Search

Two isomeric zeolite-like metal–organic frameworks with the formula of [(CH3)2NH2][Cd(TPO)]·xsolvent were successfully prepared and characterized. Both frameworks are constructed from tetrahedral TPO3− nodes and tetrahedrally connected Cd2+ nodes, representing rare examples of zeolite-like MOFs with an isomeric characteristic. Moreover, one of the frameworks shows mechanically responsive luminescence emission after the crystals are ground for different times. Additionally, it has permanent porosity, and can selectively adsorb CO2 over N2.

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 b...

In this work, two rare high-dimensional polyoxoniobates with formulas of H9 [Cu(en)(H2 O)2 ][Cu(en)2 ]8 [Dy(H2 O)4 ]3 [Nb24 -O69 (H2 O)3 ]2 ⋅ 36H2 O (1) and H9 K[Cu(en)2 (H2 O)]5 [Cu(en)2 ]4 -[Eu(H2 O)4 ]3 [Nb24 O69 (H2 O)3 ]2 ⋅ 2en ⋅ 45H2 O (2) have been obtained under hydrothermal conditions. These extended materials are constructed from lanthanide-incorporated triangular-prism-like polyoxoniobate secondary building units (SBUs) {[Ln(H2 O)4 ]3 [Nb24 O69 (H2 O)3 ]2 } (Ln=Dy, Eu). 1 and 2 represent the first examples of high-dimensional polyoxometalate materials based on such lanthanide-incorporated triangular-prism-like polyoxoniobate SBUs. Furthermore, the proton conduction property and the luminescent emission of these materials were evaluated.

A rare 3D porous chiral polyoxoniobate framework, [Cu(en)2(H2O)]2{[Cu(en)]4[Cu(en)2]5 {[Cu(en)2KNb24O72H10]2}·6en·70H2O(1) (en = ethylenediamine) based on two types of isomeric {Cu(en)2KNb24O72H10} clusters (α-CuKNb24 and β-CuKNb24) has been synthesized by a hydrothermal reaction. Interestingly, the α-CuKNb24 and β-CuKNb24 clusters are connected by cupric complexes to form chiral helical pillars with left-handedness (L-α-CuKNb24) and right-handedness (R-β-CuKNb24). To our knowledge, compound 1 is the first polyoxometalate-based MOF with a 4-connected neb-type topology structure within polyoxometalate chemistry. This compound also exhibits proton conduction and strong water vapor adsorption properties.

Two organic–inorganic hybrid polyoxotungstogermanates, HK7(H2O)6(C6H16N2)6-[Fe(C6H14N2)Dy(H2O)2Fe2(B-α-GeW9O34)(GeW7O29)]2·14H2O (1) and (Hphen)2[Fe(phen)3]2[Dy(phen)Fe(B-α-GeW9O34)]2 (2) (C6H14N2 = trans-1,2-cyclohexanediamine, phen = 1,10-phenanthroline), containing organic ligand chelated Fe–Dy heterometallic clusters have been successfully synthesized under hydrothermal conditions. Compound 1 contains a cable-like structural fragment which consists of a centrosymmetric “S”-shaped K7O14 cluster and a centrosymmetric “S”-shaped organic ligand chelated Fe–Dy heterometallic cluster substituted tungstogermanate, {[Fe(C6H14N2)Dy(H2O)2Fe2(B-α-GeW9O34)(GeW7O29)]2}20−. Compound 2 possesses a sandwich structure which contains two trilacunary [B-α-GeW9O34]10− units and one {(phen)DyFeO6}2 cluster in the middle layer. Both compounds have magnetic properties, with compound 1 having frequency dependent magnetic properties.

The combination of polyoxoniobates (PONbs) with 3d metal ions, azoles, and organoamines is a general synthetic procedure for making unprecedented PONb metal complex cage materials, including discrete molecular cages and extended cage frameworks. By this method, the first two PONb metal complex cages K4 @{[Cu29 (OH)7 (H2 O)2 (en)8 (trz)21 ][Nb24 O67 (OH)2 (H2 O)3 ]4 } and [Cu(en)2 ]@{[Cu2 (en)2 (trz)2 ]6 (Nb68 O188 )} have been made. The former exhibits a huge tetrahedral cage with more than 120 metal centers, which is the largest inorganic-organic hybrid PONb known to date. The later shows a large cubic cage, which can act as building blocks for cage-based extended assembly to form a 3D cage framework {[Cu(en)2 ]@{[Cu2 (trz)2 (en)2 ]6 [H10 Nb68 O188 ]}}. These materials exhibit visible-light-driven photocatalytic H2 evolution activity and high vapor adsorption capacity. The results hold promise for developing both novel cage materials and largely unexplored inorganic-organic hybrid PONb chemistry.

