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Three new group IIIA metal phosphate–oxalate (MPO) compounds, namely [(CH3)2NH2]2[M2(HPO4)2(H2PO4)2(C2O4)] (M = Al (1), Ga (2)) and [(CH3)2NH2]2[In2(HPO4)2(H2PO4)2(C2O4)]·H2O (3), have been synthesized. Their crystal structures feature an anionic layer with the sql topology net. In particular, 1 displays a proton conductivity (σ) of 9.09 × 10−3 S cm−1 at 85 °C and under 98% relative humidity, which is the highest among MPOs. This study not only endows the main group metal-based MPO family with new members, but also contributes to further understanding of the structure-directing roles of amines and provides a feasible idea for improving the proton conductivity of MPOs. [ABSTRACT FROM AUTHOR]

In this paper, we report a series of novel mixed‐metal‐substituted organic‐inorganic hybrid polyoxometalates (POMs) H3[(CH3)4N]14[NaLn(PW11O39)3]·18H2O (1‐Ln, Ln = Nd, Sm, Eu) via one‐pot solvothermal synthesis methods, which present the first series of polyoxometalate trimers composed of both alkali‐metal‐ and lanthanide‐substituted keggin‐type POMs. The trimeric heterometallic polyoxoanions in 1‐Ln show an interesting linear arrangement and can be further packed together to generate a packing structure with cations [(CH3)4N]+ and H3O+ filling the gaps between polyoxoanions. Compounds 1‐Ln are characterized by single‐crystal X‐ray diffraction analysis, TGA, IR and PXRD. Additionally, the luminescence and proton conductive properties of 1‐Ln are also characterized. A series of unprecedented linear mixed‐metal‐substituted organic‐inorganic hybrid polyoxometalate trimers H3[(CH3)4N]14[NaLn(PW11O39)3]·18H2O (1‐Ln, Ln = Nd, Sm, Eu), composed of both alkali‐metal‐ and lanthanide‐substituted keggin‐type POMs, show interesting luminescence and proton conductive properties. [ABSTRACT FROM AUTHOR]

The first transition-metal-bridged polyniobotungstate-based 3D framework has been hydrothermally synthesized, which is constructed from bi-[CuII(en)2(H2O)]-decorating [Nb3W3O19]5− polyoxoanions linked together by CuI ions. Interestingly, the 3D polyniobotungstate framework can undergo a solid–liquid reaction with KI solution to generate a 1D copper halide of [Cu(en)2][CuI2]2 in a single-crystal-to-single-crystal process. [ABSTRACT FROM AUTHOR]

Abstract: Three novel hetero-polyoxovanadates, [Cd(2,2′-bpy)3]{[Cd(dien)]As8V14O42(H2O)} (1, 2,2′-bpy=2,2′-bipyridine, and dien=diethylenetriamine), [Zn(2,2′-bpy)2]2[As8V14O42(H2O)]·H2O (2) and [Ni(en)2]3[As8V14O42(HPO3)]·4H2O (3, en=ethlenediamine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Crystal data: 1 monoclinic, P2(1)/n, , , , , Z=4. 2, orthorhombic, P2(1)2(1)2(1), , , , . 3, triclinic, , , , , , , , . Compounds 1–3 are all made of the {As8V14O42} shells linked by corresponding transition metal complexes into extended structures. Compound 1 and 2 present 1-D wave-like and tubular structures, respectively, while compound 3 exhibits a novel 2-D structure containing interwinding puckery layers. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interaction between VIV cations in 1 and 2. [Copyright &y& Elsevier]

