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In this research, indium ions were introduced into polyoxoniobates (PONbs) reaction systems to facilitate the construction of different {SiNb18O54}-based aggregates, including an {In(en)2{SiNb18O54}2} (en = ethylenediamine) dimer, an {[InO2][In2(en)O3]2{SiNb18O54}3} trimer, and an {[In(en)2][InO2][In7(en)5O9]{SiNb18O54}4} tetramer. Interestingly, these aggregates were further assembled into three uncommon extended PONb architectures in the presence of [Cu(en)2]2+complexes, namely, H3[Cu(en)2(H2O)][Cu(en)2]6[Cu(en)2]2{[In(en)2][K2{SiNb18O54}(H2O)6]2}·1.5en·16H2O, H9{[Cu(en)2]6{[Cu(en)2]3[Cu(en)2(H2O)][In(H2O)2][In2(en)(H2O)2(OH)]2{SiNb18O54}3}·5en·29H2O, and H14[Cu(en)2]0.5[Cu(en)2(H2O)]{[Cu(en)2]2{[Cu(en)2]3[Cu(en)2(H2O)]5[K(H2O)2][In(H2O)2][In(en)2][In7(OH)9(en)5]{SiNb18O54}4}·7en·39H2O. In addition, all of them have good water vapor adsorption capacities and moderate proton transport capabilities. The above results indicate that introducing suitable heteroatoms to induce the aggregation PONb building blocks and further assembling them into new structures is an effective strategy to enrich the PONbs’ structural diversity and develop new functional materials.

A new inorganic–organic hybrid polyoxoboroniobate {H4K2[Cu(cis-en)2(H2O)]9[Cu(cis-en)2]6[Cd2(cis-en)2(trans-en)][LiB2Nb29O86]2·79H2O} (1, en = ethylenediamine), is built from pagoda-shaped {LiB2Nb29O86} clusters, linear {Cd2(cis-en)2(trans-en)} bridging units, and copper-amine complexes. The {LiB2Nb29O86} cluster represents the first example of combining oxoboron clusters with polyoxoniobate clusters (PONbs). It consists of an unusual HPONb fragment {LiNb18O54}, a fused-ring structural boroniobate cluster {B2Nb5O13}, and a classical Lindqvist {Nb6O19} fragment. The {Cd2(cis-en)2(trans-en)} and [Cu(cis-en)2]2+complexes link the pagoda-shaped {LiB2Nb29O86} clusters into 1D infinite ladder chains. This is the first instance of simultaneous coordination of the cis-en and trans-en ligands with a single metal cation in the inorganic–organic hybrid PONb family. Furthermore, 1exhibits good proton conductivity.

In this work, a novel organodiphosphate-containing inorganic–organic hybrid polyoxoniobate (PONb) ring {(PO3CH2CH2PO3H)4Nb8O16}4–(Nb8P8) has been achieved by a one-pot hydrothermal method. The ring is constructed from a tetragonal {Nb8O36} motif and four {PO3CH2CH2PO3H} ligands. Interestingly, Nb8P8can be joined together via K–H2O clusters {K2(H2O)4(OH)2} to form one-dimensional chains {[K2(H2O)4(OH)2]Nb8P8}nand further linked by {Cu(en)2}2+(en = ethylenediamine) complexes, resulting in a three-dimensional supramolecular framework {[Cu(en)2]2[K2(H2O)4(OH)2]Nb8P8}·3en·H2O (1). 1exhibits good chemical and thermal stability and has a high water vapor adsorption capacity of ≤224 cm3g–1(22.71 mol·mol–1) at 298 K, outperforming most of the known polyoxometalate-based materials. Impedance measurements prove that 1can transfer protons with moderate conductivity. This study not only contributes to the structural diversity of organodiphosphate-containing PONbs and PONb rings but also provides a reference for the development of PONb-based materials with unique performance.

