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A new Co4-added polyoxometalate (CoAP) Cs4[(Co(H2O)5)2{(μ2-Co(H2O)4)2Co4(H2O)2(B-α-GeW9O34)2}]·6H2O (1) has been made using a lacunary directing strategy under hydrothermal conditions. Single-crystal X-ray diffraction analysis demonstrated that 1 is a one-dimensional (1D) chain, in which CoAP is linked by cobalt-oxygen octahedra to form a 1D structure with excellent chemical stability. The visible light-driven H2 evolution test demonstrated that 1 has high activity, with an H2 evolution rate of 1485.95 μmol h−1 g−1. PXRD and FT-IR tests demonstrated that compound 1 exhibits excellent heterogeneous catalytic stability. [ABSTRACT FROM AUTHOR]

Two structurally new Lindqvist hexaniobate-templated silver thiolate clusters, [Nb6O19@Ag45(iPrS)23(CH3COO)14] (Ag45) and (H3O)4[Nb6O19@Ag41KS2.5O2(H2O)7.5(iPrS)24(CH3COO)5] (Ag41), were synthesized using a facile one-pot solvothermal approach. Single crystal X-ray diffraction analyses revealed the presence of a classical Lindqvist-type [Nb6O19]8− anion template, with iPrS− and CH3COO− surface-protecting ligands in both silver clusters, which can further form two-dimensional Ag45 assembly and one-dimensional Ag41 chain packing structures. Both Ag45 and Ag41 clusters exhibited intriguing photothermal conversion properties and temperature-dependent emission behavior. [ABSTRACT FROM AUTHOR]

A polyanion cluster H6Na8Cs3[Co9(μ3-OH)3(H2O)6(HPO4)2(B-α-PW9O34)3]Cl·40H2O (1) was made with the guidance of the lacunary directing strategy under hydrothermal conditions. Compound 1 was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analysis, respectively. Single-crystal X-ray diffraction analyses showed that 1 consists of three anions [B-α-PW9O34]9− and a cyclic cationic [Co9(μ3-OH)3(H2O)6]15+ and two anions HPO42−. Variable-magnetic properties indicate antiferromagnetic interactions in 1. Visible-light-driven hydrogen evolution tests demonstrated that 1 was an efficient water reduction catalyst with an H2 evolution rate of 1217.6 μmol h−1 g−1. [ABSTRACT FROM AUTHOR]

Two new hexa-Ni-substituted polyoxometalates (POMs), [Ni6(μ3-OH)3(en)2(dien)(H2O)5(B-α-PW9O34)]·3H2O (1, en = ethylenediamine, dien = diethylenetriamine) and [Ni6(μ3-OH)3(dap)2(py)6(H2O)(B-α-PW9O34)]·H2O (2, dap = 1,3-diaminopropane, py = pyridine), were successfully isolated under hydrothermal conditions. Compounds 1 and 2 were structurally characterized via single-crystal X-ray diffraction (XRD), infrared (IR) spectrometry, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). Single-crystal X-ray structure analyses indicate that the {Ni6PW9} cluster units were modified via different organic ligands through Ni–N bonds, giving rise to the formation of 1 and 2. Interestingly, the formation of 1 involves new in situ ligand reactions under hydrothermal conditions: the intermolecular deamination coupling reactions of en. Compound 2 is a new Z-shaped 1-D chain, which is connected by Ni–O＝W bonds from two adjacent [Ni6(μ3-OH)3(dap)2(py)6(H2O)(B-α-PW9O34)] units. In addition, their photocatalytic activities, and electrochemical and magnetic properties have been investigated. [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 novel octa-Mn-substituted silicotungstate (ST) [H2N(CH3)2]8H19Na4{[K(H2O)4WO4][SiMn II2 W10O38]3}[SiMn III2 W10O38]·27H2O (1) has been made by the hydrothermal reaction of the trivacant [A-α-SiW9O34]10− ({SiW9}) building block with Mn2+ and Mn7+ cations in the presence of dimethylamine hydrochloride and systematically characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. 1 is a tetrameric cluster formed by a hexa-MnII substituted cyclic trimeric {[K(H2O)4WO4][SiMn II2 W10O38]3} unit and a {SiMn III2 W10O38} fragment via two W–O–MnIII linkers. Furthermore, its electrochemistry, thermal stability and magnetic properties have been studied. [ABSTRACT FROM AUTHOR]