Abstract: Two new arsenic–vanadium clusters, [Zn(2,2′-bpy)3]2[As8V14O42(H2O)]·4H2O (1, 2,2′-bpy =2,2′-bipyridine) and [Zn(2,2′-bpy)(dien)]2[As8V14O42(H2O)]·2H2O (2, dien=diethylenetriamine), have been hydrothermally synthesized and characterized by IR, elemental analysis, EPR, XRD, TGA, magnetic measurements, and single-crystal X-ray diffraction analysis. Crystal data: 1, triclinic,, a=14.3793(2)Å, b=16.7706(2)Å, c=24.7077(1)Å, α=93.740(1)°, β=93.182(1)°, γ=113.363(1)°, Z=2; 2 orthorhombic, P4(3)2(1)2, a=21.3442(7)Å, b=21.3442(7)Å, c=15.8837(7)Å, Z=4. X-ray crystallographic study showed that compound 1 is composed of the discrete [As8V14O42(H2O)]4- polyoxoanions and chiral [Zn(2,2′-bpy)3]2+ cations, while compound 2 is constructed from [As8V14O42(H2O)]4− cluster anions and novel [Zn(2,2′-bpy)(dien)]2+ complex fragments linked through hydrogen bonds into a network. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interaction between VIV cations in 1 and 2. [Copyright &y& Elsevier]

Abstract: Two new hybrid vanadium arsenates (2,2′-bpy)2(VVO2)2(AsO4)⋅H3O⋅H2O 1 and (2,2′-bpy)2V4O7(HAsO4)2 2 (2,2′-bpy=2,2′-bipyridine) were synthesized under hydrothermal reaction conditions and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis (TGA), IR, powder XRD and elemental analyses. Crystal data for 1: monoclinic, , , , , , , . Crystal data for 2: triclinic, P-1, , , , , , , , . Compound 1 is composed of discrete {(VO2)2(AsO4)} 3-membered rings bonded to two 2,2′-bpy ligands. Compound 2 exhibits a 2D arsenic vanadate network decorated with 2,2′-bpy ligands. [Copyright &y& Elsevier]

Abstract: A new arsenic–vanadium clusters, [NH2(CH2CH2)2NH2]3[As8V14O42(SO4)]·6.5H2O (1), have been hydrothermally synthesized and characterized by IR, elemental analysis, TGA, magnetic property, and single crystal X-ray diffraction analysis. Crystal data: Monoclinic, P2(1)/n, a=21.963(2)Å, b=14.508(1)Å, c=23.054(3)Å, β=118.316(3)°, Z=4. X-ray crystallographic study showed that crystal 1 is composed of the discrete cluster anions [As8V14O42(SO4)]6-, organic amine molecules providing charge-compensation, space-filling, and structure-directing roles, and lattice water molecules occupying in the structure. The study of the magnetic susceptibility of 1 demonstrates the presence of antiferromagnetic interaction between VIV cations in 1. [Copyright &y& Elsevier]

A new inorganic–organic hybrid open-framework zinc phosphite, (C6N3H12)2·Zn5(HPO3)6, has been hydrothermally synthesized in the presence of 1-(3-aminopropyl)imidazole amine as a structure-directing agent. Its structure was determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction (PXRD), IR spectroscopy, ICP, elemental, and TG analyses. This compound crystallizes in the orthorhombic system, space group C2221 (no. 20), a=9.9512(4), b=14.7129(6), c=22.50660(10) Å, V=3295.21(19) Å3, Z=4. The connectivity of the strictly alternating Zn-centered tetrahedra and HPO3 pseudopyramids results in a 3D framework with intersecting 8- and 12-membered ring channels, where organic amines reside. It is worth noting that the title compound is the first metal phosphite to be prepared with a metal: phosphorus ratio of 5:6. [Copyright &y& Elsevier]

CaYGaO 4 was synthesized by conventional solid-state method. Its crystal structure was determined by single-crystal X-ray diffraction technique to be olivine structure type. CaYGaO 4 comprises an orthorhombic space group Pnma , with lattice constants of a = 11.3484(1) Å, b = 6.5712(6) Å and c = 5.2818(8) Å. All three cations occupy their specific atomic positions and the structure is fully ordered. The crystallographic ordering scheme in the new gallate system, is different from those reported for the previously studied silicate and germanate olivines. The partial replacement of the Ga 3+ by Fe 3+ ions could be achieved, resulting in a series of solid solutions with the chemical composition of CaYGa 1− x Fe x O 4 (0 < x ⩽ 0.50). The unit cell volumes of the doped variants are consistent with Vegard’s law. [ABSTRACT FROM AUTHOR]