By variation of the amount of GeO2, two organic–inorganic hybrid germanoniobate frameworks with 6-connected pcuand 10-connected bcttopologies were constructed from peanut-shaped {α-Ge12Nb38} and {β-Ge12Nb38} clusters, respectively. The {α-Ge12Nb38} and {β-Ge12Nb38} clusters contain the most Ge centers of germanoniobates reported so far. The compounds exhibit proton conduction properties with a conductivity of 3.04 × 10–4S·cm–3for 1and 1.62 × 10–4S·cm–3for 2at 85 °C and 98% RH. The water vapor adsorption capacities for 1and 2are 5.86 and 4.40 mmol·g–1, respectively.

A 3D Co(III)-complex hybrid polyoxoniobate framework Na10(H2O)36[Co2(phen)2(4,4′-bipy)(Nb6O19)2]·19H2O (1) has been constructed from [Co2(phen)2(4,4′-bipy)(Nb6O19)2]10–dimer units and 2D inorganic Na–O cluster layers. The Co(III) centers are coordinated with {Nb6O19}, 4,4′-bipy and phen simultaneously. The [Co2(phen)2(4,4′-bipy)(Nb6O19)2]10–fragments link the Na–O cluster layers to generate a 3D metal complex-modified hybrid polyoxoniobate framework with π–π interactions between phenanthroline rings. Compound 1shows reversible thermochromic behavior resulting from electron transfer from {Nb6O19} to 4,4′-bipy and subsequent formation of radical products, which is first observed in polyoxoniobates. Furthermore, the compound exhibits stable nonvolatile storage behavior and rewritable resistive switching with a low switching voltage (1.12 V) and high current on/off ratio (1.18 × 103) along with stable cyclic performance during stability test for 200 cycles. Charge-transfer mechanism has been studied by analyzing the relationship between current and voltage in the process of resistance switching.

A unique heteropolyoxotantalate (hetero-POTa) cluster [P2O7Ta5O14]7–(P2Ta5) was first developed using pyrophosphate as a key to open the ultrastable skeleton of the classical Lindqvist-type [Ta6O19]8–precursor. The P2Ta5cluster can serve as a general and flexible secondary building unit to create a family of brand-new multidimensional POTa architectures. This work not only promotes the limited structural diversity of hetero-POTa but also provides a practical strategy for new extended POTa architectures.

An oxalate-assisted lanthanide (Ln) incorporation strategy is first demonstrated for creating rare high-nuclearity Ln-containing polyoxoniobates (PONbs). With the strategy, a series of high-nuclearity Ln-containing PONbs of 50-nuclearity Dy2Nb48, 103-nuclearity Dy7Nb96, 200-nuclearity Dy10Nb190, and 206-nuclearity Dy14Nb192have been made, showing an increasingly large structure evolution from Dy2Nb48monomer to Dy7Nb96dimer and to distinct Dy10Nb190and Dy14Nb192tetramers. Among them, Dy14Nb192presents the largest heterometallic PONb and also the PONb with the greatest number of Ln ions reported thus far. Interestingly, both giant Dy14Nb192and Dy10Nb190molecules can further undergo single-crystal to single-crystal intermolecular aggregations, forming infinite {Dy14Nb192}∞and {Dy10Nb190}∞chains, respectively. The former structural transformation shows a reversible humidity-dependent aggregation–disaggregation process accompanied by a proton conductivity response, while the latter structural transformation is irreversible. These new species largely enrich the very limited members of Ln-containing PONb family and offer rare examples for studying structural transformations between giant molecular aggregates and infinitely extended structures at the atomic level.

A stable 3d–4fheterometallic cluster, namely, {Dy4Ni5L10(NO3)4(CO3)4(CH3OH)2}·CH3CN (Dy4Ni5, HL = 8-hydroxyquinoline), has been solvothermally synthesized and structurally characterized. The compound exhibits an interesting structure in which a tetrahedron based on 4fions interpenetrates with a square pyramid based on 3dions. Besides, a unique intermolecular interaction was found in Dy4Ni5, giving rise to its high stability not only when it is in the solid state but also when it dissolves in organic solvents. In addition, the magnetic behavior of solid Dy4Ni5and the magneto-optical activity of the Dy4Ni5solution were also studied.

