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Widespread concern has been raised over the synthesis of highly nucleated lanthanide clusters with special shapes and/or specific linkages. Construction of lanthanide clusters with specific shapes and/or linkages can be achieved by carefully regulating the hydrolysis of lanthanide metal ions and the resulting hydrolysis products. However, studies on the manipulation of lanthanide-ion hydrolysis to obtain giant lanthanide-oxo clusters have been few. In this study, we obtained a tetraicosa lanthanide cluster (

Two organic hybrid manganese selenoarsenates, [Mn(en)

By changing the coordination anions (OAc

A superb alkali-resistant single-molecule-magnet (SMM) material with the molecular formula [Dy2Ni4(L)8(CH3COO)4(NO3)2] (1) (HL = 8-hydroxyquinoline) has been structurally and magnetically characterized. Single-crystal X-ray diffraction revealed that 1 possesses a hexanuclear [DyIII2NiII4] cluster, which is built by two triangular [DyIIINiII2] cores double-bridged through two CH3COO- ions. Interestingly, 1 can keep its original structure in dilute acid and common basic solutions (e.g., triethylamine and NaOH). More importantly, 1 is still stable after treatment with a 20 M NaOH aqueous solution for 1 month at room temperature. Magnetic measurements uncovered that 1 is an SMM under zero applied field with Ueff = 7.43 K. To the best of our knowledge, 1 is the first example of a 3d-4f SMM with such extreme alkali resistance. This work will broaden the vision of preparing SMM materials with excellent chemical stability.

Lanthanoid metal ions have large ionic radii, complex coordination modes, and easy distortion of coordination spheres, but the design and synthesis of high-nucleation lanthanoid clusters with high stability in solution (especially aqueous solution) are challenging. Herein, a diacylhydrazone ligand (H

The aggregation and formation of heterometallic nanoclusters usually involves a variety of complex self-assembly processes; thus, the exploration of their assembly mechanisms through process tracking is more challenging than that for homometallic nanoclusters. We explored here the effect of solvent on the formation of heterometallic clusters, which gave two heterometallic nanoclusters, [Dy2Co8(μ3-OCH3)2(L)4(HL)2(OAc)2(NO3)2(CH3CN)2]·CH3CN·H2O (1) and [Dy4Co6(L)4(HL)2(OAc)6(OCH2CH2OH)2(HOCH2CH2OH)(H2O)]·9CH3CN (2), with the H3L ligand formed from the in situ condensation reaction of 3-amino-1,2-propanediol with 2-hydroxy-1-naphthaldehyde in the presence of Co(OAc)2·4H2O and Dy(NO)3·6H2O. It is worth noting that the skeleton of cluster 1 has a high stability under high-resolution electrospray ionization mass spectrometry (HRESI-MS) conditions with a gradually increasing energy of the ion source. Cluster 2 underwent a multistep fragmentation even under a zero ion-source voltage for the measurement of HRESI-MS. Further analysis showed that cluster 2 underwent a possible fragmentation mechanism of Dy4Co6L6 → Dy2Co6L5/DyL → DyCo2L3/DyCo2L → DyL/Co2L2. Most notably, the species emerging in the formation process of cluster 1 were tracked using time-dependent HRESI-MS, from which we proposed its possible formation mechanism of H2L → Co2L2 → Co2DyL2/Co3L2 → Co3DyL2 → Co4DyL2 → Co5Dy2L4 → Co8Dy2L6. As far as we know, it is the first time to track the formation process of Dy-Co heterometallic clusters through HRESI-MS with the proposed assembly mechanism. The magnetic properties of the two titled DyIIIxCoII10-x (x = 2, 4) clusters were studied. Both of them exhibit slow magnetic relaxation, and 1 is a single-molecule magnet at zero direct-current field.

Two new one-dimensional (1D) vanadium(III) chalcogenidostannates, [H2tepa]0.5n[VIII(tepa)(μ-Sn2Q6)]n [Q = S (1), Se (2); tepa = tetraethylenepentamine], were achieved by solvothermal methods, which offer the first examples of organic hybrid polymeric chalcogenidostannates incorporating [V(tepa)]3+ complexes as bridging groups. Both 1 and 2 feature the 1D sinusoidal chains of [VIII(tepa)(μ-Sn2Q6)]n containing two types of novel bridging modes of the [μ-Sn2Q6]4- anion. Their magnetic, photocurrent response, and optical properties are also studied.

One novel octasubstituted trisalkoxotetradecavanadate cluster, [V14O18(tri)2(Htri)6(HCOO)2]·2H2O [1; H3tri = tris(hydroxymethyl)aminomethane], was revealed by a hydrothermal method. 1 shows a new type of fully reduced trisalkoxotetradecavanadate cluster, incorporating the highest number of H3tri ligands, that is constructed by the interconnection of two rare trisalkoxoheptavanadate units via two O bridges. The magnetic and photocurrent response properties were investigated.