[Display omitted] • The developments of POM-based macrocycles including their syntheses, structures, properties, and related applications are summarized. • The interesting modular hierarchical assembly of POM-based macrocycles was summarized. • The structure–property/application relationships of POM-based macrocycles are summarized. • The development prospects and the present challenges in the study of POM-based macrocycles are discussed. Polyoxometalate (POM) macrocycles have been extensively investigated due to their potential applications in various fields, including sensing, optics, magnetism, proton conduction, catalysis, and host–guest chemistry, leveraging the advantages offered by their unique wheeled structures. In this review, the recent progress of POM macrocycles, including their assembly strategies, crystal structures, properties, and various applications, is reviewed. Additionally, the current obstacles and challenges regarding the design and construction of POM macrocycles are also discussed. [ABSTRACT FROM AUTHOR]

Abstract: Hydrothermal reactions of VOSO4·3H2O, CdAc2·2H2O, NiCl2·6H2O, H3PO4, and H2O yield the first example of trimetallic phosphate materials, [Ni(H2O)4]Cd(VO)(PO4)2 1. The single-crystal X-ray diffraction shows that its structure consists of Cd/V/O binary metal oxide lamellas decorated by PO4 tetrahedra, which are further pillared by NiO2(H2O)4 octahedra to generate a neutral 3-D framework containing two intercrossing 8-MR channels where the coordinated water molecules protrude into. Thermal and magnetic behaviors of this material were also measured. Crystal data: CdNiVP2O13H8, orthorhombic Ibca (No.73), a=7.1307(2)Å, b=18.6248(3)Å, c=14.8046(2)Å, V=1966.17(7)Å3, Z=8. [Copyright &y& Elsevier]

Abstract: A new hydrated borate compound, [NH3CH2CHCH3NH3]][B8O11(OH)4]·H2O 1, has been synthesized in the presence of 1,2-diaminopropane acting as a structure-directing agent under mild conditions. Its structure was determined by single crystal X-ray diffraction and further characterized FTIR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P21 /c (No. 14), a=10.0787(7)Å, b=8.8482(6)Å, c=19.3097(4)Å, β=91.352(6)°, V=1721.53(2)Å3, and Z=4. The structure consists of infinite open-branched borate chains constructed from [B3O6(OH)] units, onto which the [B5O7(OH)3] groups are grafted. It represents the first example of one-dimensional borate templated by an organic amine. The adjacent borate chains are further linked together by extensive hydrogen bonds to form a 3D supramolecular network. The diprotonated organic amines and guest water molecules are filled in the free space of the hydrogen-bonded network and interact with the inorganic framework by extensive hydrogen bonds. [Copyright &y& Elsevier]

Abstract: A new inorganic–organic hybrid solid, Cd(phen)(H2PO4)2⋅H2O (phen=1,10-phenanthroline), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis, ICP analysis, powder X-ray diffraction and fluorescent spectrum. The compound crystallizes in the triclinic system, space group P-1 (No. 2), , , , , , , , . The structure is built from strictly alternating CdO4N2 octahedra and H2PO4 tetrahedra through their vertices, forming an infinite ladder-like architecture. This compound shows intense photoluminescence upon photoexcitation at 358 nm. [Copyright &y& Elsevier]