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-Dy display the lanthanide characteristic emission bands. The temperature-dependent magnetic susceptibility indicates that there are antiferromagnetic interactions in 1-Tb and 1-Dy.

During the past two decades, the search of strategies to introduce polyoxometalate (POM) clusters as secondary building units (SBUs) to construct porous extended POM-organic frameworks (POMOFs) and discrete POM-organic polyhedra (POMOPs) have attracted sustained interests because such materials not only integrate the advantages of both POMs and framework/polyhedra structures, but also exhibit good prospects in photo-/electro-catalysis, separation, molecular recognition, host-guest chemistry and so on. In this review, the recent advancements of POMOFs and POMOPs, including their assembly methodologies, classification and related applications are summarized. Moreover, the current challenges in the design and fabrication of POMOFs and POMOPs as well as the great potential in these two areas are also discussed.

This work reported an unpresented rare-earth-ion bearing metal–organic framework (MOF) Y10(C8H4O4)6(CO3)3(OH)12 built of inorganic slabs as structural units. Eu3+ has been introduced into the latti...

Two unique heterometallic cluster organic frameworks, [Cd4 MnIII 4 MnII 6 (Tri)4 (CH3 COO)14 (μ4 -O)2 (μ3 -O)2 (H2 O)2 ] Cd(H2 O)2 ⋅9 H2 O (1) and Cu[Cd5 Cu6 (Tri)4 (CH3 COO)9 (H2 O)4 ]2 (CH3 COO)3 ⋅24 H2 O (2) (H3 Tri=2-(hydroxymethyl)-2-(pyridine-4-yl)-1,3-propanediol), have been successfully prepared by employing a bifunctional tripodal alcohol ligand as a structure-directing agent. Crystal structure analyses reveal that 1 represents a rare example of frameworks constructed from Cd-Mn heterometallic chains, and 2 is the first heterometallic MOF based on highest-nuclear Cd-Cu heterometallic cluster building blocks. Furthermore, the magnetic properties and gas adsorption abilities of 1 and 2 were systematically studied.

By introduction of trilacunary Keggin-type polyoxometalate to the hydrothermal reaction system of Cr3+, Ln3+ and phthalic acid, a series of novel {Cr4Ln4} heterometallic clusters with the formula Cs2[Cr4Ln4(μ4-O)4(μ3-O)4(C8H4O4)4(H2O)12](H3SiW12O40)Cl·23H2O (1-Ln, Ln = Ce, Pr, Nd) and [Cr4Ln4(μ4-O)4(μ3-O)4(C8H4O4)4(H2O)10](H6SiW12O40)Cl2·18H2O (2-Ln, Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er) have been obtained. Single-crystal structural analyses show that 1-Ln and 2-Ln constitute the first cases of Cr–Ln heterometallic clusters stabilized by inorganic polyoxometalate anions and organic ligands. Optical spectra studies demonstrate that 1-Ln and 2-Ln are narrow-gap semiconductors with band gaps of about 1.5 eV. Magnetic investigation shows that compound 2-Dy is a potential single molecule magnet.

A series of new Ln14-substituted polyoxometalates, H27Na16[(Ln14(H2O)W4(OH)O14)(WO4)4(GeW10O38)6]·nH2O (n ≈ 86) (1-Ln, Ln = Eu, Gd, Tb, Dy, Ho, Er), which contain 14 Ln3+ and 6 {α(1,5)-[GeW10O38]12−} units, has been synthesized in one-pot reactions. As the first 14-Ln-containing polyoxometalates, the octahedron-shaped three-shell structure of the [(Ln14(H2O)W4(OH)O14)(WO4)4(GeW10O38)6]43− polyanion is made up of a W4 tetrahedron, a Ln14W4 tetrahedron and a Ge6W60 octahedron. Compound 1-Dy exhibits frequency dependent magnetic properties. Compounds 1-Eu, 1-Tb and 1-Dy exhibit the characteristic emission bands of the Ln3+ ion.

The first two inorganic-organic hybrid three-dimensional (3D) polyoxotantalates (POTas) and the first two inorganic-organic hybrid 2D POTas have been obtained. All of these high-dimensional POTas are built from a new-type POTa dimeric cluster {Cu(en)(Ta6O19)}2/{Cu(enMe)(Ta6O19)}2 (en = ethylenediamine, enMe = 1,2-diaminopropane) bridged by copper complexes. Interestingly, extended POTas 1 and 3 can undergo single-crystal to single-crystal structural transformations triggered by water.