The search for polyoxometalate-based catalysts has long attracted interest. Being designable in structure, stable and effective, polyoxoniobate-based catalysts have an exciting prospect for industrial applications. This paper not only summarizes recent advances in classic polyoxoniobate-catalyzed reactions, including chemical warfare agents and organic dyes degradation, epoxidation reactions, photocatalytic hydrogen evolution and base-catalyzed reactions but also discusses some representative cases and the speculative mechanism related to structures. In addition, the current challenges and perspectives in the fabrication of more efficient and promising polyoxoniobate-based catalysts are also presented.

A rare 3D Indium-containing polyoxoniobate framework {H9[Cu(en)2(H2O)2][Cu(en)2]12[In(en)]5[Nb23–O65(OH)3(H2O)2]{Nb24O67(OH)2(H2O)3]2}·68H2O(1), based on the In-containing polyoxoniobate cluster, {[In(en)]5[Nb23O65(OH)3(H2O)2][Nb24O67(OH)2(H2O)3]2}35–({In5Nb71}) and [Cu(en)2]2+linkers has been successfully synthesized. The nest-like cluster {In5Nb71} is constructed from one brand-new V-shaped {Nb23O70}, two triangle-shaped {Nb24O72} and five [In(en)]3+. The [In(en)] fragments link {Nb24O72} and {Nb23O70} units into unique {In5Nb71}nhelical pillars. The copper-amine complexes connect the {In5Nb71}nhelical pillars into a three-dimensional (3D) inorganic–organic hybrid In–Cu-containing framework. This material also exhibits good ionic conductivity and vapor adsorption capacity properties.

A rare 3D porous inorganic–organic polyoxoniobate framework based on the cubic polyoxoniobate-cupric-complex cage {[Cu(en)2]@{[Cu2(en)2(trz)2]6(Nb68O188)}} (1a), has been successfully synthesized by a hydrothermal method. The cubic cages 1aare connected with 4-(tetrazol-5-yl)pyridine to form a 1D pillar-like chain structure, and every 1D pillar-like chain is further linked with four adjacent pillar-like chains by the [Cu(en)2]2+complex to form a 3D porous inorganic–organic polyoxoniobate framework with 4-connected CdSO4-type topology. To our knowledge, it is the first time that three different types of organic ligands are simultaneously introduced into one polyoxoniobate. This material also exhibits a high vapor adsorption capacity and good ionic conductivity properties.

The discovery of novel high-nuclearity oxo-clusters considerably promotes the development of cluster science. We report a high-nuclearity oxo-cluster-based compound with acid/alkali-resistance and radiation stabilities, namely, (H3O)7[Cd7Sb24O24(l-tta)9(l-Htta)3(H2O)6]·29H2O (FJSM-CA; l-H4tta = l-tartaric acid), which features a two-dimensionally anionic layer based on the largest Sb-oxo-clusters with 28-metal-ion-core [Cd4Sb24O24]. It is challenging to efficiently capture Sr2+, Ba2+(analogue of 226Ra), and [UO2]2+ions from aqueous solutions due to their high water solubility and environmental mobility, while it is unprecedented that a novel Sb-oxo-cluster-based framework material FJSM-CA can efficiently remove these hazardous ions accompanied with intriguing structural transformations. Especially, it shows fast ion-exchange abilities for Sr2+, Ba2+, and [UO2]2+(reaches equilibrium within 2, 10, and 20 min, respectively) and high exchange capacity (121.91 mg/g), removal rate R(96%), and distribution coefficient KdU(2.46 × 104mL/g) for uranium. Moreover, the underlying mechanism is clearly revealed, which is attributed to strong electrostatic interactions between exchanged cations and highly negative-charged frameworks and the strong affinity of (COO)−groups for these cations. Proton conduction of the pristine and Sr2+, Ba2+, [UO2]2+-loaded products was investigated. This work highlights the design of new oxo-cluster-based materials for radionuclide remediation and proton conduction performance.