Two new open-framework germanates, [Cd2(C2N2H8)3][Ge9O18(OH)4] (1) and (C8N4H26)[Ge9O18(OH)4] (2), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic space group, Pbca, with a=14.318(3), b=13.106(3), c=14.580(3) Å, V=2736.0(9) Å3, Z=4. The compound is the first organically templated cadmium germanate. The structure of 1 is constructed from two distinct motifs, a body-centered [Ge9O18(OH)4] cluster and a cadmium complex [Cd2(C2N2H8)3O6], which integrate to generate a 3D architecture with neutral framework. The structures of 2 is closely related to that of 1 and has identical Ge9O18(OH)4 clusters. It crystallizes in the orthorhombic space group, Pbca, with a=14.158(3), b=13.213(3), c=14.553(3) Å, V=2722.5(9) Å3, Z=4. The connectivity between the Ge9 clusters result in a 3D open-framework structure. The quadruply protonated N,N′-bis(3-aminopropyl)ethylene diamine molecules are located in the free voids and interact with the macroanionic inorganic framework by extensive hydrogen bonds. [Copyright &y& Elsevier]

A new layered inorganic–organic hybrid gallium phosphate, Ga2(phen)(HPO4)3 (phen=1,10-phenanthroline), has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, FTIR, elemental analysis, ICP, power X-ray diffraction and thermogravimetric analysis. This compound crystallizes in the triclinic system, space group P-1 (No. 2), a=7.7730(6) Å, b=11.7968(10) Å, c=12.1458(9) Å, α=114.089(2)°, β=102.310(2)°, γ=102.905(2)°, V=931.28(13) Å3, Z=2. The structure is built from strictly alternating GaO4N2 octahedra, GaO4 tetrahedra and HPO4 tetrahedra through their vertices, forming a neutral layered architecture grafted with phen ligands. The adjacent sheets are stacked in an AAAA sequence along [0 0 1] direction and held together by strong π–π interactions. [Copyright &y& Elsevier]

Two organically templated zinc phosphites, (C2N2H10)Zn2(HPO3)3 (1) and (C4N2H12)Zn3(HPO3)4 (2), were hydrothermally synthesized and structurally characterized. Compound 1 crystallized in the triclinic system, space group P-1 (No. 2), a=8.6357(14) A˚, b=8.8197(14) A˚, c=9.9665(16) A˚, α=64.645(2), β=65.922(2), γ=81.049(2)°, V=626.12(17) A˚3, Z=2. The connectivity of the strictly alternating ZnO4 and HPO3 polyhedra results in infinite macroanionic layers with 4.8-net. The organic cations locate in the interlayer region and hold the macroanionic sheets together by strong H-bonds. Compound 2 crystallized in the monoclinic system, space group P21/c (No. 14), a=9.9352(14) A˚, b=10.1487(14) A˚, c=17.8257(13) A˚, β=95.701(7), V=1788.5(4) A˚3, Z=4. The structure of 2 consists of ZnO4 tetrahedra and HPO3 pseudo-pyramids with shared vertices, forming a 3D framework with 8-ring channels. Both compounds were characterized by FTIR, elemental analysis, ICP analysis and thermogravimetric analysis. [Copyright &y& Elsevier]

A new inorganic–organic hybrid solid, (4,4′-bipy)[Zn(HPO3)]2 (4,4′-bipy=4,4′-bipyridine), has been hydrothermally synthesized in the presence of 4,4′-bipy ligand. Its structure was determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, ICP analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectrum. It crystallized in the monoclinic space group, P21/c, with a=9.741(2), b=7.4423(16), c=10.271(2) A˚, β=100.038(4)°, V=733.3(3) A˚3, Z=2. The structure consists of neutral sheets of zinc phosphite which is pillared through 4,4′-bipy ligands to generate a 3D framework. The compound shows relatively high thermal stability and exhibits intense photoluminescence upon photo-excitation at 362 nm. [Copyright &y& Elsevier]