A nested Cu24@Cu72 copper-organic framework, [Cu5(bdc)4(ina)2(H2O)3]·solvent (1, H2bdc = 1,3-benzenedicarboxylic acid and Hina = isonicotinic acid) based on paddlewheel Cu2(COO)4 SBUs, has been synthesized. There are three types of cages with different sizes and shapes: Cu24-cage, Cu60-cage and Cu72-cage. The Cu72-cage, which is the highest-nuclearity Cu-cage reported to date, encapsulates a Cu24-cage to form a double-walled Cu24@Cu72 cage-within-cage structure. Dye adsorption studies reveal that compound 1 can rapidly and selectively adsorb cationic dyes.

A tetratellurium-substituted heteropolyoxoniobate with the formula K2H[Cu(phen)(H2O)]4[Cu(phen)]2[(LiNb8Te4O40)]·34H2O (1; phen = 1,10-phenanthroline) was hydrothermally prepared and structurally characterized. The compound represents the first hexavalent tellurium-substituted Keggin-type polyoxometalate (POM) so far. What is more, the POM cluster in 1 can elaborately self-assemble into a stable supramolecular framework with an ion conduction property through unique intermolecular π-π stacking.

Two novel molecules TAP and TAH with pronounced reversible halochromic properties have been synthesized and fully characterized. Their butterfly-like structures have been confirmed through single-crystal X-ray diffraction. Their UV-Vis absorption after protonation dramatically red-shifted with naked-eye-visible color change in a very dilute concentration of 10-5 M. Note that the original color of the solution can be recovered after the neutralization with a base. Ministry of Education (MOE) Q.Z. acknowledges financial support from AcRF Tier 1 (RG 111/17,RG 2/17, RG 114/16,RG 113/18)and Tier 2 (MOE2017-T2-1-021and MOE 2018-T2-1-070),Singapore.X.L. thank the support from the National Natural Science Foundation of China(21676188) and the Science and Technology Plan Project of Tianjin(19ZXNCGX00020).J.Z. acknowledges financial support from Na-tional Natural Science Foundation of China, Grant Nos. 21773016.QZ also thanks the support from State Key Laboratory of Supramolecular Structure and Materials, Jilin University (sklssm2020041)

Preparing low-dimensional perovskite materials with novel building units is highly desirable because such materials have already been demonstrated to show unusual physical properties. In this report, we first reported a new and unusual two-dimensional perovskite framework, [B(HIm)4]4Pb13Br38 (1), constructed from novel Lindqvist-type [Pb6Br19]7- nanoclusters. The as-prepared material shows good water resistance and chemical/heat stability. More importantly, 1 has been proven to exhibit temperature/excitation-wavelength-dependent emission. A possible mechanism has been provided. Ministry of Education (MOE) Accepted version Q. Zhang acknowledges financial support from AcRF Tier 1 (RG 2/17, RG 111/17, RG 8/16, RG 114/16) and Tier 2 (MOE 2017- T2-1-021), Singapore. Q. Xiong gratefully acknowledges the financial support from Singapore Ministry of Education via AcRF Tier 1 grants (RG 194/17 and RG 113/16).

The assemblies of a p-conjugated organic luminophore ligand (p-tr2Ph) and d10 transition 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 1 is 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 2 possesses a 3D 3-fold interpenetrated neutral framework with one-dimensional distorted hexagonal channels in each MIL-88 type single-net. The compounds 1 and 2 both exhibit blue fluorescence. Notably, the intensity-based luminescent thermometer measurements reveal that compound 2 is extremely more linear with temperature, has finer reversibility within three cycles, and a wider temperature range than those of compound 1, indicating that compound 2 is a more desirable low-temperatur...

