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A heterometallic 3d–4f compound formulated as {[Co III2 Dy3Na(CH3CH2COO)6(OH)6(NO3)4(H2O)2]·H2O}n (1) has been synthesized and structurally characterized. The Co2Dy3 metal core adopts trigonal bipyramidal (TBP) geometry. Compound 1 displays single-molecule magnet behavior with an energy barrier of 60.3 K under a zero dc field. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) provide a tunable platform for hierarchically integrating multiple components to effect synergistic functions that cannot be achieved in solution. Here we report the encapsulation of a Ni-containing polyoxometalate (POM) [Ni4(H2O)2(PW9O34)2]10− ( Ni4P2) into two highly stable and porous phosphorescent MOFs. The proximity of Ni4P2 to multiple photosensitizers in Ni4P2@MOF allows for facile multi-electron transfer to enable efficient visible-light-driven hydrogen evolution reaction (HER) with turnover numbers as high as 1476. Photophysical and electrochemical studies established the oxidative quenching of the excited photosensitizer by Ni4P2 as the initiating step of HER and explained the drastic catalytic activity difference of the two POM@MOFs. Our work shows that POM@MOF assemblies not only provide a tunable platform for designing highly effective photocatalytic HER catalysts but also facilitate detailed mechanistic understanding of HER processes. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) provide a tunable platform for hierarchically integrating multiple components to effect synergistic functions that cannot be achieved in solution. Here we report the encapsulation of a Ni-containing polyoxometalate (POM) [Ni4(H2O)2(PW9O34)2]10− ( Ni4P2) into two highly stable and porous phosphorescent MOFs. The proximity of Ni4P2 to multiple photosensitizers in Ni4P2@MOF allows for facile multi-electron transfer to enable efficient visible-light-driven hydrogen evolution reaction (HER) with turnover numbers as high as 1476. Photophysical and electrochemical studies established the oxidative quenching of the excited photosensitizer by Ni4P2 as the initiating step of HER and explained the drastic catalytic activity difference of the two POM@MOFs. Our work shows that POM@MOF assemblies not only provide a tunable platform for designing highly effective photocatalytic HER catalysts but also facilitate detailed mechanistic understanding of HER processes. [ABSTRACT FROM AUTHOR]

The one‐step efficient separation of high‐purity C2H4 from C2H4/C2H6 mixtures by hydrogen‐bonded organic frameworks (HOFs) faces two problems: lack of strategies for constructing stable pores in HOFs and how to obtain high C2H6 selectivity. Herein, we have developed a microporous Mortise‐Tenon‐type HOF (MTHOF‐1, MT is short for Mortise‐Tenon structure) with a new self‐assembly mode for C2H4/C2H6 separation. Unlike previous HOFs which usually possess discrete head‐to‐head hydrogen bonds, MTHOF‐1 is assembled by unique consecutive side‐by‐side hydrogen bonds, which result in mortise‐and‐tenon pores decorated with orderly arranged amide groups and benzene rings. As expected, MTHOF‐1 exhibits excellent stability under various conditions and shows clear separation trends for C2H6/C2H4. The IAST selectivity is as high as 2.15 at 298 K. More importantly, dynamic breakthrough experiments have demonstrated that MTHOF‐1 can effectively separate the C2H6/C2H4 feed gas to obtain polymer‐grade C2H4 in one step even under high‐humidity conditions. [ABSTRACT FROM AUTHOR]

The one‐step efficient separation of high‐purity C2H4 from C2H4/C2H6 mixtures by hydrogen‐bonded organic frameworks (HOFs) faces two problems: lack of strategies for constructing stable pores in HOFs and how to obtain high C2H6 selectivity. Herein, we have developed a microporous Mortise‐Tenon‐type HOF (MTHOF‐1, MT is short for Mortise‐Tenon structure) with a new self‐assembly mode for C2H4/C2H6 separation. Unlike previous HOFs which usually possess discrete head‐to‐head hydrogen bonds, MTHOF‐1 is assembled by unique consecutive side‐by‐side hydrogen bonds, which result in mortise‐and‐tenon pores decorated with orderly arranged amide groups and benzene rings. As expected, MTHOF‐1 exhibits excellent stability under various conditions and shows clear separation trends for C2H6/C2H4. The IAST selectivity is as high as 2.15 at 298 K. More importantly, dynamic breakthrough experiments have demonstrated that MTHOF‐1 can effectively separate the C2H6/C2H4 feed gas to obtain polymer‐grade C2H4 in one step even under high‐humidity conditions. [ABSTRACT FROM AUTHOR]

Three enantiopure isostructural sandwich-type clusters, LnIII3MnIII6(Ln = Dy (1), Tb (2) and Gd (3)) have been synthesized through reactions of a chiral Schiff-base ligand ((S,E)-4-(2-hydroxybenzylideneamino)-2-hydroxybutanoic acid, H3L) with manganese and lanthanide ions, showing intramolecular antiferromagnetic interaction. [ABSTRACT FROM AUTHOR]

A nanosized heterometallic cluster containing 60 La(iii) and 76 Ni(ii) ions, which are arranged into a four-shell, nest-like framework structure, was obtained by the hydrolytic reaction of the mixed La(NO3)3–Ni(NO3)2system using iminodiacetate as an ancillary ligand to control the hydrolysis. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A new family of trinuclear windwheel complexes with molecular formula [MII3(tpa)3(μ‐ttc)](ClO4)3·n(sol) (ttc = 1,3,5‐triazine‐2,4,6‐trithiol; tpa = tris(2‐pyridylmethyl)amine; M = Mn, n = 2, sol = CH3CN, 1; M = Co, n = 1, sol = CH3CN, 2; M = Ni, n = 0, 3) were synthesized and characterized. Single‐crystal X‐ray diffraction revealed that three metal centers in 1—3 are connected by ttc bridge, forming a regular triangular MII3 core. Each metal center is bonded by chelating S, N atoms from ttc and by N atoms from tpa. Magnetic studies showed that 1—3 displayed antiferromagnetic behavior and further gave the easy‐axis anisotropy (D = −0.77 cm−1 for 1 and −8.13 cm−1 for 2) and easy‐plane anisotropy (D = 5.08 cm−1 for 3). Moreover, 2 exhibited field‐induced slow magnetic relaxation behavior and their effective energy barriers were roughly evaluated Ueff = 6.9 K. [ABSTRACT FROM AUTHOR]