Abstract: In the presence of the larger [H2N(CH3)2]+ and K+ counter cations as structure‐stabilizing agents, a class of unprecedented selenium and lanthanide (Ln) simultaneously bridging tetra‐vacant Dawson‐like selenotungstate aggregates [H2N(CH3)2]2Na9K2H19{[Ln4W4 Se4O22(H2O)5](Se2W14O52)2}2⋅60 H2O [Ln=TbIII (1), DyIII (2), HoIII (3), ErIII (4), TmIII (5), YbIII (6)] have been obtained by the one‐pot assembly reaction of Na2WO4⋅2 H2O, Ln(NO3)3⋅6 H2O, and Na2SeO3 under moderately acidic aqueous conditions and the complexes were structurally characterized by elemental analyses, IR spectra, single‐crystal X‐ray diffraction, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. It should be noted that the appropriate molar ratio of Se/W is extremely important in the formation of 1–6 and can effectively ameliorate the yield of 1–6. Moreover, dimethylamine hydrochloride is also indispensable and plays a considerably important role in improving the solubility of Ln ions and stabilizing the structures of 1–6. The main polyoxoanion skeletons of 1–6 are constructed from two sandwich‐type tetra‐vacant Dawson‐like {[Ln4W4Se4O22(H2O)5](Se2W14O52)2}16− half‐units linked through two W‐O‐Ln bridges. The sandwich‐type half‐unit comprises two tetra‐vacant Dawson‐like [Se2W14O52]12− fragments encapsulating a unique dodecanuclear Se‐Ln‐W [Ln4W4Se4O22(H2O)5]8+ oxo cluster. Their solid‐state visible and NIR fluorescent properties and lifetime decay behaviors were measured and their solid‐state luminescent spectra mainly demonstrate the characteristic emission bands of Ln3+ ions. Moreover, the dominant wavelengths, the color purity, and correlated color temperatures of 1–5 have been also calculated. In addition, the luminous flux values of 1–5 are 2031, 6992, 3071, 921, and 477 lumen, respectively. [ABSTRACT FROM AUTHOR]

Abstract: The grafts of fluorophores 9‐anthraldehyde (AD) and 9‐phenanthrenecarboxaldehyde (PD), respectively, on the one‐dimensional spin‐crossover compound [Fe(L)3](ClO4)2 (FeL, L=4‐amino‐1,2,4‐triazole) by post‐synthetic aldimine condensation reactions produced two spin‐crossover (SCO)–fluorescent hybrid materials, that is, FeL‐AD and FeL‐PD. The spin‐crossover critical temperatures of the two materials both centered at Tc↓=254 and Tc↑=256 K, whereas the fluorescence intensities of the two materials featured functions of the temperature that strictly synchronized with the spin‐crossover processes, which showed that the ligand‐centered fluorescence was dominated by the spin states of the ferrous ions. The bifunctional entities (spin‐crossover centers and fluorophores) in FeL‐AD or FeL‐PD showed spectral band overlap that purported the Förster resonance energy transfer mechanism of such spin‐crossover–fluorescence correlation. The post‐synthetic modification of SCO materials and the relationship between the fluorescence and the SCO may be helpful in the development of multifunctional materials that can be sensitive to multiple stimuli. [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 new Zr-substituted sandwich-type polyoxometalate, HK[ZrK(μ-O)(μ-OH)(HO)(A- α-PWO)]·2Cl·7HO ( 1), has been made under hydrothermal conditions. 1 was characterized by IR spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction, respectively. Crystal data for 1: tetragonal space group P422, a = 24.0096(3), b = 24.0096(3), c = 14.7416(3) Å, V = 8498.0(2) Å and Z = 4. Single crystal X-ray structure analysis reveals that 1 exhibits a three-dimensional framework structure based on ZrK-substituted sandwich-type polyanions [ZrK(μ-O)(μ-OH)(HO)(PWO)] linked by K-O chains. UV-Vis spectrum indicates that 1 is a wide-gap semiconductor. In addition, the SHG of 1 was also investigated. [ABSTRACT FROM AUTHOR]