This work demonstrates that the use of high-negative and high-symmetry lacunary polyoxometalates (POMs) for the clustering of alkali metal ions is a feasible strategy not only for the formation of rare high-nuclearity alkali-metal clusters but also for the construction of new-type all-inorganic ionic porous materials. By the strategy, an unprecedented high-nuclearity K-H2 O cluster {K42 (H2 O)60 } with core-shell K6 @K36 configuration is stabilized by 8 C3v -symmetry trivacant POMs [GeW9 O34 ]10- , forming a novel giant ionic alkali-metal-POM composite cluster {K42 Ge8 W72 O272 (H2 O)60 } with more than 100 metal centers. The incorporated 42-nuclearity K-H2 O cluster {K42 (H2 O)60 } exhibits the highest-nuclearity alkali-metal-water cluster known to date in POM chemistry. Further, the giant {K42 Ge8 W72 O272 (H2 O)60 } clusters can be linked by another kind of alkali metal ions Na+ to generate a fascinating three-dimensional all-inorganic ionic porous framework with high chemical stability, proton conductivity, and water vapor adsorption.

Success in obtaining higher-order twistarenes with precise structures is very important for fundamentally understanding the relationship between the structures and physical properties/optoelectronic applications. In this research, by using the advantages from a retro-Diels-Alder process (clean reaction) and the cross-conjugated nature of the pyrene unit, a novel dodeca-twistarene was prepared for the first time. Its structure, confirmed by single-crystal XRD analysis, indicates that it possesses a twisted angle (≈30°), and two neighboring molecules in the crystal lattice are perpendicular to each other because of the twisted character and the strong intermolecular CH-π interactions. However, its basic physicochemical properties suggest its instability in air derives from its elevated HOMO energy level, although NICS calculations confirm that the pyrene units contribution poorly to the π conjugation of the overall molecule. Ministry of Education (MOE) Accepted version Q.Z acknowledges financial support from AcRF Tier 1 (RG 111/17, RG 2/17, RG 114/16, RG 8/16) and Tier 2 (MOE 2017- T2-1-021), Singapore. Dr. Liu acknowledges funding support from M4062018.

Two unprecedented examples of cluster organic frameworks (TBA)3Cu[V6O13(L)2]2·4DEF (2) (TBA)Ag[V6O13(L)2] solvent (3) (TBA = tetrabutylammonium, H3L = tris(hydroxymethyl)-4-picoline, DEF = N, N'-diethylformamide) based on Lindqvist-type polyoxometalate (POM) secondary building units (SBUs) have been constructed successfully. Compounds 2 and 3 are the second cases of cluster organic frameworks based on Lindqvist-type POM cluster SBUs. Furthermore, the cluster organic framework of 2 exhibits efficient electrocatalytic activity and strong durability in oxygen reduction reaction.

A protein-sized (ca. 4.2×4.2×3.6 nm3 ) non-biologically derived molecule {Nb288 O768 (OH)48 (CO3 )12 } (Nb288 ) containing up to 288 niobium atoms has been obtained, which is by far the largest and the highest nuclearity polyoxoniobate (PONb). Particularly, in terms of metal nuclearity number, Nb288 is the second largest cluster so far reported in classic polyoxometalate chemistry (V, Mo, W, Nb, and Ta). Nb288 can be described as a giant windmill-like cluster aggregate of six nanoscale high-nuclearity PONb units {Nb47 O128 (OH)6 (CO3 )2 } (Nb47 ) joined together by six additional Nb ions. Interestingly, the 47-nuclearity Nb47 units generated in situ can be isolated and bridged by copper complexes to form an inorganic-organic hybrid three-dimensional PONb framework, which exhibits effective catalytic activity for hydrolyzing nerve agent simulant of dimethyl methylphosphonate. The unique Nb47 cluster also provides a new type of topology to very limited family of Nb-O clusters.

A rare porous zinc-organic framework with ultrahigh thermal stability over 500 °C was obtained, which exhibits a CaF2-type topology formed by 8-connected tetranuclear Zn4 clusters and 4-connected phosphonocarboxylate ligands. Interestingly, the similar reactions to the zinc-organic framework but in the absence of H2O or by the replacement of Zn2+ with Co2+ can yield three different 3D cluster-based frameworks but 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-Ln contain 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.

Two rare mixed-cluster-organic frameworks (CH3NH3)3[Cu4-(μ3-O)2(Lb)4][MnMo6O18(La)2]·4NMF·5H2O (1) and [(CH3)2NH2]3[Co5-(μ3-O)2(Lb)6]-[MnMo6O18(La)2]·5DMF (2) (La = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol; Lb = 4-(2-(4-pyridyl)ethenyl) benzoic acid; NMF = N-methylformamide; DMF = N,N-dimethylformamide) have been obtained, exhibiting the first two porous materials simultaneously integrating polyoxometalates and transition-metal–oxygen clusters as secondary building units (SBUs).

