-4f clusters containing up to 50 metal ions. [18,19] These clusters display both stunningly beautiful structures and magnetic behaviors ranging from ferromagnetic to antiferromagnetic couplings. Herein we report the synthesis, structure, and magnetic studies of a giant heterometallic cluster containing 108 metal ions. [20] was obtained under hydrothermal conditions from a mixture of Ni(NO 3 ) 2 ·6 H 2 O, Gd(NO 3 ) 3 ·6 H 2 O, and iminodiacetic acid in deionized water and its composition was verified by satisfactory microanalysis.The four-shell, nesting doll-like structure of the cationic cluster is shown in Figure 1 a. Moving outward, the innermost shell (shell 1) contains six Ni II and two Gd III ions and is followed by shell 2 with 20 Gd III ions, shell 3 with 32 Gd III ions, and the outermost shell (shell 4) with 48 Ni II ions (Figure 1 b). The geometry of the shells approximates that of a cube. Inter-shell connections are provided primarily by triply bridging hydroxo groups, which afford a highly compact, brucite-like core structure. Similar structural motifs have been observed in both transition metal [21] and lanthanide clusters.[22] The appearance of the multi-shell structure is comparable to those of multi-shell Pd/Pt clusters, [23,24] nanocapsules of polyoxometalates, [25] and fullerene-like structures built from interpenetrating reciprocal polyhedra. [26,27] Six Ni II and two Gd III ions occupy the vertices of the cube in shell 1 (Figure 2 a). The Gd III ions, which are disposed diagonally, are bridged by an aqua ligand. Triply bridging OH groups, each of which bridges two neighboring metal ions (Gd or Ni) within the cube and a Gd III ion at the edge center of shell 2, form the 12 cube sides (Figure 2 b). The coordination sphere of each of the eight metal ions is completed by three additional m 3 -OH groups. All Ni II ions are therefore hexa-

Stepwise and Controllable Synthesis of Mesoporous Heterotrimetallic Catalysts Based on Predesigned Al4Ln4 Metallocycles

“…[1,2] In addition, the accurate and periodic distribution of metal ions throughout a lattice of crystalline compounds enables the customized atomically precise structural regulation for specific performance, which could not realized in macroscopic nanomaterials. So far, the developed mixed-metal approach mainly includes one-step self-assembly based on hard-soft acid-base theory, [3][4][5][6][7][8] DOI: 10.1002/advs.202305833 and post-synthetic metalation (redox). [1,[9][10][11] The first method involves the use of mixed-donor ligands that discriminate between two types of metal ions through differential binding affinities.…”

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

“…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][22][23][24][25][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 (H 2 IDA) 24,37 . Recently, Zheng's group constructed a wheel {Gd 102 Ni 36 } high-nuclearity cluster without H 2 IDA ligand, through utilizing SO 4…”

Family of Chiral ZnII–LnIII (Ln = Dy and Tb) Heterometallic Complexes Derived from the Amine–Phenol Ligand Showing Multifunctional Properties

“…Magnetic bistability exhibits quantum tunneling effect which is not found in classical physical properties, and makes associated metal clusters attractive in information storage and quantum computing. − In addition, large magnetocaloric effect has been observed in some multinuclear complexes, which have the potential to be applied to cryogenic magnetic refrigeration. , In the field of environmental science, multinuclear complexes can fix carbon dioxide in the air by controlling reaction conditions, which are in favor of preventing the rise of global temperature and sea level. Recently, 3d–4f heterometallic complexes have attracted increasing attentions due to their extraordinary and fascinating structures, − as well as many potential applications in molecular magnetism, , optical materials, − and catalysis. − After the first example of 3d–4f heterometallic complex was reported, , more 3d–4f heterometallic complexes have been synthesized and investigated. − Compared with the other 3d–4f complexes, Zn II -Ln III complexes have aroused more remarkable attention due to the following reasons: (a) Diamagnetic Zn II ions can increase the negative charge on the bridged oxygen center between the diamagnetic metal ion and the 4f metal ion to stabilize the ground states of the lanthanide ions, resulting in the enhancement of energy barriers of such complexes; and (b) Ln III ions such as Eu III and Tb III are good luminescent centers, and the combination of Ln III and Zn II ions may promote luminescent properties via f–d energy transfer . Many Zn II –Ln III heterometallic complexes have been reported, and their magnetic and luminescent properties have been well investigated. − …”