Two new tetraborates, namely [Li(HO)][Cu(HO)][Cu(HO)][BO(OH)]·4HO ( 1) and [Cu(en)(HO)][Cu(en)(B(OH))][BO(OH)]·HO ( 2) have been made under solvothermal conditions and characterized by FT-IR spectroscopy, powder X-ray diffraction, single crystal X-ray diffraction and thermogravimetric analysis, respectively. 1: triclinic, Pī, a = 7.0400(2) Å, b = 7.8779(3) Å, c = 25.8958(11) Å, α = 90.827(3)º, β = 95.985(3)º, γ = 105.816(3)º, Z = 1. 2: monoclinic, P2 /c, a = 12.5723(6) Å, b = 9.1508(5) Å, c = 15.9800(6) Å, β = 94.742(4)º, Z = 2. In structure 1, the BO(OH) clusters join together via H-bonding interactions to produce 3-D supramolecular framework with three types of channels located by the Cu(HO), Cu(HO) and Li(HO) polyhedra, respectively. While in 2, the BO(OH) clusters link each other to form 2-D layers and then further pillared by Cu(en)(B(OH)) complexes via H-bonding interactions, resulting in 3-D supramolecular framework with hexagonal and rectangle channels, in which the rectangle channels are filled by Cu(HO)(en) complexes. [ABSTRACT FROM AUTHOR]

Two new pentaborate clusters, [MPD][BO(OH)] ( 1, MPD = 2-methyl-1,4,5,6-tetrahydropyrimidine-3-ium) and SrBO(OH) HO ( 2), have been hydro(solvo)thermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray structural analysis, respectively. Crystal data for 1: monoclinic, P2, a = 9.3384(3) Å, b = 17.3774(5) Å, c = 9.1886(3) Å, β = 93.172(3)°, Z = 4. Crystal data for 2: triclinic, P-1, a = 6.6406(6) Å, b = 6.6784(8) Å, c = 10.2162(15) Å, α = 98.905(11)°, β = 92.237(9)°, γ = 119.446(11)°, Z = 2. In compound 1, all the terminal O atoms of [BO(OH)] clusters are hydroxyl groups, which hinder the further connection of the [BO(OH)] clusters, only forming 3-D supramolecular frameworks via extensive hydrogen-bonding interactions. In compound 2, the [BO(OH)] clusters link each other to form a 2-D layer, which are further extended to 3-D supramolecular frameworks via extensive hydrogen-bonding interactions. Interestingly, a novel in situ organic reaction between 1,3-diaminoprapane and CHCOO group has been observed during the formation of compound 1. [ABSTRACT FROM AUTHOR]

A new layered organic-inorganic hybrid lead borate [Pb(en)][BO(OH)] ( 1, en = ethylenediamine), has been hydro(solvo)thermally synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, FT-IR spectroscopy and thermogravimetric analysis, respectively. Compound 1 crystallizes in triclinic system space group P-1 (No. 2), a = 6.6537(6) Å, b = 6.7157(6) Å, c = 10.6911(9) Å, α = 99.015(7)°, β = 93.657(7)°, γ = 118.915(9)°, V = 407.59(6) Å, Z = 2. The structure consists of two infinite borate layers constructed from [BO(OH)] cluster building units, then two such layers are further connected by the linear [Pb(en)] complex linkers to form the novel bilayer structure. [ABSTRACT FROM AUTHOR]

A novel hydroxo-lanthanide cluster organic framework, SmL( μ-OH)(HO)·HO ( 1), derived from the 4-pyridin-4-ylbenzoic acid (HL) has been hydrothermally made and structurally characterized by single crystal X-ray diffraction. Structure analysis shows the hexanuclear Sm cluster unit is composed of inorganic tetranuclear hydroxo [Sm(OH)] (Sm) cluster and dimeric [Sm(COO)] (Sm) core. The Sm cluster units are connected by L ligands to form a 2D Ln-based cluster organic framework. From the topological point of view, the layer architecture can be described as 4-connected sql net. Furthermore, the elemental analysis, PXRD, IR and TGA are also studied. [ABSTRACT FROM AUTHOR]

A novel cluster organic framework, ErCuIL(HO) ( 1, L = 4-pyridin-3-yl-benzonate), has been hydrothermally made and structurally characterized by single crystal X-ray diffraction. Structure analysis shows [Er(COO)] (Er) clusters are linked by carboxylate groups generating one dimensional wave-like chain, which further extended by CuI (Cu) clusters into three dimensional heterometallic cluster organic framework. From the perspective of topology, such framework defines a new (7,9)-connected net, considering Er and Cu cores as the nodes. Furthermore, the elemental analysis, powder X-ray diffraction, infrared spectra and thermogravimetric analysis are also studied. [ABSTRACT FROM AUTHOR]