A series of heterometallic cluster organic frameworks based on cuprous-halide Cu4I4 clusters and lanthanide clusters, [Ln2(H2O)8]2(Cu4I4)(pdc)4][NO3]4·solvent (1-Ln, Ln = Y, Tb, Eu, H2pdc = 3,5-pyridinedicarboxylic acid), have been successfully synthesized under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1-Ln show fascinating three-dimensional porous framework structures constructed from two dissimilar types of nanosized coordination cages. Gas sorption measurements indicate that 1-Ln show moderate gas uptake capacities. The UV/vis spectroscopy measurements reveal that 1-Ln are a class of potential materials for the removal of Cr2O72− from aqueous solution. Additionally, the luminescence properties of 1-Tb and 1-Eu have also been investigated.

Two zeolite-like cluster organic frameworks based on Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units have been successfully constructed under solvothermal conditions, namely, Cu[Cd4Cu6(L)4(H2O)18](Ac)9⋅DMA⋅3 H2O (1), and Cu[Mn4Cu6(L)4(Ac)3(H2O)12](Ac)6⋅CH3CN⋅13 H2O (2), where H3L=2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol, Ac=CH3COO−, DMA=N,N′-dimethylacetamide. Single-crystal X-ray structural analysis reveals that both 1 and 2 exhibit 3-dimensional zeolite-like architectures with similar 4-connected components, but possess definitely different topologies of diamondoid (dia) and uncommon lonsdaleite (lon), respectively. 1 and 2 represent the first cases of zeolite-like cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units. Furthermore, the magnetic properties and porous nature of 1 and 2 were also studied.

A series of the highest-nuclearity polyoxoniobate (PONb) nanoclusters ranging from dimer, trimer, to tetramer have been obtained. They include one 114-nuclearity {Li8⊂Nb114O316}, one 81-nuclearity {Li3K⊂Nb81O225}, and one 52-nuclearity {H4Nb52O150}. The Nb nuclearity numbers of these PONbs are remarkably larger than those of all known high-nuclearity PONbs (≤ 32). Furthermore, the introduction of 3d Cu2+ ions can lead to the generation of extended inorganic-organic hybrid frameworks built from novel, high-nuclearity, nanoscale heterometallic PONb building blocks {H3Cu3Nb78O222} or {H3Cu4(en)Nb78O222}. These building blocks also contain the largest number of Nb centers of any heterometallic PONbs reported to date. The synthesis of new-type PONbs has long been a challenging subject in PONb chemistry. The achievement of these record high-nuclearity PONbs with diverse structures represents an exciting progress in PONb chemistry.

Four indium-based heterometallic metal-organic frameworks In3M(IMDC)3(NO3)2(H2O)6*solvent (2-M, M = Mn, Co, Zn, Mg, H3IMDC = imidazole-4,5-dicarboxylic acid) have been made under solvothermal conditions, and characterized by single-crystal X-ray diffractions, energydispersive X-ray spectroscopy, infrared spectroscopy, thermogravimetric analysis and powder X-ray diffractions. Structural analysis indicates that 2-M exhibit 3-dimensional porous frameworks generated by linking three intersected 1-dimensional In-IMDC helical chains with different M2+ ions, respectively. Powder X-ray diffractions reveal that 2-M exhibit good thermal and water stability. What's more, 2-M show moderate gas adsorption abilities that can be modulated by introducing different M2+ ions. Finally, the solid-state luminescent emissions of 2-M are also elucidated at room temperature.

The first two tetra-Sc-substituted polyoxotungstates H2K2Na2[Sc4(H2O)10(B-β-SbW9O33)2]·21H2O (1) and H20K2Na6[Sc4(C2O4)4(B-β-SbW9O33)2][Sc4(H2O)2(C2O4)4(B-β-SbW9O33)2]·64H2O (2) have been synthesized and characterized by IR spectroscopy, AC impedance measurements, TG, PXRD, and single-crystal X-ray diffractions. Compound 1 represents an isolated inorganic sandwich-type dimeric POM constructed from two trilacunary Keggin [B-β-SbW9O33]9 − moieties and four Sc3 + ions, while compound 2 shows an extended organic–inorganic hybrid POM which composes of two kinds of distinct tetra-Sc-substituted polyoxotungstate building units and oxalate ligands. Notably, these two compounds also are the first Sc-containing polyoxotungstates based on trilacunary Keggin [B-β-SbW9O33]9 − clusters. Electrochemical study showed that compound 2 has good proton conductivity.