A series of 3D porous lanthanide-substituted polyoxometalate frameworks, Na2[Ln2(H2O)11]2[Ln3(H2O)3(α-SiW11O39)2]2·69H2O (1-Ln, Ln = Sm, Eu, Gd, Tb, and Dy), are built from novel hexadecahedral {Ln6W8O28} heterometallic cage-shaped clusters. Intriguingly, every tetrameric {[Ln3(H2O)3(α-SiW11O39)2]2}14–cage-cluster is linked with another eight tetrameric cage-clusters by Ln3+cations, leading to a novel 3D inorganic porous framework, which exhibits good thermal and chemical stability, excellent water vapor adsorption capacity, and moderate proton conductive properties. Furthermore, the solid state luminescence spectra demonstrate that 1-Sm, 1-Eu, 1-Tb, and 1-Dydisplay the lanthanide characteristic emission bands. The temperature-dependent magnetic susceptibility indicates that there are antiferromagnetic interactions in 1-Tband 1-Dy.

Ln-containing polyoxoniobates (PONbs) have appealing applications in luminescence, information encryption and magnetic fields, but the synthesis of PONbs containing high-nuclearity Ln-O clusters is challenging due to the easy hydrolysis of Ln3+ions in alkaline environments. In this paper, we are able to integrate CO32−and high-nuclearity Ln-O clusters into PONb to construct an inorganic giant Eu19-embedded PONb H49K16Na13(H2O)63[Eu21O2(OH)7(H2O)5(Nb7O22)10(Nb2O6)2(CO3)18]·91H2O (1), which contains the highest nuclearity Eu-O clusters and the largest number of Eu3+ions among PONbs. In addition, the film that was prepared by mixing 1with gelatin and glycerol, exhibits reversible luminescence switching behavior under acid/alkali stimulation and has been used to create a fluorescence-encoded information approach. This work paves a feasible strategy for the construction of high-nuclearity Ln-O cluster-containing PONbs and the expansion of the application of Ln-containing PONbs in information encryption.

Two novel heterometallic organic frameworks built from trinuclear indium and cuprous halide clusters, [(In3O)2(Cu2I2)3(ina)12(H2O)6](NO3)2·7DMA·10H2O (1) and [NH2(CH3)2][In3(OH)2(H2O)2(ina)8(Cu4I4)2]·5DMA·8H2O (2), where Hina = isonicotinic acid, have been successfully constructed with the orientation of the ina ligand. 1shows a fascinating highly porous honeycomb-like 3D cationic framework with a trigonal-bipyramid-type cage based on a planar [In3O(CO2)6]+trimer and a rhombohedral Cu2I2cluster. Comparably, 2displays a 3D negative network with irregular hexagonal channels constructed from a [In3(OH)2(CO2)8]−trimer and a cubane-like Cu4I4cluster. Especially, 1displays a reversible I2adsorption/release performance with high adsorption capacity, whose mechanism has been disclosed by theoretical simulation. Also, the green/red emission of 2stems from iodocuprate centers with quenched indium-centered emission.

Here, a case of bilayer heterojunction Pd-containing polyoxotungstate (POW), connecting a Te3Pd3ring and an Anderson-like TeW6cluster, has been synthesized. The Anderson-like cluster is the first example in POW. The coordination of Pd in the ring with the S atom on the sulfo group breaks the traditional coordination configuration of Pd and O in polyoxometalates (POMs), enriching the structural types of Pd-containing POMs. In addition, the hybrid bilayer heterojunction structure at the molecular level not only provides high thermal stability but also results in spatial arrangement anisotropy, leading to up to five times the anisotropic proton conductivity.