A three-dimensional supermolecule structure is easily formed due to the diverse coordination modes of high-oxidation-state lanthanide metal ions. However, the design and construction of zero-dimensional (0 D) dish-shaped high-nuclearity lanthanide clusters are difficult. Herein, for the first time, we synthesized a series of the largest dish-shaped high-nuclearity lanthanide nanoclusters (

The design and synthesis of simple lanthanide complexes with multiple functions have been widely studied and have faced certain challenges. Herein, we successfully synthesized the series of binucle...

The serialized expansion of high-nuclear clusters usually includes the controlled variable method and changes only a single variable. However, changing both variables will greatly increase the complexity of the reaction simultaneously. Therefore, the use of a two-component regulation reaction is rare. Herein, we used a diacylhydrazone ligand (H4L1) with multidentate chelating coordination sites for the reaction with Gd(NO3)3·6H2O under solvothermal conditions to obtain an example of 16-nucleus disc-shaped cluster 1 with a brucite structure. The overall structure of cluster 1 can be regarded as an equilateral triangle, which is formed by three (L1)4- ions that can be regarded as "sides" and wrap the four-layer metal center Gd(III) ions. Notably, upon simultaneous regulation of the substituent of the ligand and the coordination anion, heptanuclear gadolinium cluster 2 was obtained. Cluster 2 can be regarded as a butterfly structure, which was formed by connecting two Gd3L2 molecules that were not in the same plane and through the central Gd(III) ion as an intersection. Moreover, hexanuclear gadolinium cluster 3 was obtained by changing the ligand substituent and adding an auxiliary ligand. Cluster 3 can be regarded as a chair structure, which was composed of two molecules of diacylhydrazone ligand (L2)4- wrapping vacant cubane shared by four vertices. This study was the first to construct a series of high-nuclear gadolinium clusters through two-component regulation manipulation. The study of the magnetocaloric effect showed that the maximum values of -ΔSm for clusters 1-3 were 34.05, 29.04, and 24.32 J kg-1 K-1, respectively, when T = 2 K and ΔH = 7 T.

Two mononuclear dysprosium complexes (Et3NH)[Dy(BrMQ)4]·H2O·DMF(BrMQ-Dy) and (Et3NH)[Dy(ClMQ)4]·H2O·DMF (ClMQ-Dy) (H-BrMQ = 5,7-dibromo-2-methyl-8-quinolinol, H-ClMQ = 5,7-dichloro-2-methyl-8-quinolinol) were synthesized and characterized. The Dy(III) ions in complexes BrMQ-Dy and ClMQ-Dy have a pseudo-D4d local symmetry. Magnetic characterizations reveal that complex BrMQ-Dy is a single-ion magnet and complex ClMQ-Dy exhibits field-induced slow magnetic relaxation behaviors. The calculated effective barriers of BrMQ-Dy, BrMQ-Dya, ClMQ-Dy, and ClMQ-Dya are 47.8, 27.3, 96.0, and 65.5 cm-1, respectively (BrMQ-Dya and ClMQ-Dya represent the desolvated samples of BrMQ-Dy and ClMQ-Dy, respectively). Ab initio calculations confirmed that coordination symmetry of the Dy(III) ions, electron-withdrawing ligands, and the guest molecules is a key factor affecting the magnetic dynamics of the two complexes. The IC50 values of BrMQ-Dy and ClMQ-Dy against BEL-7404, HeLa, and Hep-G2 cancer cells were 1.01-22.06 μM. Interestingly, two Dy(III) complexes were less toxic to normal HL-7702 cells. BrMQ-Dy and ClMQ-Dy significantly induced cell arrest at G2 phase and down-regulated the G2 phase-related protein levels. Various experiments suggested that BrMQ-Dy and ClMQ-Dy also caused dysfunction of mitochondrial pathways in HeLa cells. Taken together, the different in vitro anticancer activity of complexes BrMQ-Dy and ClMQ-Dy in the order of 5,7-dichloro substitution > 5,7-dibromo substitution.

The aggregation and formation of heterometallic nanoclusters usually involves a variety of complex self-assembly processes; thus, the exploration of their assembly mechanisms through process tracking is more challenging than that for homometallic nanoclusters. We explored here the effect of solvent on the formation of heterometallic clusters, which gave two heterometallic nanoclusters, [Dy

Two new one-dimensional (1D) vanadium(III) chalcogenidostannates, [H

The design and synthesis of simple lanthanide complexes with multiple functions have been widely studied and have faced certain challenges. Herein, we successfully synthesized the series of binuclear lanthanide complexes [Ln

The generation of two types of complexes with different topological connections and completely different structural types merely via the substitution effect is extremely rare, especially for −CH3 a...