Two new inorganic frameworks HLa(H2O)5[La(H2O)6]2[La(H2O)2(GeW11O39)]2·7H2O (1) and HK(H2O)La3(H2O)15[La(H2O)3(GeW11O39)]2·38H2O (2) based on 1:1 type lanthanide-substituted polyoxometalates (LSPs) have been synthesized under hydrothermal reactions. Compounds 1 and 2 are characterized by single-crystal X-ray diffraction analysis, thermogravimetry analysis, infrared spectroscopy and X-ray powder diffraction analysis. Interestingly, Compounds 1 and 2 can be selectively obtained by simply controlling the reaction temperatures under similar conditions. Both 1 and 2 are three-dimensional structures built from lanthanide-substituted polyoxoanions [La(H2O)n(GeW11O39)]5 − building blocks. Furthermore, the ion-conducting properties of 1 and 2 were investigated.

Polyoxoniobate [GeNb18O54]14 − and polyniobotungstate [Nb3W3O19]5 − are firstly found to co-crystallize at the same crystal to form a rare organic–inorganic hybrid polyoxometalate H[Cu(en)2(H2O)]8[Cu(en)2(H2O)2]2{K4[Cu(en)2]2[Cu(en)2(GeNb18O54)]2}[Nb3W3O19]·32H2O (1). Interestingly, in 1, the crescent-shaped polyoxoanions [GeNb18O54]14 − can form dimeric secondary building units (SBUs) {[GeNb18O54]2[K2(H2O)5]2} via the linkage of K+ cations. These dimeric SBUs can be further bridged by copper complexes to generate 1D infinite double strand chains with completely different isolated polyoxoanions [Nb3W3O19]5 − filling the gaps between chains.

A metal-organic cage (termed FJI-C9) based on six square-shaped Cu 2 (CO 2 ) 4 paddle-wheel building units and eight flexible 1,3,5-trimethyl-2,4,6-tris(3-phenoxymethyl)benzoic acid (TTBA) linkers has been constructed. The porous FJI-C9 containing large cage of 1.5 nm shows high CO 2 adsorption uptake.

Two novel vanadogermanates [Cd(en)(H2O)2][Cd(en)2][Cd(en)]{[Cd(en)]2[Ge8V12O42.5(OH)5]}·2H2O (1) and [Cd(en)3][Cd(en)]2{[Cd(en)]2[Ge8V12O42(OH)6]}·10H2O (2, en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analysis, infrared spectroscopy, powder X-ray diffractions, thermogravimetric analysis, UV–vis spectroscopy, and single-crystal X-ray diffractions. Structural analysis reveals that the Ge–V–O cluster anions in the two compounds are derived from the classical saturated {V18O42} cluster by replacing four VO5 square pyramids with four Ge2O7 groups. Especially, the Ge–V–O cluster anion in 2 is a new configuration of Ge–V–O clusters with four Ge2O7 groups and first reported in this work. 1 is the first 1-dimensional (1-D) chain based on the linkage of centrosymmetric dimeric clusters {[Cd(en)]2[Ge8V12O42.5(OH)5]}212– and trinuclearity [Cd3O4(en)4(H2O)2]2– complexes. 2 is an unprecedented 2-D network built from unique {[Cd(en)]2[Ge8V12O42(OH)6]}8– clusters...

A series of rare metal–organic frameworks based on In-M heterometallic clusters [(CH3)2NH2][In3M2(BTC)4(DMF)2(H2O)4Cl2]·solvent (1-M, M = Ca, Sr, Ba, H3BTC = 1,3,5-benzenetricarboxylic acid, DMF = N,N-dimethylformamide) have been successfully synthesized. Structural analysis reveals that 1-M represent fascinating three-dimensional porous frameworks constructed from different nanoscale cages. What is more, these new materials exhibit interesting gas adsorption properties that can be tuned by encapsulating different alkaline earth metal ions.

A series of polyoxometalates (POMs) that incorporate the highest-nuclearity Ln clusters that have been observed in such structures to date (Ln26 , Ln=La and Ce) are described, which exhibit giant multishell configurations (Ln⊂W6⊂Ln26⊂W100). Their structures are remarkably different from known giant POMs that feature multiple Ln ions. In particular, the incorporated Ln–O clusters with a nuclearity of 26 are significantly larger than known high-nuclearity (≤10) Ln–O clusters in POM chemistry. Furthermore, they also contain the largest number of La and Ce centers for any POM reported to date and represent a new kind of rare giant POMs with more than 100 W atoms. Interestingly, the La26-containing POM can undergo a single-crystal to single-crystal structural transformation in the presence of various transition-metal ions, such as Cu2+, Co2+, and Ni2+, from an inorganic molecular nanocluster into an inorganic–organic hybrid extended framework that is built from POM building blocks with even higher-nuclearity La28 clusters bridged by transition-metal complexes.