An unusual crystalline porous framework constructed from four types of cages, including all-inorganic Keggin-type polyoxometalate (POM) cages [H3W12O40]5–, organic hexamethylenetetramine (Hmt) cages, nanosized silver-Hmt coordination cages, and giant POM-silver-Hmt cages, was hydrothermally synthesized and structurally characterized. The framework features a highly symmetrical structure with one-dimensional nanoscale channels and holds good thermal/solvent stability, which endow it with proton conduction properties and heterogeneous catalytic activity for pyrazole. This paper not only contributes to broadening the structural diversity of cage-based crystalline porous framework materials but also sheds new light on the design of new functional framework materials.

An extremely long ribbon-shaped polyoxometalate (POM) octamer, {Eu16Co7Se16W128O448(CIT)10(HCIT)2(NO3)4(OH)4(H2O)52} (H4CIT = citric acid), with a maximum length of ca. 6 nm has been obtained, which is the longest molecular POM reported to date and the first Dawson-based 3d–4f-containing selenotungstate(IV). The nanoscale octamer is built from 8 new Dawson-type Eu2W2-substituted selenotungstates {(Eu2W2O4)Se2W14O52} bridged by 12 H4CIT ligands and 3 Co2+ions, giving rise to a rare giant inorganic–organic hybrid molecular POM with more than 150 metal centers (7 CoII, 16 EuIII, 16 SeIV, and 128 WVI). Especially, with 128 W centers and more than 800 non-H atoms, the POM octamer also represents the largest known 3d–4f-containing polyoxotungstate.

A rare and novel Cr-substituted polyoxoniobate (PONb), [Cr2.5Nb27.5O66(OH)20(H2O)2]7–, has been synthesized by a combination of hydrothermal and conventional solution methods. The PONb shows an unknown tetrameric structure, which is the largest Cr-containing PONb to date. Interestingly, every two PONb tetramers can be joined together by alkali-metal cations to form a discrete cubelike ionic cluster. The obtained PONb not only enriches the very limited members of the Cr-substituted PONb family but also exhibits high ionic conductivity.

By adopting trilacunary [A-α-GeW9O34]4–as precursor under hydrothermal conditions, two novel polyoxometalates (POMs) substituted by crescent-shaped Ln5clusters, namely, Na4K4(H2pip)6(H2O)10{Ln10(μ3-OH)2(H2O)10[α(1,8)-GeW10O38]2[β(4,11)-GeW10O38]2}·29H2O (1-Lafor Ln = La, 1-Cefor Ln = Ce, pip = piperazine) were successfully synthesized. The one-dimensional chains of two lanthanide substituted POMs are constructed from edge-sharing of nanoclusters with size of 2.5 × 2.9 × 1.0 nm3, which contain two crescent-shaped five-nuclearity Ln5clusters and two [β(4,11)-GeW10O38]12–polyanions. Furthermore, 1-Laexhibits good ion-conducting performance with proton conduction activation energy of 0.49 eV, which follows vehicular mechanism. 1-Ceillustrates anti-ferromagnetic behavior, which can be attributed to spin–orbital coupling interactions within the crescent-shaped Ln5clusters.

The assemblies of a p-conjugated organic luminophore ligand (p-tr2Ph) and d10transition metal cations produce two metal–organic frameworks (MOFs), [Zn(μ4-p-tr2Ph)(μ2-NO3)]·NO3(1), and {[Cd2(μ4-1,4-BDC)2(μ4-p-tr2Ph)(μ2-DMF)(H2O)2]}·2H2O (2) (p-tr2Ph = 1,4-phenylene-4,4′-bis(1,2,4-triazole), DMF = N,N′-dimethylformamide, 1,4-H2BDC = 1,4-dicarboxybenzene). Compound 1is a new three-dimensional (3D) cationic framework with left-handed helical channels constructed from a right-handed helical chain [Zn(μ2-tr)2(μ2-NO3)]n. Compound 2possesses a 3D 3-fold interpenetrated neutral framework with one-dimensional distorted hexagonal channels in each MIL-88 type single-net. The compounds 1and 2both exhibit blue fluorescence. Notably, the intensity-based luminescent thermometer measurements reveal that compound 2is extremely more linear with temperature, has finer reversibility within three cycles, and a wider temperature range than those of compound 1, indicating that compound 2is a more desirable low-temperature detector.