Water splitting based on first‐row transition metal (3d) photocatalysts is a cost‐effective technology for the conversion of abundant solar energy into useful energy on a large scale. The catalytic core of photosynthetic enzymes is a cubic CaMn4O5 cluster. Illuminated by natural photosynthesis, artificial solar water splitting photocatalysts composed of metal clusters are now being designed and tested. Ideally, such photocatalysts composed of atomically precise metal clusters with regular crystal structures are promising model catalysts that can be used to study structure–performance relationships. Recent advances based on metal cluster designs have improved our understanding of photoinduced charge separation and catalytic water redox reactions. This Minireview summarizes the recent advances in 3d metal cluster photocatalysts with well‐defined structures for photocatalytic water splitting and focuses on different clusters with tunable structures that are capable of achieving better photocatalytic properties. [ABSTRACT FROM AUTHOR]

Graphical abstract The synthetic strategy and building block about high-nuclearity lanthanide clusters are summarized, demonstrating the role of template anion in their assembly. Highlights • High-nuclearity lanthanide clusters, because of their unique physical and chemical properties and their potential application, have attracted great much attention in different fields. Owing to the final structures of the lanthanide clusters not only sensitive to starting materials used in the synthesis, but also to reaction conditions including metal ions/ligands ratio, pH, solvents, temperature, duration, rational design and synthesis of lanthanide clusters remains a great challenge. Thus, it is necessary to review the recent advance in the assembly of high-nuclearity lanthanide clusters. • In this review, the synthesis of high-nuclearity lanthanide clusters using the anion template strategy was outlined based on recently reported results. The presence of small anionic species appears to be essential as a template for modular build-up of higher-nuclearity cluster complexes. Compared with a single-anion template, the slow release of anions, multiple anions or mixed anions as templates is more conducive to the assembly of high-nuclearity lanthanide clusters because of their dispersive effect on the positive charges of the clusters. • Based on the structures of the lanthanide clusters recently achieved, the building blocks in the lanthanide clusters were analysed. Some of the high-nuclearity lanthanide clusters with sophisticated structures are assembled from two or more types of structural motifs. Using this building block strategy, abundant clusters featuring multiple combinations of these basic motifs have appeared at a fast rate. • Perspective in future study on the high-nuclearity clusters is discussed. For the rational design and synthesis of lanthanide clusters, future investigations should focus on the assembly mechanism of the lanthanide clusters, which not only being helpful to the rational design and construction of the high-nuclearity lanthanide clusters, but also to the properties study on the high-nuclearity lanthanide clusters. Abstract High-nuclearity lanthanide clusters have attracted much attention in different fields because of their unique physical and chemical properties and their potential applications. In this review, the synthetic strategy and building blocks for the assembly of high-nuclearity lanthanide clusters are outlined based on recently reported high-nuclearity lanthanide clusters. Perspectives for future studies on high-nuclearity lanthanide clusters are also discussed. We hope this review will provide insight into future research on high-nuclearity lanthanide clusters. [ABSTRACT FROM AUTHOR]

Heterometallic lanthanide–transition‐metal (4f–3d) clusters with well‐defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f–3d clusters Ln52Ni56 on a CdS photoabsorber surface. Interestingly, some Ni2+ ions in the clusters Ln52Ni56 were exchanged by the Cd2+ to form Ln52Ni56−xCdx/CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu52Ni56−xCdx cluster enable high visible‐light‐driven hydrogen evolution at 25 353 μmol h−1 g−1. This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f–3d clusters on semiconductor materials. Assembling lanthanide–transition‐metal (4f–3d) clusters Ln52Ni56 (Ln=Eu, Pr, Nd and Gd) onto CdS composites achieved enhanced photocatalytic H2 production. Some Ni2+ ions in the clusters were exchanged by Cd2+ to form Ln52Ni56−xCdx/CdS composites. An Eu52Ni56−xCdx/CdS species shows the highest activity of 25 353 μmol h−1 g−1 and an apparent quantum efficiency of 42.4 %. [ABSTRACT FROM AUTHOR]

Heterometallic lanthanide–transition‐metal (4f–3d) clusters with well‐defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f–3d clusters Ln52Ni56 on a CdS photoabsorber surface. Interestingly, some Ni2+ ions in the clusters Ln52Ni56 were exchanged by the Cd2+ to form Ln52Ni56−xCdx/CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu52Ni56−xCdx cluster enable high visible‐light‐driven hydrogen evolution at 25 353 μmol h−1 g−1. This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f–3d clusters on semiconductor materials. [ABSTRACT FROM AUTHOR]

The designed synthesis of chiral luminescent molecules with excellent circularly polarized luminescence (CPL) performance and high quantum yield (QY) levels has attracted great interest but remains very challenging. Herein, we report three pairs of chiral europium-titanium-oxo clusters featuring both modest CPL characteristics and high QY levels (up to 79%), which can be regulated by switching between different ligand substituents. [ABSTRACT FROM AUTHOR]