A novel inorganic-organic hybrid polyoxotungstate H4[Ni(en)2]2[Ni(en)(dap)]2[Ni(dap)2]2[Ni4(en2)(PW9O34)2]-{[Ni(H2O)5]2[Ni4(en)2(PW9O34)2]}·12H2O (1, en = ethylenediamine, dap = 1,2-diaminopropane) has been successfully synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis, respectively. Single-crystal structure analysis reveals that 1 exhibits a 2-D network structure based on two kinds of tetra-Ni-substituted sandwich-type Keggin polyoxoanions linked by different types of Ni-organoamine complexes.

We report a temperature-resolved assembly of a series of novel nanoscale hexameric Sc-containing polyoxometalates of {Sb6Sc11W60}, {Sb8Sc7W60}, and {Sb8Sc6W60}. These compounds include the largest Sc-containing polyoxotungstates and contain the largest number of Sc3+ ions of any polyoxotungstates reported to date.

A new organic–inorganic hybrid polyoxometalate H2[Cu(en)2(H2O)]2[Cu(en)2]{[Cu(en)2]3 (CuSiW11O39)2}·6H2O (1) (en = ethylenediamine) have been hydrothermally synthesized and characterized by IR spectrum, thermogravimetric analysis, power X-ray diffraction and single-crystal X-ray diffraction. Crystal data for 1: monoclinic, P21/c, a = 18.8077(3) A, b = 23.0703(5) A, c = 26.0723(6) A, β = 96.438(2)°, Z = 4. Single-crystal X-ray diffraction analysis revealed that 1 exhibits a 2-dimensional network constructed from mono-Cu-substituted [CuSiW11O39] 6− chains and [Cu(en)2]2+ bridges. A new organic–inorganic hybrid polyoxometalate H2[Cu(en)2(H2O)]2[Cu(en)2]{[Cu(en)2]3(CuSiW11O39)2}·6H2O (1) (en = ethylenediamine) have been hydrothermally synthesized and characterized, which exhibits a 2-dimensional network constructed from mono-Cu-substituted [CuSiW11O39] 6− chains and [Cu(en)2]2+ bridges.

An unusual high-valent Sb(V)-based unit [SbL2]− (L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol) was developed for the first time to combine with various cuprous-halide clusters for the construction of a brand-new class of heterometallic MOFs. This work not only promotes the limited development of Sb-based MOFs, but also provides a practical strategy for developing new types of composite materials.

This work demonstrates a new Lindqvist-like [FeIII6(μ6-O)L4Cl6]2- (Fe6, L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol) cluster for the construction of a novel class of Fe-cluster organic frameworks. The novel Fe6 cluster can be used to build not only a homometallic MOF, but also a heterometallic MOF by introducing copper halide clusters to the reaction system. In particular, the heterometallic MOF achieved a skillful combination of Fe6 SBU and cuprous-halide clusters for the first time. Our synthesis strategy opens up an effective avenue to novel Fe-cluster-based MOF materials.

Treatment of tetrakis(dimethylamino)diboron (B₂(NMe₂)₄) with 1,4-bis (2-(triisopropylsilyl)ethynyl)naphthalene-2,3-diamine (1) generated a large NBBN polycyclic compound 1,1-B₂{2,3-(NH)₂ -1,4-(ⁱPr₃ SiC₂)₂C₁₀H₄} (2). The X-ray structure analysis reveals that 2 has a twisted structure (dihedral angle ≈ 21.75°) with a rather short B-B bond (1.667(9) Å). Theoretical calculations on 1,1-B₂ isomer 2 and its counterpart 1,2-B₂ isomer 3 have been conducted to understand their frontier orbital energy levels. Compound 2 shows strong emission with a high quantum yield of 0.52, despite the presence of many unbeneficial non-radiative behaviors such as the vibration of the TIPS groups and the rotation of the B-B single bond.

