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A new noncentrosymmetric strontium borate, P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O (1), has been synthesized under the hydrothermal condition. The P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O shows a layered B−O network with 9‐ring windows in the ab plane. Sr2+ cations, H3BO3, and H2O molecules are located in the voids of layers and interlayers, respectively. The P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O is the first synthetic phase of veatchite, while the other three polymorphs are found in different natural minerals. This strontium borate is a potential deep‐ultraviolet‐transparent nonlinear‐optical (NLO) crystal whose second‐harmonic‐generation (SHG) intensity is 1.7 times that of KH2PO4 (KDP) and is phase‐matchable. The short wavelength cutoff edge of compound 1 is below 190 nm. Density functional theory (DFT) calculations show that the B−O units are responsible for the nonlinear optical property. [ABSTRACT FROM AUTHOR]

A new Zr-substituted polyoxotungstate, [H2N(CH3)2]11KNa5H7[Zr4K2(β-GeW10O38)2(A-α-PW9O34)2]·39H2O (1), has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, UV–vis diffuse-reflectance spectrum, elemental analysis, powder X-ray diffraction, ICP-MS test and thermogravimetric analysis. The prominent feature of 1 is that mixed Keggin-type dilacunary [β-GeW10O38]12− fragment and trilacunary [A-α-PW9O34]9− fragment construct the basic framework of 1. And 1 displays special 1D double-chain and 2D thick layer formed by K+/Na+ ions. 1 exhibits well electrocatalytic behavior in the reduction of BrO3−. Also, the experimental results of catalytic oxidation of representative thioethers manifest that 1 possesses a good catalytic capacity. [ABSTRACT FROM AUTHOR]

A new 3 D polyoxometalate, H7K3[Na2Cu3(H2O)(B-α-SbW9O33)2]·8H2O (1), has been hydrothermally made and characterized by IR spectroscopy, thermogravimetric analyses, powder X-ray diffraction and single crystal X-ray diffraction analysis. 1 crystallizes in the tetragonal system, space group P-421m, with a = 16.7532(7) Å, b = 16.7532(7) Å, c = 13.8335(11) Å and Z = 2. Structure analysis reveals that the polyanion in 1 consists of two B-α-SbW9O33 ({SbW9}) units sandwiched by a U-shaped {Na2Cu3} cluster made by two Na+ and three Cu2+ ions. The most prominent structural feature of 1 is that the [Na2Cu3(H2O)(B-α-SbW9O33)2]10– ({Na2Cu3(SbW9)2}) units are connected to construct a 2 D network through Cu–O = W bridges. To the best of our knowledge, 1 represents the first sample with an unclosed central belt between two {SbW9} fragments. Furthermore, neighboring 2 D networks connect by K+ cations to form a 3 D framework. The semiconductor behavior, electrochemical properties and photocatalytic activities have been investigated, showing excellent photocatalytic and electrocatalytic activities for the photodegradation of MB/RhB and bromate reduction. [ABSTRACT FROM AUTHOR]

A new hexa‐TiIV‐substituted sandwich‐type silicotungstate, Na2(H2enMe)4[Ti6(µ‐O)9(A‐α‐SiW9O34H2)2]·16H2O (1, enMe = 1,2‐diaminopropane) has been synthesized under mild hydrothermal conditions and characterized by FT‐IR spectroscopy, elemental analysis, thermogravimetric analysis, single‐crystal and powder X‐ray diffraction. Compound 1 contains a dimeric polyoxoanion with two [A‐α‐SiW9O34]10– Keggin moieties sandwiching a trigonal‐prismatic [Ti6(µ‐O9)]6+ cluster. The catalytic performance of 1 was evaluated for the oxidative decontamination of chemical warfare agent, i.e. sulfur mustard simulant, 2‐chloroethyl ethyl sulfide (CEES), using H2O2 under ambient conditions, showing that 1 is an excellent catalyst for the rapid and complete transformation from CEES to nontoxic 2‐chloroethyl ethyl sulfoxide (CEESO) with 100 % selectivity. In addition, 1 exhibits good stability and recyclability. [ABSTRACT FROM AUTHOR]