A series of Schiff base LH ((E)-2-((pyridin-2-ylmethylene)amino)phenol) supported phenoxo bridged symmetric [Dy2(L)2(hfac)4] (1), [Dy2(L)2(tfac)4] (2) and asymmetric [Dy2(L)2(thd)3(NO3)]·1.5H2O (3) binuclear complexes were isolated using differently substituted β-diketonate co-ligands (Hhfac = hexafluoroacetylacetonate, Htfac = trifluoroacetylacetonate, and Hthd = 2,2,6,6-tetramethyl-3,5-heptanedione). In all the three complexes 1–3, the two LH ligands provide phenoxo bridging and N-donor atoms. The {Dy2(μ2-O)2} magnetic core structures with LH ligands are found to be the same in 1–3 while the dissimilar functionalities of the axially coordinated different β-diketonate co-ligands play a crucial role in modulating the magnetic anisotropy of individual DyIII sites and magnetic exchange between them. The experimental static magnetic behaviour suggests the presence of intramolecular antiferromagnetic interactions in all the three complexes 1–3. The strength of the magnetic exchange coupling decreases with increasing magnetic anisotropy of individual DyIII ions from complex 1 to complex 3 and simultaneously their zero-field slow magnetic relaxation behaviors were found to increase with effective energy barriers (ΔE/kB) of 9.04 K, 24.06 K and 25.65 K, respectively. Furthermore, the DFT and ab initio theoretical calculations performed on the X-ray structures of complexes 1–3 support our experimental findings. [ABSTRACT FROM AUTHOR]

Porous supramolecular assemblies constructed by noncovalent interactions are promising for adsorptive purification of methane because of their easy regeneration. However, the poor stability arising from the weak noncovalent interactions has obstructed their practical applications. Here, we report a robust and easily regenerated polyhedron‐based cationic framework assembled from a metal–organic square. This material exhibits a very low affinity for CH4 and N2, but captures other competing gases (e.g. C2H6, C3H8, and CO2) with a moderate affinity. These results underpin highly selective separation of a range of gas mixtures that are relevant to natural gas and industrial off‐gas. Dynamic breakthrough studies demonstrate its practical separation for C2H6/CH4, C3H8/CH4, CO2/N2, and CO2/CH4. Particularly, the separation time is ≈11 min g−1 for the C2H6/CH4 (15/85 v/v) mixture and ≈49 min g−1 for the C3H8/CH4 (15/85 v/v) mixture (under a flow of 2.0 mL min−1), respectively, enabling its capability for CH4 purification from light alkanes. [ABSTRACT FROM AUTHOR]

Porous supramolecular assemblies constructed by noncovalent interactions are promising for adsorptive purification of methane because of their easy regeneration. However, the poor stability arising from the weak noncovalent interactions has obstructed their practical applications. Here, we report a robust and easily regenerated polyhedron‐based cationic framework assembled from a metal–organic square. This material exhibits a very low affinity for CH4 and N2, but captures other competing gases (e.g. C2H6, C3H8, and CO2) with a moderate affinity. These results underpin highly selective separation of a range of gas mixtures that are relevant to natural gas and industrial off‐gas. Dynamic breakthrough studies demonstrate its practical separation for C2H6/CH4, C3H8/CH4, CO2/N2, and CO2/CH4. Particularly, the separation time is ≈11 min g−1 for the C2H6/CH4 (15/85 v/v) mixture and ≈49 min g−1 for the C3H8/CH4 (15/85 v/v) mixture (under a flow of 2.0 mL min−1), respectively, enabling its capability for CH4 purification from light alkanes. [ABSTRACT FROM AUTHOR]

Five novel trinuclear nickel(II) clusters were successfully synthesized, namely Ni3(fshz)2(L)4·n(sol) (H3fshz = N-formylsalicylhydrazide; L = pyridine, n = 0, 1; L = 4-methylpyridine, n = 1, sol = CH3CN, 2; L = 4-ethylpyridine, n = 2, sol = CH3OH, 3; L = 4-vinylpyridine, n = 1, sol = CH3OH, 4; and L = 2,6-pyridinedimethanol, n = 2, sol = CH3OH, 5). Single-crystal X-ray diffraction revealed that the metallic skeletons of 1–5 were built by three Ni(II) ions, two fshz3− units, and four auxiliary ligands. The coordination geometry of the Ni(II) ions in 1–5 are followed in two modes: square-planar and/or octahedral. Magnetic studies showed that 1–5 displayed intermolecular antiferromagnetic behavior and all the square-planar Ni(II) ions were diamagnetic as certified. Moreover, 1–4 presented easy-axis anisotropy with D = −4.02, −5.31, −4.82, and −3.65 cm−1, respectively, while 5 presented easy-plane anisotropy (D = 11.06 cm−1) due to the different coordination mode. [ABSTRACT FROM AUTHOR]

The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. Herein we report the Gd44Co28 crown and Gd95Co60 cage, formulated as [Gd44Co28(IDA)20 (OH)72(CO3)12(OAc)28(H2O)64]⋅(ClO4)24 and [Na4Gd95 Co60(IDA)40(OH)150(CO3)40(OAc)58(H2O)164] ⋅ (ClO4)41 (H2IDA=iminodiacetic acid), respectively, by providing a library containing multiple low‐nuclearity units. The heart‐like units and crown‐like tetramer found in both compounds indicate unprecedented assembly levels, leading to an atypical geometry characteristic compared to the giant clusters directly assembled by regular units. These two clusters not only significantly increase the size of Ln−Co clusters but also exhibit the enhanced magnetic entropy change at ultra‐low temperatures. This work provided an effective way to fabricate cluster compounds with giant size and geometry complexity simultaneously. [ABSTRACT FROM AUTHOR]

The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. Herein we report the Gd44Co28 crown and Gd95Co60 cage, formulated as [Gd44Co28(IDA)20 (OH)72(CO3)12(OAc)28(H2O)64]⋅(ClO4)24 and [Na4Gd95 Co60(IDA)40(OH)150(CO3)40(OAc)58(H2O)164] ⋅ (ClO4)41 (H2IDA=iminodiacetic acid), respectively, by providing a library containing multiple low‐nuclearity units. The heart‐like units and crown‐like tetramer found in both compounds indicate unprecedented assembly levels, leading to an atypical geometry characteristic compared to the giant clusters directly assembled by regular units. These two clusters not only significantly increase the size of Ln−Co clusters but also exhibit the enhanced magnetic entropy change at ultra‐low temperatures. This work provided an effective way to fabricate cluster compounds with giant size and geometry complexity simultaneously. [ABSTRACT FROM AUTHOR]

Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi‐component building block [Ln3Ti(HSA)6(SA)4(H2O)]− ({Ln3Ti‐SA}, H2SA=salicylic acid, Ln=Eu/Gd) to form new building blocks {Ln3Tix‐MSA} (H2MSA=5‐methoxysalicylic acid, x=1, 2, 3) by constructing [Ti(MSA)3]2− units. The obtained {Ln3Tix‐MSA} can further assemble into a chiral Ln22Ti14 ring with the formulae [Eu22Ti14(MSA)48(HMSA)22(CH3COO)4(H2O)10(iPrOH)] and [Gd22Ti14(MSA)46(HMSA)26(CH3COO)4(H2O)8]. Parallel experiments without Ti4+ result in linear Ln chains. Detailed analysis shows that the [Ti(MSA)4]4− unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA)3]2− further triggers interesting chiral‐sorting behavior. Finally, the electronic adsorption and magneto‐optic responses of these molecular rings are investigated. [ABSTRACT FROM AUTHOR]

Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi‐component building block [Ln3Ti(HSA)6(SA)4(H2O)]− ({Ln3Ti‐SA}, H2SA=salicylic acid, Ln=Eu/Gd) to form new building blocks {Ln3Tix‐MSA} (H2MSA=5‐methoxysalicylic acid, x=1, 2, 3) by constructing [Ti(MSA)3]2− units. The obtained {Ln3Tix‐MSA} can further assemble into a chiral Ln22Ti14 ring with the formulae [Eu22Ti14(MSA)48(HMSA)22(CH3COO)4(H2O)10(iPrOH)] and [Gd22Ti14(MSA)46(HMSA)26(CH3COO)4(H2O)8]. Parallel experiments without Ti4+ result in linear Ln chains. Detailed analysis shows that the [Ti(MSA)4]4− unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA)3]2− further triggers interesting chiral‐sorting behavior. Finally, the electronic adsorption and magneto‐optic responses of these molecular rings are investigated. [ABSTRACT FROM AUTHOR]

[Display omitted] • Lanthanide-containing clusters (LnCC) as unique catalysts for water splitting and CO 2 conversion are summarized. • Typical examples are illustrated from structures-properties-mechanisms perspective. • The current challenges and the development prospects for LnCC catalysts are outlined. Water splitting and CO 2 conversion involving the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), overall water splitting, CO 2 reduction, and CO 2 chemical fixation are promising strategies to alleviate the energy crisis and excessive CO 2 emissions. Lanthanide-containing clusters (LnCCs) are emerging as unique catalysts for these reactions owing to their unparalleled advantages such as their unique electronic structures, high coordination numbers, abundant coordination geometries, and adjustable crystal structures. In this review, we summarize recent progress made in the catalytic application of LnCCs, including lanthanide clusters, lanthanide–transition metal clusters, lanthanide-cluster-based metal–organic frameworks, and cluster composites for water splitting and CO 2 conversion. In particular, we emphasize the synthesis, crystal structure, and catalytic mechanism of these complexes, as well as their synergistic effects in catalytic water splitting and CO 2 conversion reactions. Moreover, based on issues discovered in the current applications of LnCCs, we provide our own perspectives for future research in this field. [ABSTRACT FROM AUTHOR]

Threeisomorphic decanuclear heterometallic 3d–4f Ln2Cu8clusters, formulated as [Ln2Cu8(μ2-OH)2(μ3-OH)2(ClO4)2(HTMHSA)4(H2O)10]·15H2O (Ln = La (1,La2Cu8); Ln = Gd (2, Gd2Cu8); Ln = Dy (3, Dy2Cu8), H5TMHSA =3-[N-tris(hydroxymethyl)methylamino]-2-hydroxyprop-anesulfonicacid), were obtained through the reaction of H5TMHSA, Ln(ClO4)3, and Cu(NO3)2·3H2O. The present three Ln2Cu8compoundsare rare examples of alkylsulfonate-based polynuclear 3d–4fclusters. Magnetic studies indicate that the cluster La2Cu8exhibits antiferromagnetic behavior, Gd2Cu8displays ferromagnetic behavior and a large magnetocaloriceffect at low temperature, while Dy2Cu8showsslow magnetic relaxation. [ABSTRACT FROM AUTHOR]

Photosynthesis in nature uses the Mn4CaO5 cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo3 (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMn4O5 cluster. Anchoring LnCo3 on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo3/PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption spectroscopy revealed the transfer of a photoexcited electron and hole into the PCN and LnCo3 for hydrogen and oxygen evolution reactions, respectively. A density functional theory (DFT) calculation showed the cooperative water activation on lanthanide and O−O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of a bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting. [ABSTRACT FROM AUTHOR]

Here we report for the first time soluble lanthanide-transition-metal clusters Ln36Co12 (Ln = Eu, Gd and Dy) as effective homogeneous water oxidation electrocatalysts. The stable 48-metal Ln36Co12 clusters show an effective water oxidation activity under acidic conditions because of the synergistic effect between lanthanide and transition metals in O-O bond formation. [ABSTRACT FROM AUTHOR]

The assembly of gigantic heterometallic metal clusters remains a great challenge for synthetic chemistry. Herein, based on the slow release strategy of lanthanide ions and in situ formation of lacunary polyoxometalates, two giant 3d‐4f polyoxometalate inorganic clusters [LaNi12W35Sb3P3O139(OH)6]23− (LaNi12) and [La10Ni48W140Sb16P12O568(OH)24(H2O)20]86− (La10Ni48) are obtained. The nanoscopic inorganic cluster La10Ni48 possesses a super tetrahedron structure, which can be viewed as assembly from four LaNi12 molecules encapsulating a central [La6(SbO3)4(H2O)20]6+ octahedron core. This giant aesthetic La10Ni48 tetrahedron containing 214 metal ions is the largest 3d‐4f cluster reported thus far in polyoxometalate system. More interestingly, the LaNi12 and La10Ni48 display high stability in solution and La10Ni48 displays excellent proton conductivity. [ABSTRACT FROM AUTHOR]