The hydrothermal synthesis, crystal structure and some properties of a zinc phosphite with a neutral cluster, [Zn(2,2′-bipy)]2(H2PO3)4, are reported. This compound crystallizes in the triclinic system of space group P-1 (No. 2), a=8.3067(5) A˚, b=8.9545(4) A˚, c=10.0893(6) A˚, α=95.448(2)°, β=99.7530(10)°, γ=103.461(2)°, V=712.23(7) A˚3, Z=1. The cluster consists of 4-membered rings formed by alternating ZnO3N2 square pyramids and H2PO3 pseudo pyramids, with two “hanging” H2PO3 groups attached to each of the Zn centers. The clusters are linked together by extensive multipoint hydrogen bonding involving the phosphite units to form a sheet-like structure. This compound represents the first example of zinc phosphite with P&z.sbnd;OH bonds. An intense photoluminescence was observed from this compound upon photoexcitation at 388 nm. [Copyright &y& Elsevier]

A neutral zincophosphate monomer [Zn(2,2′-bipy)]2(H2PO4)4 has been synthesized under hydrothermal condition in the presence of 2,2′-bipyridine ligands. The structure consists of a 4-membered ring formed by vertex-sharing ZnO3N2 square pyramids and H2PO4 tetrahedra, with two H2PO4 groups hanging from the zinc atoms. This compound exhibits intense photoluminescence upon photoexcitation at 388 nm. [Copyright &y& Elsevier]

• An inorganic-organic hybrid lanthanide-polyoxotungstogermanate. • A 3D supramolecular network formed by N H···O and C H···O hydrogen bonds between the [Eu(α-GeW 11 O 39) 2 ]13− polyanion and dimethylammonium cations. • Strong Eu3+ characteristic emission with long decay time. A novel inorganic-organic hybrid lanthanide-polyoxotungstogermanate, [NH 2 (CH 3) 2 ] 13 [Eu(α-GeW 11 O 39) 2 ]·8H 2 O (1) is directly prepared using raw material by hydrothermal synthesis method and characterized by single-crystal X-ray diffraction, PXRD, IR, solid-state UV–visible spectra and TG analyses. Compound 1 is constructed from [Eu(α-GeW 11 O 39) 2 ] dimer anions and dimethylammonium cations. It is an unusual example of crystal structure containing {Eu(α-GeW 11 O 39) 2 } dimer and organic ammonium without alkali metal cations. The N H···O and C H···O hydrogen bonds link the [Eu(α-GeW 11 O 39) 2 ]13− cluster units and the dimethylammonium cations to a 3D supramolecular network. Compound 1 exhibits Eu3+ characteristic luminescent property with decay time of 2.342 ms. [Display omitted] [ABSTRACT FROM AUTHOR]

Four tetra-Cd-substituted vanadogermanates (V-Ge-Os) H 2 [Cd(dap) 2 {[Cd(dap)] 4 [Ge 8 V 10 O 38 (OH) 8 }·10H 2 O (1), H[Cd(phen)(H 2 O) 2 2 {[Cd(phen)] 4 Ge 8 V 10 O 39 (OH) 7 }·2H 2 O (2), [Cd(phen) 2 2 {[Cd(phen)] 2 [Cd(dap)] 2 Ge 8 V 10 O 38 (OH) 8 }·2H 2 O (3) and H 2 [Cd(phen) 2 4 {[Cd(phen)] 4 [Ge 8 V 10 O 40 (OH) 6 }{[Cd(phen)] 2 [Cd(H 2 O) 2 2 [Ge 8 V 10 O 38 (OH) 8 }·10H 2 O (4) (dap ​= ​1,2 - diaminopropane; phen ​= ​1,10 - phenanthrolinemonohydrate) have been hydrothermally prepared and structurally characterized. Single crystal X-ray structural analyses indicate that all of 1 – 4 contain uncommon tetra-Cd-substituted V-Ge-O clusters. 1 is a rare one-dimensional chain based on tetra-Cd-substituted V-Ge-O clusters, while 2–4 are unique discrete tetra-Cd-substituted V-Ge-O clusters decorated with different metal-organoamine complexes. Furthermore, the thermal/chemical stability of 1 and 2 as well as the magnetic properties of 1 , 2 and 4 were investigated. In this work, four tetra-Cd-substituted vanadogermanates was successfully prepared and characterized. The tetra-Cd-substituted vanadogermanate cluster is a flexible unit, which can be not only decorated by various transition-metal complexes to form different isolated structures, but also bridged by transition-metal complexes to generate an extended 1-dimensional chain. Image 1 • Four unique tetra-Cd-substituted vanadogermanates have been hydrothermally made. • Compound 1–4 represent the second series of tetra-Cd-substituted V-Ge-Os. • Compound 1 is a novel 1-dimensional chain based on tetra-Cd-substituted V-Ge-O cluster. • Compound 3 is an uncommon tetra-Cd-substituted V-Ge-O containing mixed chelating organoamine ligands. • Compound 4 is the first V-Ge-O containing two electrically different tetra-Cd-substituted V-Ge-O clusters in one structure. [ABSTRACT FROM AUTHOR]