A rare porous metal-phosphonocarboxylate framework with ultrahigh thermal stability over 500°C was obtained, which can be transformed into three different cluster-based frameworks with the same CaF2-type topology.

Four seven-nuclearity 3d-4f heterometallic cluster {Fe6LnO28} substituted polyoxometalates (HPz)11K4Fe6Ln(μ3-O)2(B-α-GeW9O34)2(GeW6O26)·xH2O (1-Ln, Pz = piperazine, Ln = Tb, Dy, Ho, Er for x= 27, 25, 25, 24, respectively) have been hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectrometry, thermogravimetric analyses, elemental analyses, and electrospray ionization mass spectrometry. Single-crystal X-ray diffraction analyses revealed that 1-Lncontain an unprecedented banana-shaped polyanion constructed from an iron-lanthanide heterometallic {Fe6LnO28} cluster, two trilacunary {B-α-GeW9O34} units, and one hexalacunary {GeW6O26} fragment. The magnetic susceptibility surveying proved the presence of antiferromagnetic coupling in 1-Ln.

The integration of lanthanide (Ln) ions and polyoxoniobates (PONbs) is challenging, and the known Ln-substituted PONbs are still scarce. This work introduces high-nuclear iso-Ln-oxo clusters into the PONb system. The first series of high-nuclear Ln-oxo clusters encapsulated heterometallic polyoxoniobates H9[Na(H2O)4][Cu(en)2]10{Ln6(μ3-OH)6(SiNb18O54)3}∙18H2O (1-Ln, en = ethylenediamine, Ln = Dy, Gd, Tb, Ho, Er, Tm, Yb, Lu) based on flower-like {Ln6(µ3-OH)6(SiNb18O54)3} ({Ln6Si3Nb54}) clusters have been successfully synthesized viaone-pot hydrothermal synthesis strategy. The flower-like polyoxoanion {Ln6Si3Nb54} is consisted of three heteropolyoxoniobate {SiNb18O54} clusters and one unique planar equilateral triangle-shaped {Ln6(μ3-OH)6} cluster, which presents the highest nuclear iso-Ln-oxo cluster in PONb chemistry. In {Ln6(μ3-OH)6} cluster, each pair of μ3-OH groups link three Dy3+ions to form a small approximate equilateral triangle-shaped {Dy3(OH)2} cluster. Furthermore, the three {Dy3(OH)2} clusters comprise a bigger approximate equilateral triangle-shaped {Dy6(μ3-OH)6} cluster. The reported hexanuclear {Ln6} cluster skeletons are mostly octahedral, however, such equilateral triangle-shaped skeleton of the hexanuclear Ln-oxo cluster is first observed. The 1-Dyexhibits good water vapor adsorption capacity and ferromagnetic properties.

The two novel cluster organic frameworks based on heterometallic supertetrahedral cluster secondary building units (SBUs) [Cd4Cu6(L)4(Ac)7(H2O)4](Ac)·7H2O (1) and [Mn4Cu6(L)4(Ac)4.5(H2O)9]CuCN(Ac)3.5·H2O (2), where H3L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol and Ac = CH3COO–, have been prepared under solvothermal conditions. 1and 2are the first cases of cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral cluster SBUs. Furthermore, 1and 2show an integration of magnetic properties and adsorption properties from both the heterometallic cluster secondary building units and the framework in a porous material.