A novel di-ZrIV-substituted sandwich-type silicotungstate (NH4)2(TMA)6[Zr2(μ-OH)2(α-HSiW11O39)2]·18H2O (1, TMA = tetramethylammonium) and a previously unknown EDTA bridging mono-ZrIV-substituted silicotungstate dimeric cluster (NH4)2(TMA)6[(Zr2EDTA)(α-HSiW11O39)2]·26H2O (2, EDTA = C10H14N2O8) have been synthesized under mild hydrothermal conditions and characterized by FTIR spectroscopy, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction. 1 and 2 contain a centrosymmetric polyoxoanion structures with two [α-SiW11O39]8− units sandwiching a [Zr2(μ-OH)2]6+ cluster and [Zr2EDTA]6+ moiety, respectively. The catalytic activities of 1 and 2 on oxygenation of thioethers by H2O2 were evaluated, showing that both 1 and 2 are excellent catalysts for the catalytic oxidation of thioethers to sulfoxides/sulfones. [ABSTRACT FROM AUTHOR]

A previously unknown inorganic–organic hybrid polyoxidometalate constructed from oxalate‐functionalized tetra‐ZrIV‐substituted dimeric silicotungstate, (NH4)3Na5K6[Zr4(µ3‐O)2(µ‐OH)2(ox)2(SiW10O37)2]·23H2O (1, ox = oxalate) has been synthesized under mild hydrothermal conditions and characterized by FTIR spectroscopy, elemental analysis, thermogravimetric analysis, single‐crystal and powder X‐ray diffraction. Compound 1 contains a centrosymmetric polyoxidoanion structure with two [SiW10O37]10– units sandwiching a [Zr4(µ3‐O)2(µ‐OH)2(ox)2]6+ cluster. The catalytic performances of 1 involving oxygenation reactions of thioethers by H2O2 were evaluated, showing that 1 is an excellent catalyst for the catalytic oxidation of thioethers to sulfoxides/sulfones. A new tetra‐ZrIV‐substituted dimeric silicotungstate with two [SiW10O37]10– units sandwiched by an oxalate‐functionalized Zr4 cluster was made and characterized. This was used as a catalyst for catalyzing the oxidation of various thioethers with H2O2, showing excellent catalytic performance. [ABSTRACT FROM AUTHOR]

Two novel isomorphic decaborates, [M(1,2-dap)][BO(OH)] (M = Co ( 1) and Ni ( 2); dap = 1,2-diaminopropane), with transition metal complexes [M(1,2-dap)] as templates have been synthesized successfully under mild hydrothermal conditions and characterized by powder X-ray diffraction, thermogravimetric analysis, IR spectrum, single crystal X-ray diffraction and UV-Vis spectroscopy. The noodle-like orange/purple crystals crystallize in triclinic space group P-1. Their structure contain the isolated [BO(OH)] clusters and further link together to produce a 3-D supramolecular framework with large channels by H-bonding interactions. The UV-Vis-NIR diffuse reflectance spectrum showed a wide-band-gap of 1 and 2. Notice that compounds 1 and 2 are not only the first isolated decaborate cluster and fill the gap left by the absence of isolated structures in the borate family but also could be considered as the structural building units to construct extended oxoboron cluster frameworks. [ABSTRACT FROM AUTHOR]

A trizirconium(IV)-substituted sandwich-type polyoxotungstate, K7.5H6.5[Zr3(µ2-OH)2(µ2-O)(A-α-GeW9O34)(1,4,9-α-P2W15O56)] ·16.5H2O ( 1), was hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and single-crystal X-ray diffraction. The structural unit of 1 consists of trilacunary Dawson-type phosphotungstate and trilacunary Keggin-type germanotungstate units that are linked by a trizirconium(IV) cluster. [ABSTRACT FROM AUTHOR]