A new inorganic-organic dimeric polyoxoniobate containing "S"-shaped {[Cu 3 (en) 6 (β-H 4 Nb 52 O 150) 2 } polyoxoanion was prepared and characterized. • A new inorganic-organic dimeric polyoxoniobate contains "S"-shaped {[Cu 3 (en) 6 (β-H 4 Nb 52 O 150) 2 } polyoxoanions. • Novel high-nuclearity {β-H 4 Nb 52 O 150 } cluster enriches the limited structures of the polyoxoniobate family. • The compound 1 shows effective catalytic activity for hydrolytic decomposition of nerve agent simulant DMMP. A new inorganic-organic hybrid polyoxoniobate, H 16 K 24 Na 26 [Cu 3 (en) 6 [(β -H 4 Nb 52 O 150) 2 ·88H 2 O (1) (en = ethylenediamine), decorated with [Cu(en) 2 2+ complex, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, and Uv-vis. Crystal structure analysis shows that 1 contains a "S"-shaped {[Cu 3 (en) 6 (β -H 4 Nb 52 O 150) 2 } polyoxoanion which is built from novel high-nuclearity {[Cu(en) 2 (β-H 4 Nb 52 O 150)} fragments. The compound 1 shows effective catalytic activity for hydrolytic decomposition of nerve agent simulant of dimethyl methylphosphonate (DMMP). [ABSTRACT FROM AUTHOR]

A series of novel 4s–4f heterometallic cluster substituted polyoxometalates (POMs) with formula of H 9 Na 12 K 2 [K 3 Ln 4 (NO 3) 2 (GeW 10 O 37) 2 (Ge 2 W 18 O 66)]·34H 2 O (1-Ln) (Ln = Dy, Ho, Er) have been hydrothermally made by adopting a trilacunary [A-α-GeW 9 O 34 ]10− as a precursor. 1-Ln represent the first examples of metal-substituted POM clusters based on mixed POM fragments including dilacunary [α-GeW 10 O 37 ]10− and multilacunary open Well-Dawson [Ge 2 W 18 O 66 ]16− fragments. • Novel 4s–4f heterometallic substituted POMs have been prepared and characterized. • The compounds contain mixed Keggin/ open Well-Dawson POM fragments. • The Luminescent properties of these compounds were systematically studied. • The work enriches the diversity of heterometallic metal cluster substituted POMs. • This work provides a new route for making new POMs based on mixed POM units. By adopting a trilacunary [A-α-GeW 9 O 34 ]10− as a precursor under hydrothermal conditions, a series of novel 4s–4f cluster substituted polyoxometalates (POMs) containing two types of in situ generated lacunary POM fragments have been made. These compounds were characterized by single-crystal X-ray diffractions, powder X-ray diffractions, infrared spectroscopy, thermogravimetric analyses, respectively. Structural analyses indicate that these compounds constructed from a seven-nuclearity K-O-Ln (Ln = Dy, Ho, Er) heterometallic cluster stabilized by mixed dilacunary Keggin [α-GeW 10 O 37 ]10−/multilacunary open Wells-Dawson [Ge 2 W 18 O 66 ]16− fragments. Furthermore, the solid luminescent properties of the compounds at room temperature were studied. [ABSTRACT FROM AUTHOR]