Two novel cluster–organic frameworks based on the 12-nuclearity manganese-cluster secondary building unit (SBU), [MnIII4MnII8(L)4(Ac)8(MeO)2(μ5-O)2(H2O)4](Ac)2·16H2O (1) and [MnIII4MnII8(L)4(Ac)8(MeO)2(μ5-O)2(H2O)4](Ac)2·12H2O (2), where Ac = CH3COO–and MeO = CH3O, have been constructed from solvothermal reactions of the 3-nuclearity manganese cluster [Mn3(μ3-O)(Ac)6(py)3](ClO4) (Mn3, where py = pyridine) with a tripodal alcohol ligand containing a 4-pyridyl group. 1and 2represent the first examples of metal–organic frameworks containing 12-nuclearity manganese-cluster SBUs. In addition, 1exhibits an integration of the porosity and magnetic properties from both the framework and cluster in a porous material.

The development of core-shell nanoclusters with controllable composition is of utmost importance as the material properties depend on their constituent elements. However, precisely tuning their compositions at the atomic scale is not easily achieved because of the difficulty of using limited macroscopic synthetic methods for atomic-level modulation. In this work, we report an interesting example of precisely regulating the core composition of an inorganic core-shell-type cobalt polyoxoniobate [Co26Nb36O140]32−by controlling reaction conditions, in which the inner Co-core composition could be tune while retaining the outer Nb-shell composition of resulting product, leading to a series of isostructural species with a general formula of {Co26-nNb36+nO140} (n = 0-2). These rare species not only can display good powder and single-crystal proton conductivities, but also might provide helpful and atomic-level insights into the syntheses, structures and composition modifications of inorganic amorphous core-shell heterometal oxide nanoparticles.

Three high‐nuclearity Ni‐substituted polyoxotungstates (POTs)—[Ni(enMe)2(H2O)2]2[Ni(H2O)6]2‐ [Ni(enMe)2][Ni(H2O)2]1.5[HNi20X4W34‐ (OH)4O136(H2O)6(enMe)8]⋅11 H2O (3), [Ni(en)2(H2O)]2[H8Ni21X4W34(OH)4‐ O136(en)10(H2O)5]⋅22 H2O (4), and [Ni‐(enMe)2]2[H6Ni22X4W34(OH)4O136(H2O)6(enMe)10]⋅18 H2O (5), in which en=ethylenediamine, enMe=1,2‐diaminopropane, X=0.5 P+0.5 Ge—were made under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The structures of 3–5can be viewed as novel derivatives of [H6Ni20P4W34(OH)4O136(enMe)8‐ (H2O)6]⋅12 H 2O (1) and [Ni(en)2‐ (H2O)]2[H8Ni20P4W34(OH)4O136(en)9‐ (H2O)4]⋅16 H 2O (2), which both contain 20 nickel ions per structural unit. Compound 3is the first example of a 1D cluster chain constructed from Ni20‐substituted polyanions [HNi20X4‐ W34(OH)4O136(H2O)6(enMe)8]11−and [Ni(enMe)2]2+bridges. Compound 4is a novel cluster–organic chain built by Ni21‐substituted polyanions [H8Ni21X4W34(OH)4O136(en)10(H2O)5]4−and en molecule bridges. Compound 5is a discrete POT with 22 Ni centers, and is not only the largest nickel‐substituted POT, but also contains the highest number of nickel ions in one polyanion to date. Magnetic measurements illustrate that overall ferromagnetic interactions exist in 1–5. The magnetic behavior of 1and 2was theoretically simulated by the MAGPACK magnetic program package.

Indium‐Bausteine: Die Entdeckung eines dimeren und eines supertrimeren Indiumclusters in fünf porösen Indium‐organischen Gerüsten offenbart ein System hinter Indium‐Bausteinen und ihrer Kooperation und Konkurrenz bei der Kristallisation chiraler und achiraler poröser Strukturen. Eines dieser Materialien enthält das kleinstmögliche organische Kation zum Ladungsausgleich und verfügt über eine sehr große Langmuir‐Oberfläche.