A new family of heptanuclear lanthanide complex [Ln7(L)2(LH)4(dbm)5(OH)2(CH3OH)4]⋅xCHCl3⋅yCH3OH⋅zH2O {Ln=TbIII (1), DyIII (2) and ErIII (3) and LH3=(E)‐2‐(hydroxymethyl)‐6‐(((2‐hydroxyphenyl) imino) methyl)‐4‐methylphenol} [in 1, x=6, y=3, z=3; in 2, x=5, y=1, z=6; and in 3, x=4, z=2] has been prepared in presence of lanthanide chloride(III) salts and β‐diketonate co‐ligand dibenzoylmethane (dbm). Single crystal XRD reveals heptanuclear ensemble formed by collective action of two fully deprotonated [L]3− ligands, four double deprotonated [LH]2−, two μ3‐OH− ligands, five anionic [dbm]− β‐diketonate co‐ligands and two terminal methanol solvent molecules. This heptanuclear unit comprises of two [Dy4(μ2‐O)5(μ3‐OH)]+6 core sharing a common metal vertex Dy1 through which centre of inversion has passed for overall molecule. All the complexes have been magnetically characterized and dynamic AC magnetic studies reveals slow relaxation of magnetism present in dysprosium analogue (2). [ABSTRACT FROM AUTHOR]

A decanuclear cerium-oxo cluster CeIII 4 CeIV 6 featuring mixed valence was prepared by only using the trivalent cerium salt. Single-crystal structure and the distribution of Ce ions in different valence states are determined. The oxidation process and influencing factors of CeIII to CeIV was revealed. Based on the unique structure with mixed valence, the CeIII 4 CeIV 6 cluster exhibits efficient photocurrent response with photocurrent density 0.98 μA cm−2 at 0.5 V. [Display omitted] • A mixed valence cerium-oxo cluster CeIII 4 CeIV 6 only using the trivalent cerium salt was prepared. • The oxidation process of CeIII to CeIV in the initial reaction was revealed. • The unique structure and composition lead to the effective photocurrent response. Cerium-oxo clusters with mixed valence exhibit distinctive redox properties due to cerium ions switch between +3/+4 valence states. However, the design and synthesis of these clusters present formidable challenges, resulting in limited availability of such species, often necessitating the use of both CeIII and CeIV reactants. Herein, we successfully obtained a mixed valence cerium-oxo cluster CeIII 4 CeIV 6 (µ 3 -O) 4 (µ 4 -O) 4 (acac) 14 (CH 3 O) 6 (CH 3 OH) 2 (CeIII 4 CeIV 6 , Hacac = acetylacetone) through low-temperature crystallization only using the trivalent cerium salt. The coexistence as well as the distribution of Ce ions in different valence states have been determined from a multifaceted analysis. In addition, the stability of the synthesized cluster was confirmed by the HRESI-MS study through redissolution of the single crystal sample in fresh methanol. Importantly, Importantly, this study reveals the mechanism for the generation of +4 valence state. Under alkaline conditions, the presence of trace oxygen and the involvement of acetylacetone ligand facilitated the partial oxidation of CeIII to CeIV. The cluster CeIII 4 CeIV 6 has strong ultraviolet absorption and long visible light absorption. As the electrode precursor, CeIII 4 CeIV 6 showed clear photocurrent response and high photocurrent intensity due to CeIII/CeIV redox reaction. [ABSTRACT FROM AUTHOR]

Incorporating metal clusters within the skeleton of the organic polymers through a click reaction cannot only effectively prepare cluster–polymer composites, but also effectively avoid the cluster aggregation. Herein, an azide‐containing lanthanide–titanium oxo cluster of Eu8Ti10‐N3 (Eu8Ti10‐N3=[Eu8Ti10(μ3‐O)14(H2O)4(OAc)2(tbba)30(paza)4(THF)2]⋅4 THF⋅8 H2O (1), Htbba=4‐tert‐butylbenzoic acid, Hpaza=4‐azidobenzoate, HOAc=acetic acid, THF=tetrahydrofuran) through an in situ solvothermal reaction of 4‐azidobenzoic acid and 4‐tert‐butylbenzoic acid. Reaction of 1 with PEG (PEG=methoxypoly(ethyleneglycol)alkyne, 2000 g mol−1) through CuI‐catalyzed click chemistry generates a lanthanide–polymer composite of Eu8Ti10‐N3@PEG (2). Investigation with IR, 1H NMR and ICP‐OES of 2 indicates that the structural integrity of 1 is maintained in 2. Study of the luminescent properties of 1 and 2 reveals that the quantum yield of 1 itself basically remains unchanged in 2. Significantly, the formation of 2 cannot only effectively prevent the cluster 1 from aggregation, but also greatly enhance its solubility and adhesion to the substrate. Owing to the solubility and adhesion of luminescent materials being the key to their practical application, present work is thus of great significance for the development of metal cluster–polymer composite luminescent materials. [ABSTRACT FROM AUTHOR]

The formation mechanism of ferrihydrite is the key to understand its treatment of pollutants in waste water and purification of surface water and groundwater. Although emerging evidence suggests that formation of the ferrihydrite occurs through the aggregation of prenucleation clusters, rather than classical atom‐by‐atom growth, its formation mechanism remains unclear. Herein, an iron–oxo anionic cluster of [Fe22(μ4‐O)8(μ3‐OH)20(μ2‐OH)18(CH3COO)16(H2O)2]4− viewed as a dimer of bivacant β‐Keggin‐Fe13 clusters was for the first time obtained by using lanthanide ions as stabilizers. Upon dissolution in a mixed solution of isopropanol and water, the lacunary β‐Keggin‐Fe13 cluster can transform into an α‐Keggin‐Fe13 cluster, distinctly demonstrating that the Keggin‐Fe13 cluster rotational isomerization can be realized through the vacant Keggin‐Fe13 cluster. [ABSTRACT FROM AUTHOR]