Two novel alkali/alkaline-earth borates, Ba6[B6O9(OH)6]2(H3BO3) ( 1) and Li7MAlB12O24 (M=Ba, Sr, Ca) ( 2 a- c), with 1D and 3D structures have been made hydrothermally and characterized. 1 features a rare 1D anionic chain built by hexaborate clusters of B6O11(OH)6; each made of six BO4/BO2(OH)2 tetrahedra. The anionic chains are embedded in the channels of a Ba6-based wheel-cluster open-framework. On the basis of the structural analyses of 1, by incorporating Al atoms as the linkers and tuning the reaction conditions, the novel anhydrous 3D aluminoborates (ABOs) 2 a- c have been successfully obtained, constructed from B6O14-based cluster chains and AlO6 octahedra. The 3D ABO framework and 3D Ba-O-Li network are interpenetrated to give a final dense structure. The study not only realized the expansion of the structure from the 1D chain of 1 to the 3D dense ABOs 2 a- c, but also obtained the first 3D AlO6-containing ABOs made under hydrothermal conditions. Different from the previously known 4-connected zeolite-type ABOs, alternately arranged from AlO4 tetrahedra and oxo-boron clusters, the AlO6 octahedra in 2 a- c as the linkers join to six 1D B6O14-based cluster chains to produce 3D ABOs. The optical diffuse reflectance spectra reveal that 2 a- c have wide range transparency. In addition, the thermal property analysis proves that 2 a- c are congruently melting compounds and possess high thermostability. [ABSTRACT FROM AUTHOR]

Two inorganic-organic hybrid borates, [Zn(en){BO(OH)}] ( 1, en = ethylenediamine) and [Cd(TREN){BO(OH)}] ( 2, TREN = tris(2-aminoethyl)amine) have been made under hydro(solvo)thermal conditions and characterized by IR spectroscopy, elemental analysis, single crystal X-ray diffraction, diffuse-reflectance spectroscopy, thermogravimetric analyses, and powder X-ray diffraction. Crystal data for 1: triclinic, P−1, a = 8.7091(5) Å, b = 8.8731(2) Å, c = 12.7642(8) Å, α = 87.042(4)°, β = 78.198(5)°, γ = 80.816(4)°, V = 952.96(9) Å. Crystal data for 2: monoclinic, P2/ c, a = 11.5051(4) Å, b = 8.7879(4) Å, c = 19.9322(7) Å, β = 91.433(3)°, V = 2014.63(14) Å. They both contain [BO(OH)] cluster units, which linked each other to form 1-D chains. These 1-D chains are further joined together to produce 3-D supramolecular frameworks via H-bonding interactions. Interestingly, the [BO(OH)] cluster in 1 is made of [BO(OH)] and [BO(OH)] sub-cluster units with two O atoms in common, while in 2 consists of [BO(OH)] and [BO(OH)] sub-cluster units with two O atoms in common. The [BO(OH)] ligands in 1 and 2 are coordinated to the supporting metal complexes in different ways. The anion in 1 is coordinated to the Zn(en) by a terminal OH group whereas the anion in 2 is coordinated by a bridging O atom. The in situ organic rearrangement reaction from triethylene tetramine (TETA) to tris(2-aminoethyl)amine (TREN) has been observed in the formation of 2. [ABSTRACT FROM AUTHOR]

A new organic-inorganic hybrid polyoxometalate H[Cu(en)(HO)][Cu(en)]{[Cu(en)] (CuSiWO)}·6HO ( 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, P2/ c, a = 18.8077(3) Å, b = 23.0703(5) Å, c = 26.0723(6) Å, 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 [CuSiWO] chains and [Cu(en)] bridges. Graphical Abstract: A new organic-inorganic hybrid polyoxometalate H[Cu(en)(HO)][Cu(en)]{[Cu(en)](CuSiWO)}·6HO ( 1) (en = ethylenediamine) have been hydrothermally synthesized and characterized, which exhibits a 2-dimensional network constructed from mono-Cu-substituted [CuSiWO] chains and [Cu(en)] bridges. [ABSTRACT FROM AUTHOR]