The search for feasible strategies to construct high-nuclear silver clusters has been attracting continuous interests because such materials not only exhibit aesthetic structures and fascinating properties, but also show promising applications in photoluminescence, antibiosis materials, photochromism, nano-materials, and electron transfer/communication materials. Anions are well-known as templates to direct the formation of silver clusters and control the shapes, sizes, and functions of the final products. As a unique class of anionic metal-oxo species, polyoxometalates (POMs) have been widely employed as templates in the syntheses of many intriguing silver clusters. In this review, the advances in POM-templated high-nuclear silver clusters in the past decade are summarized. Additionally, the different templating effects between POMs and simple inorganic anions are discussed. Actually, POMs can do much more than templates for the formation of diverse high-nuclear silver architectures, they also are significant in stabilizing the final products, functionalizing the composite clusters, and so on. Based on the current development in this area, the present challenges and perspectives for such materials are also presented. We hope that this review will be of reference value to accelerate the further development of silver clusters.

Metal-halide open frameworks is a family of important inorganic porous crystalline materials not only due to their intriguing architectures for crystal engineering but also for their wide applications in optoelectronic devices, photocatalysis, luminescence, thermochromism, photochromism, and so on. In this review, a survey of the structural chemistry of three-dimensional non-perovskite-type metal-halide open frameworks is presented. In addition, on the basis of current advances in metal-halide open frameworks, the development prospects and the current challenges for such materials are also discussed.

The first series of niobium–tungsten–lanthanide (Nb-W-Ln) heterometallic polyoxometalates {Ln12W12O36(H2O)24(Nb6O19)12} (Ln=Y, La, Sm, Eu, Yb) have been obtained, which are comprised of giant cluster-in-cluster-like ({Ln12W12}-in-{Nb72}) structures built from 12 hexaniobate {Nb6O19} clusters gathered together by a rare 24-nuclearity sodalite-type heterometal–oxide cage {Ln12W12O36(H2O)24}. The Nb-W-Ln clusters present the largest multi-metal polyoxoniobates and a series of rare high-nuclearity 4d-5d-4f multicomponent clusters. Furthermore, the giant Nb-W-Ln clusters may be isolated as discrete inorganic alkali salts and can be used as building blocks to form high-dimensional inorganic–organic hybrid frameworks.

A series of imidazolium-based porous organic polymers (POP-Ims) was synthesized through Yamamoto reaction of 1,3-bis(4-bromophenyl)imidazolium bromide and tetrakis(4-bromophenyl)ethylene. Porosities and hydrophilicity of such polymers may be well tuned by varying the ratios of two monomers. POP-Im with the highest density of imidazolium moiety (POP-Im1) exhibits the best dispersity in water and the highest efficiency in removing Cr2O7(2-). The capture capacity of 171.99 mg g(-1) and the removal efficiency of 87.9% were achieved using an equivalent amount of POP-Im1 within 5 min. However, no Cr2O7(2-) capture was observed using nonionic analogue despite its large surface area and abundant pores, suggesting that anion exchange is the driving force for the removal of Cr2O7(2-). POP-Im1 also displays excellent enrichment ability and remarkable selectivity in capturing Cr2O7(2-). Cr(VI) in acid electroplating wastewater can be removed completely using excess POP-Im1. In addition, POP-Im1 can serve as a luminescent probe for Cr2O7(2-) due to the incorporation of luminescent tetraphenylethene moiety.

A rare 3-D Mn–organic framework, [(CH3)2NH2]3[Mn5(btc)4(Ac)(H2O)4]·5H2O (1), based on pentanuclear manganese clusters as building blocks has been prepared and structurally characterized by EA, IR, TGA, PXRD, and single-crystal X-ray diffraction. Structural analysis indicates the pentanuclear manganese cluster in 1 has a bow-like configuration, which is the first found to act as secondary building unit in the field of metal–organic framework. Gas adsorption measurements reveal that 1 can absorb a considerable amount of N2 and CO2.

A new approach to prepare heterometallic cluster organic frameworks has been developed. The method was employed to link Anderson-type polyoxometalate (POM) clusters and transition-metal clusters by using a designed rigid tris(alkoxo) ligand containing a pyridyl group to form a three-fold interpenetrated anionic diamondoid structure and a 2D anionic layer, respectively. This technique facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework.

A cationic lanthanide metalloligand with 3 dangling carboxylate groups on its periphery co-assembles with nitrate into a porous thermochromic solid responsive to both external cations and anions, owing to the presence of exchangeable NO3(-) as well as cation cavities arising from cooperative orientation of free carboxylate groups. An especially interesting feature is the structural memory effect during crystallization exhibited by the metalloligand, even after dissolution and binding to secondary cations (Cu(2+), Cd(2+)…). Moreover, the porous solid can undergo ion-exchange with various anions, leading to tunable thermochromic temperature and color range.