Atomically precise molecular metal‐oxo clusters provide ideal models to understand metal oxide surfaces, self‐assembly, and form‐function relationships. Devising strategies for synthesis and isolation of these molecular forms remains a challenge. Here, the synthesis of four Ln‐Fe oxo clusters that feature the ϵ‐{Fe13} Keggin cluster in their core is reported. The {Fe13} metal‐oxo cluster motif is the building block of two important iron oxyhydroxyide phases in nature and technology, ferrihydrite (as the δ‐isomer) and magnetite (the ϵ‐isomer). The reported ϵ‐{Fe13} Keggin isomer as an isolated molecule provides the opportunity to study the formation of ferrihydrite and magnetite from this building unit. The four currently reported isostructural lanthanide‐iron‐oxo clusters are fully formulated [Y12Fe33(TEOA)12(Hyp)6(μ3‐OH)20(μ4‐O)28(H2O)12](ClO4)23⋅50 H2O (1, Y12Fe33), [Gd12Fe33(TEOA)12(Hyp)6(μ3‐OH)20(μ4‐O)32(H2O)12](ClO4)15⋅50 H2O (2, Gd12Fe33) and [Ln16Fe29(TEOA)12(Hyp)6(μ3‐OH)24(μ4‐O)28(H2O)16](ClO4)16(NO3)3⋅n H2O (Ln=Y for 3, Y16Fe29, n=37 and Ln=Gd for 4, Gd16Fe29n=25; Hyp=trans‐4‐Hydroxyl‐l‐proline and TEOA=triethanolamine). The next metal layer surrounding the ϵ‐{Fe13} core within these clusters exhibits a similar arrangement as the magnetite lattice, and Fe and Ln can occupy the same positions. This provides the opportunity to construct a family of compounds and optimize magnetic exchange in these molecules through composition tuning. Small‐angle X‐ray scattering (SAXS) and high‐resolution electrospray ionization mass spectrometry (HRESI‐MS) show that these clusters are stable upon dissolution in both water and organic solvents, as a first step to performing further chemistry towards building magnetic arrays or investigating ferrihydrite and magnetite assembly from pre‐nucleation clusters. [ABSTRACT FROM AUTHOR]

A photoactive MOF-based composite with simultaneously incorporated Ru-photosensitizer and Ni(II) molecular catalyst via a "ship-in-a-bottle" synthetic strategy, exhibits highly active, selective and robust, for photocatalytic CO 2 to CO conversion under visible-light illumination. Photocatalytic reduction of CO 2 to CO is a promising strategy for reducing atmospheric CO 2 levels and storing solar radiation as chemical energy. Here, we demonstrate that a molecular catalyst [NiII(bpet)(H 2 O) 2 ] successfully encapsulated into a highly robust and visible-light responsive metal–organic framework (Ru-UiO-67) to fabricate composite catalysts for photocatalytic CO 2 reduction. The composite Ni@Ru-UiO-67 photocatalysts show efficient visible-light-driven CO 2 reduction to CO with a TON of 581 and a selectivity of 99% after 20-h illumination, because of the facile electron transfer from Ru-photosensitizer to Ni(II) active sites in Ni@Ru-UiO-67 system. The mechanistic insights into photoreduction of CO 2 have been studied based on thermodynamical, electrochemical, and spectroscopic investigation, together with density functional theory (DFT) calculations. This work shows that encapsulating molecular catalyst into photoactive MOF highlights opportunities for designing efficient, stable and recyclable photocatalysts. [ABSTRACT FROM AUTHOR]

Syntheses, structures, and magnetic properties of two hexanuclear [5×1 + 1×1] lanthanide cocrystal complexes [Ln5(L)4(LH2)2(tfa)4]·[Ln(tfa)4]·2CH3OH [Ln = Dy(1) and Tb(2)] derived from the polyhydroxy ligand 2‐(hydroxymethyl)‐6‐carbaldehyde‐4‐methylphenol (LH2) are reported. Compounds 1 and 2 crystallize in the triclinic system with space group P1. X‐ray crystallography reveals that 1 and 2 are cocrystals comprising one cationic pentanuclear [Ln5(L)4(LH2)2(tfa)4]+ unit and one anionic mononuclear [Ln(tfa)4]–unit as well as two molecules of methanol as solvent of crystallization. Both complexes form a [2.2] spirocyclic topology fashioned core due to merging of two triangular geometries composed of Ln(III) ions through a common vertex. The central Ln(III) ion in the spirocyclic pentanuclear assembly is eight‐coordinate with distorted square antiprism geometry. On the other hand, the peripheral eight‐coordinate Ln(III) ions are in a distorted trigonal dodecahedron geometry. The comprehensive magnetic study reveals that compound 1 displays slow relaxation of magnetism. [ABSTRACT FROM AUTHOR]

Abstract: A building blocks strategy is an effective approach for constructing the large molecular systems. Herein, we demonstrate that high‐resolution electro‐spray ionization mass spectrometry (HRESI‐MS) provides an effective chance to insight the assemble process of the building blocks and guides the construction of high‐nuclearity metal clusters on the basis of the reaction of Ti(OiPr)4, Eu(acac)3, and salicylic acid. The time‐dependent HRESI‐MS indicates that not only a Eu3Ti building block can be formed, but that it can further assemble into a Eu24Ti8 compound. Temperature‐dependent HRESI‐MS reveals that increase of the reaction temperature favors the formation and crystallization of the stable Eu24Ti8 structure. Single‐crystal structural analysis demonstrates that the Eu24Ti8 has a wheel‐like structure with diameter of ca. 4.1 nm and is the highest nuclearity lanthanide‐titanium oxo cluster reported to date. [ABSTRACT FROM AUTHOR]