A new indium telluride, [Mn4.78In2.22(ea)12]n[In9.79Mn0.21Te17]n (where Hea = ethanolamine), containing unprecedented nonsupertetrahedral [In9.79Mn0.21Te21] units is the first example of a two-dimensional indium telluride framework templated by a rare high-nuclearity wheel-shaped heterometallic [Mn4.78In2.22(ea)12]4.22+ cluster. The photocurrent response and magnetic properties were investigated.

A series of lanthanide selenidogermanates, (H2peha)[Ln2(μ-OH)2(tepa)2Cl2]{[Ln2(μ-OH)2(tepa)2Cl]2(μ-Ge2Se6)}[Ge2Se6]Cl2 [Ln = Y (1a) and Er (1b); peha = pentaethylenexamine, tepa = tetraethylenepentamine], [Sm2(μ-OH)2(tepa)2(μ-Ge2Se6)]n (2), [Ho2(μ-OH)2(tepa)2(μ-Ge2Se6)]n (3), and [Ce4(tepa)4(μ-GeSe4)(μ-GeSe5)(μ-Ge2Se6)]n (4), were made under solvothermal conditions. Compounds 1a and 1b contain a protonated H2peha2+ ion, the complex cation [Ln2(μ-OH)2(tepa)2Cl2]2+, a [Ge2Se6]4- anion, free Cl- ions, and a {[Ln2(μ-OH)2(tepa)2Cl]2(μ-Ge2Se6)}2+ cation constructed by two unsaturated [Ln2(μ-OH)2(tepa)2Cl]3+ groups connecting via the trans terminal Se atoms of the [Ge2Se6]4- anion, which provides the first example of an organic decorated lanthanide selenidogermanate cation. Both compounds 2 and 3 contain one-dimensional chains [Ln2(μ-OH)2(tepa)2(μ-Ge2Se6)]n constructed by a combination of unsaturated complex cations [Ln2(μ-OH)2(tepa)2]4+ and [Ge2Se6]4- anions, but their stacking patterns of neutral chains are different. Compound 4 contains one-dimensional chain [Ce4(tepa)4(μ-GeSe4)(μ-GeSe5)(μ-Ge2Se6)]n, where three different selenidogermanate units acting as bridging ligands connect unsaturated [Ce(tepa)]3+ ions. Compound 4 represents the first example of the coexistence of three different selenidogermanate anions in the same architecture. Their optical properties are studied, and the magnetic properties of compounds 1b and 2-4 are also investigated.

A series of lanthanide–germanate oxo clusters, [Ln8(phen)2Ge12(μ3-O)24T12(H2O)16]·2H2O [Ln = Dy (1a) and Er (1b); T = −CH2CH2COO– group; phen = 1,10-phenanthroline], [Ln8(phen)2Ge12(μ3-O)24T12(H2O)16]·2phen·16H2O [Ln = Sm (2a), Eu (2b), and Gd (2c)], and [Ho8(phen)2Ge12(μ3-O)24T12(H2O)14]·2phen·13H2O (3), have been hydrothermally synthesized from the reactions of bis(carboxyethylgermanium sesquioxide) and Ln2O3 with auxiliary phen chromophores. Compounds 1a and 1b consist of cage clusters [Ln8(phen)2Ge12(μ3-O)24T12(H2O)16] and free H2O molecules, where cage clusters are arranged in a CsCl type, while compounds 2a–2c consist of cage clusters [Ln8(phen)2Ge12(μ3-O)24T12(H2O)16], free phen, and free H2O molecules, where cage clusters are arranged in a NaCl type. Compound 3 consists of the one-dimensional neutral chain [Ho8(phen)2Ge12(μ3-O)24T12(H2O)14]n and free H2O molecules. These compounds provide the first examples of p–f heterometallic [Ge–O–Ln] oxo clusters decorated by phen chromophores. The photolumin...

High-nuclear lanthanide clusters are generally formed by the rapid accumulation of simple building units. Thus, tracking and observing the stepwise assembly process, which is vital for understanding the assembly mechanism, are extremely difficult. Herein, the decanuclear nanocluster [Dy10(L1)6(μ5-NO3)2(OAc)10(HOAc)2]·8H2O (Dy10, H3L1 = (E)-3-((3-ethoxy-2-hydroxybenzylidene)amino)propane-1,2-diol) was obtained from the reaction of Dy(NO3)3·6H2O, Dy(OAc)3·6H2O, 3-ethoxy-2-hydroxybenzaldehyde (L2), and 3-amino-1,2-propanediol (L3). The reaction process was further tracked by time-dependent high-resolution electrospray ionization mass spectrometry, and seven reaction intermediate fragments were screened. A stepwise assembly mechanism was observed based on these fragments, that is, L → Dy1 → Dy2 → Dy3 → Dy4 → Dy5 → Dy6 → Dy10. This study is the first to discover a stepwise assembly mechanism during the formation of high-nuclear lanthanide clusters (cluster nucleus > 3). Magnetic studies have shown the multiple relaxation behavior of Dy10.