Two new copper borates, namely H6[(μ4-O)Cu4@B20O32(OH)8]⋅25 H2O ( 1) and H6[(μ4-O)Cu4@B20O32(OH)8]⋅34 H2O⋅8 H3BO3 ( 2), with 3D supramolecular framework have been made under solvothermal conditions, which built by novel cubic supramolecular cages with mesoscale cavities via the H-bondings. Interestingly, the cage is assembled by [(μ4-O)Cu4@B20O32(OH)8] ({Cu4@B20}) cluster units with different point-group symmetry. Owing to extra H3BO3 molecules participated in building the supramolecular framework, 2 has a larger cubic cage size and higher non-framework volume, leading to the cage size extended to mesoporous size set as a version of '' 1 plus'. [ABSTRACT FROM AUTHOR]

Under hydrothermal conditions, replacement of the water molecules in the [MnIII4MnII2O4(H2O)4]8+ cluster of mixed-valent Mn6 sandwiched silicotungstate [(B-α-SiW9O34)2MnIII4MnII2O4(H2O)4]12− ( 1 a) with organic N ligands led to the isolation of five organic-inorganic hybrid, Mn6-substituted polyoxometalates (POMs) 2- 6. They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse-reflectance spectroscopy, and powder and single-crystal X-ray diffraction. Compounds 2- 6 represent the first series of mixed-valent {MnIII4MnII2O4(H2O)4− n(L) n} sandwiched POMs covalently functionalized by organic ligands. The preparation of 1- 6 not only indicates that the double-cubane {MnIII4MnII2O4(H2O)4− n(L) n} clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [MnIII4MnII2O4(H2O)4]8+ cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed-valent POMs substituted with transition-metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single-molecule magnet behavior. [ABSTRACT FROM AUTHOR]

Six new lanthanide (Ln) germanate cluster organic frameworks (LnGeCOFs) derived from {Ln8Ge12} cage cluster units {[Nd(pza)2(H2O)] [Nd8Ge12(μ3-O)24E12(pza)(H2O)12]}·3H2O (1), {[Dy(CH3COO)(CO3)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)12]}·11H2O (2), {[TbGeE(HO)2O(pza) (H2O)]2[Tb8Ge12(μ3-O)24E12(H2O)6]}·18H2O (3), {[DyGeE(HO)2O(C3H5NO2)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)8]}·8H2O (4), {[Tb(pca)2 (H2O)]3[Tb8Ge12(μ3-O)24E12(H2O)4]}·(OH)3·10H2O (5) and {[Dy(pza)2(H2O)][Dy(pza)2(H2O)2][Dy(pza)3(H2O)][Dy8Ge12(μ3-O)24E12(pza)(HCOO) (H2O)6]}·5H2O (6) have been hydrothermally synthesized and structurally characterized. Increasing the amount of the second ligands can induce not only the assembly from 1 to 5, 6 based on Ln oxides as the starting sources, but also the assembly from 2 to 3, 4 based on Ln salts as the starting sources. The successful preparation of these LnGeCOFs suggests the importance of the second ligands in the structural construction of 1–6. To our knowledge, 1 is the first example that includes right- and left-handed helical chains among LnGeCOFs based on bis(carboxyethylgermanium)sesquioxide. 2, 4 and 6 are the first dysprosium incorporated organogermanates based on bis(carboxyethylgermanium)sesquioxide. 4 and 5 display very open framework structures with a solvent-accessible volume of 34.6% for 4 and 35.0% for 5. Moreover, the solid-state photoluminescence properties of 1, 3 and 5 have been investigated at room temperature and they exhibit the characteristic emission bands derived from Ln cations. [ABSTRACT FROM AUTHOR]

A new borate LiBa3(OH)[B9O16][B(OH)4], which combines the uniform porosity of open-frameworks with the extraordinary NLO properties of borates, has been obtained under hydrothermal conditions by using mixed lithium and barium ions as templates. The framework displays an acs-type net with large 21-ring channels. The second harmonic generation (SHG) measurement shows that it is a type I phase-matchable material with a strong SHG signal intensity about 3.1 times that of KDP (KH2PO4). UV/Vis-NIR diffuse reflectance analysis indicates that the compound has a wide transparency range with the short-wavelength absorption edge below 200 nm. These characteristics reveal that the compound is a promising deep-UV nonlinear optical material. [ABSTRACT FROM AUTHOR]