Abstract: A building blocks strategy is an effective approach for constructing the large molecular systems. Herein, we demonstrate that high‐resolution electro‐spray ionization mass spectrometry (HRESI‐MS) provides an effective chance to insight the assemble process of the building blocks and guides the construction of high‐nuclearity metal clusters on the basis of the reaction of Ti(OiPr)4, Eu(acac)3, and salicylic acid. The time‐dependent HRESI‐MS indicates that not only a Eu3Ti building block can be formed, but that it can further assemble into a Eu24Ti8 compound. Temperature‐dependent HRESI‐MS reveals that increase of the reaction temperature favors the formation and crystallization of the stable Eu24Ti8 structure. Single‐crystal structural analysis demonstrates that the Eu24Ti8 has a wheel‐like structure with diameter of ca. 4.1 nm and is the highest nuclearity lanthanide‐titanium oxo cluster reported to date. [ABSTRACT FROM AUTHOR]

Four high-nuclearity lanthanide–transition metal clusters, formulated as [Ln45M7(OH)68(CO3)12(CH3COO)26(CH3CH2COO)6(H2O)70]·(ClO4)25·(H2O)x (abbreviated as Ln45M7: 1, Gd45Co7; 2, Gd45Ni7; 3, Dy45Co7; 4, Dy45Ni7; x≈ 50), were obtained with the mixed protecting ligands acetate and propionate. Structural analysis shows that the cluster cationic core contains 52 metal ions featuring a bowl-like structure. 12 CO32− and 3 ClO4− anions play the role of mixed anion templates. Magnetic studies reveal that the two isotropic Gd-containing clusters Gd45Co7 and Gd45Ni7 exhibit a large magnetocaloric effect (MCE), while the anisotropic Dy-containing clusters Dy45Co7 and Dy45Ni7 show slow relaxation of magnetization. [ABSTRACT FROM AUTHOR]

The largest Ln-Fe metal cluster [Gd12Fe14(μ3-OH)12(μ4-OH)6(μ4-O)12(TEOA)6(CH3COO)16(H2O)8]⋅(CH3COO)2(CH3CN)2⋅(H2O)20 ( 1) and the core-shell monodisperse metal cluster of 1 a@SiO2 ( 1 a=[Gd12Fe14(μ3-OH)12(μ4-OH)6(μ4-O)12(TEOA)6(CH3COO)16 (H2O)8]2+) were prepared. Experimental and theoretical studies on the magnetic properties of 1 and 1 a@SiO2 reveal that encapsulation of one cluster into one silica nanosphere not only effectively decreases intermolecular magnetic interactions but also significantly increases the zero-field splitting effect of the outer layer Fe3+ ions. [ABSTRACT FROM AUTHOR]

The largest Ln-Fe metal cluster [Gd12Fe14(μ3-OH)12(μ4-OH)6(μ4-O)12(TEOA)6(CH3COO)16(H2O)8]⋅(CH3COO)2(CH3CN)2⋅(H2O)20 ( 1) and the core-shell monodisperse metal cluster of 1 a@SiO2 ( 1 a=[Gd12Fe14(μ3-OH)12(μ4-OH)6(μ4-O)12(TEOA)6(CH3COO)16 (H2O)8]2+) were prepared. Experimental and theoretical studies on the magnetic properties of 1 and 1 a@SiO2 reveal that encapsulation of one cluster into one silica nanosphere not only effectively decreases intermolecular magnetic interactions but also significantly increases the zero-field splitting effect of the outer layer Fe3+ ions. [ABSTRACT FROM AUTHOR]

A series of heterometallic 3d–4f compounds, formulated as [Ln2Ni2(dcta)2(H2O)8(NO3)2]·8H2O (Ln = Nd (1); Ln = Dy (2)); {[DyNi(dcta)(H2O)6]·Cl·(H2O)2}n (3); {[LnNi(dcta)(H2O)6]·(ClO4)·(H2O)3}n (Ln = La (4); Ln = Nd (5)); {[Gd12Ni12(dcta)12(H2O)24]·[Ni(H2O)6]3·(ClO4)18·(H2O)80}n (6) and {[La12Ni12(dcta)12(H2O)60]·[Ni(H2O)6]3·(ClO4)18·(H2O)30}n (7), (H4dcta = trans-1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid), have been obtained through a metalloligand strategy. Structural analysis reveals that [Ni(dcta)]2− acts as a bidentate metalloligand in 1–3, tridentate metalloligand in 4 and 5, and tetradentate metalloligand in 6 and 7. These compounds can be divided into four types according to the dimensionality of the structures. Compounds 1 and 2 are 0D tetranuclear clusters comprised of symmetric [LnNi(dcta)]2 12-membered rings, compound 3 is a 1D chain which is reinforced by hydrogen bonds. Compounds 4 and 5 possess an infinite 2D layer structure with a 63-hcb topology, and compounds 6 and 7 are two 3D frameworks constructed by face-sharing Keplerate-type metal–organic polyhedra. It is interesting that different anions lead to different topology structures. The magnetic properties and thermal stabilities of them are also studied. [ABSTRACT FROM AUTHOR]

Monodisperse metal clusters provide a unique platform for investigating magnetic exchange within molecular magnets. Herein, the core-shell structure of the monodisperse molecule magnet of [Gd52Ni56(IDA)48(OH)154(H2O)38]@SiO2 ( 1 a@SiO2) was prepared by encapsulating one high-nuclearity lanthanide-transition-metal compound of [Gd52Ni56(IDA)48(OH)154(H2O)38]⋅(NO3)18⋅164 H2O ( 1) (IDA=iminodiacetate) into one silica nanosphere through a facile one-pot microemulsion method. 1 a@SiO2 was characterized using transmission electron microscopy, N2 adsorption-desorption isotherms, and inductively coupled plasma-atomic emission spectrometry. Magnetic investigation of 1 and 1 a revealed J1=0.25 cm−1, J2=−0.060 cm−1, J3=−0.22 cm−1, J4=−8.63 cm−1, g=1.95, and z J=−2.0×10−3 cm−1 for 1, and J1=0.26 cm−1, J2=−0.065 cm−1, J3=−0.23 cm−1, J4=−8.40 cm−1 g=1.99, and z J=0.000 cm−1 for 1 a@SiO2. The z J=0 in 1 a@SiO2 suggests that weak antiferromagnetic coupling between the compounds is shielded by silica nanospheres. [ABSTRACT FROM AUTHOR]

Monodisperse metal clusters provide a unique platform for investigating magnetic exchange within molecular magnets. Herein, the core-shell structure of the monodisperse molecule magnet of [Gd52Ni56(IDA)48(OH)154(H2O)38]@SiO2 ( 1 a@SiO2) was prepared by encapsulating one high-nuclearity lanthanide-transition-metal compound of [Gd52Ni56(IDA)48(OH)154(H2O)38]⋅(NO3)18⋅164 H2O ( 1) (IDA=iminodiacetate) into one silica nanosphere through a facile one-pot microemulsion method. 1 a@SiO2 was characterized using transmission electron microscopy, N2 adsorption-desorption isotherms, and inductively coupled plasma-atomic emission spectrometry. Magnetic investigation of 1 and 1 a revealed J1=0.25 cm−1, J2=−0.060 cm−1, J3=−0.22 cm−1, J4=−8.63 cm−1, g=1.95, and z J=−2.0×10−3 cm−1 for 1, and J1=0.26 cm−1, J2=−0.065 cm−1, J3=−0.23 cm−1, J4=−8.40 cm−1 g=1.99, and z J=0.000 cm−1 for 1 a@SiO2. The z J=0 in 1 a@SiO2 suggests that weak antiferromagnetic coupling between the compounds is shielded by silica nanospheres. [ABSTRACT FROM AUTHOR]

[Display omitted] • Two lanthanide − titanium oxo clusters EuTi 9 and TbTi 9 protected by four kinds of ligands were prepared. • The EuTi 9 and TbTi 9 cluster core containing ten metal ions shows pyramid-like structure. • EuTi 9 and TbTi 9 display the temperature-dependent luminescence properties. Two pyramid-like lanthanide − titanium − oxo clusters formulated as LnTi 9 (µ 2 -O) 5 (µ 3 -O) 7 (µ 3 -OH) 2 (O i Pr)(acac) 2 (TCA) 10 (THF) (LnTi 9 , Ln = Eu / Tb, HTCA = 2-thiophenecarboxylic acid) were prepared through the reaction of Ln(acac) 3 , 2-thiophenecarboxylic acid (HTCA), Ti(O i Pr) 4 and THF. The 10-nuclearity-metal-core [LnTi 9 (µ 2 -O) 5 (µ 3 -O) 7 (µ 3 -OH) 2 ]13+ is protected by four kinds of ligands. EuTi 9 and TbTi 9 exhibit characteristic emissions of Eu3+ / Tb3+ under ultraviolet excitation. The temperature-dependent luminescence results show EuTi 9 shows a good linear relationship between the luminescence intensity and temperature range of 80–320 K, while TbTi 9 has high temperature-sensitivity in different temperature ranges. [ABSTRACT FROM AUTHOR]

Two high-nuclearity 3d–4f clusters Ln24Zn4 (Ln = Gd and Sm) featuring four Ln6 octahedra encapsulating a Zn4 tetrahedron were obtained through the self-assembly of Zn(OAc)2 and Ln(ClO4)3. Quantum Monte Carlo (QMC) simulations show the antiferromagnetic coupling between Gd3+ ions. Studies of the magnetocaloric effect (MCE) show that the Gd24Zn4 cluster exhibits the entropy change (−ΔSm) of 31.4 J kg−1 K−1. [ABSTRACT FROM AUTHOR]

Two enantiomorphic 3D lanthanide coordination polymers of {[Dy5(L)4(H2O)10][Dy(H2O)7][Na(H2O)5]}·(ClO4)7·(H2O)15 (1a for R and 1b for S) with chiral helical chains were synthesized based on an achiral ligand N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid (H3L) and Dy(ClO4)3. Crystal analysis revealed that 1a and 1b were crystallized in chiral space groups P4132 and P4332, respectively. The absolute configurations of the two structures were evidenced by vibrational circular dichroism (VCD) spectra with one single crystal sample. [ABSTRACT FROM AUTHOR]

Metal--organic frameworks (MOFs) and related material classes are attracting considerable attention for their applications in gas storage/separation as well as catalysis. In contrast, research concerning potential uses in electronic devices (such as sensors) is in its infancy, which might be due to a great challenge in the fabrication of MOFs and semiconductor composites with well-designed structures. In this paper, we proposed a simple self-template strategy to fabricate metal oxide semiconductor(@MOF core--shell heterostructures, and successfully obtained freestanding ZnO@ZIF-8 nanorods as well as vertically standing arrays (including nanorod arrays and nanotube arrays). In this synthetic process, ZnO nanorods not only act as the template but also provide Zn2+ ions for the formation of ZIF-8. In addition, we have demonstrated that solvent composition and reaction temperature are two crucial factors for successfully fabricating well-defined ZnO@ZIF-8 heterostructures. As we expect, the as-prepared ZnO@ZIF-8 nanorod arrays display distinct photoelectrochemical response to hole scavengers with different molecule sizes (e.g., H2O2 and ascorbic acid) owing to the limitation of the aperture of the ZIF-8 shell. Excitingly, such ZnO@ZIF-8 nanorod arrays were successfully applied to the detection of H2O2 in the presence of serous buffer solution. Therefore, it is reasonable to believe that the semiconductor@MOFs heterostructure potentially has promising applications in many electronic devices including sensors. [ABSTRACT FROM AUTHOR]

The CoII/CoIII (9:1) mixed compounds (III) and the NiII compounds (V) are isostructural and crystallize in the monoclinic space group P21/m with Z = 2 (single crystal XRD). [ABSTRACT FROM AUTHOR]

Compounds (IV) containing cationic Ln24Zn4 cluster cores crystallize in the cubic space group Fm $\bar 3$m with Z = 8 (single crystal XRD). [ABSTRACT FROM AUTHOR]