Two new cluster open framework borates, NaB3O5·0.5H2O (1) and NH4NaB6O10 (2) have been made under solvothermal conditions and characterized by IR, emission, and diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. The common structural features contain the oxoboron cluster building units, B3O7 and B6O13 cluster units for 1 and 2, in which the B3O7 and B6O13 clusters act as 4- and 6-connected nodes to further link each other, resulting in chiral qtz and achiral pcu nets, respectively. [ABSTRACT FROM AUTHOR]

Two new pentaborates [M(dap)][BO(OH)]·HO (M = Co ( 1) and Ni ( 2); dap = 1,2-diaminopropane) have been hydrothermally synthesized. Both structures were determined by single crystal X-ray diffraction and further characterized by elemental analysis, FT-IR, thermogravimetric analysis and photoluminescence spectroscopy. Two compounds are isostructural and consist of isolated pentaborate [BO(OH)] anions and [M(dap)] complex cations. The anionic [BO(OH)] groups are linked by extensive hydrogen bonds to form a 3-D supramolecular framework with large channels, in which the transition-metal complex templates are located. The luminescent properties of 1 and 2 were studied, and blue luminescence occurs with an emission maximum at 405 and 408 nm upon excitation at 332 and 328 nm respectively. Crystal data: 1, monoclinic, space group P2/ c (No. 14), a = 9.7159(5) Å, b = 29.3372(19) Å, c = 11.5121(6) Å, β = 103.286(5)°, V = 3193.6(3) Å, Z = 4; 2, monoclinic, space group P2/ c, a = 9.7264(4) Å, b = 29.3810(16) Å, c = 11.5185(6) Å, β = 103.249(4)°, V = 3204.0(3) Å, Z = 4. [ABSTRACT FROM AUTHOR]

A tetra-Co substituted sandwich-type polyoxotungstate (HTED)Cs[Co(HO)(B- α-HPWO)]·28HO (TED = triethylenediamine) has been hydrothermally synthesized and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction, respectively. Single-crystal structure analysis reveals that the tetra-Co substituted sandwich-type phosphotungstate units [Co(HO)(B- α-PWO)] are combined together by Cs cations giving rise to the 3D framework with the 'sqc876' 3D net. [ABSTRACT FROM AUTHOR]

Two unique organic-inorganic hybrid polyoxometalates constructed from Preyssler-type [Na(H2O)P5W30O110]14− ({P5W30}) subunits and TM/Ln-carboxylate-Ln connectors (TM=transition metal, Ln=lanthanide), KNa7[{Sm6Mn(μ-H2O)2(OCH2COO)7(H2O)18}{Na(H2O)P5W30O110}] ⋅22 H2O ( 1) and K4[{Sm4Cu2(gly)2(ox)(H2O)24}{NaP5W30O110}]Cl2 ⋅25 H2O ( 2; gly=glycine, ox=oxalate) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV/Vis-NIR spectra, thermogravimetric analyses, power X-ray diffraction, and single-crystal X-ray diffraction. Compound 1 displays one interesting 3D framework built by three types of subunits, {P5W30}, [Sm2Mn(μ-H2O)2(OCH2COO)2(H2O)5]4+, and [Sm4(OCH2COO)5 (H2O)13]2+, whereas 2 also manifests the other intriguing 3D architecture created by three types of subunits, {P5W30}, [SmCu(gly)(H2O)8]4+, and [Sm2(ox)(H2O)8]4+. To our knowledge, 1 and 2 are the first 3D frameworks that contain {P5W30} units and TM/Ln-carboxylate-Ln connectors. The fluorescent properties of 1 and 2 have been investigated. [ABSTRACT FROM AUTHOR]

Three 3D heterometallic 3d–4f MOFs, formulated as [Gd4L12(Cu10I8)(H2O)10]·2ClO4·4H2O (1), [La4(Ox)2L8(Cu7I5)(H2O)4]·2ClO4·4H2O (2), and [La4Na(Ox)3L8(Cu7I6)(H2O)3]·5H2O (3) [where Ox = oxalate, HL = 4-pyridin-4-ylbenzonic acid], have been made under hydrothermal conditions. All the MOFs are characterized by elemental analysis, IR, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. These novel 3D pillared-layer frameworks are constructed from 2D lanthanide–organic layers based on tetranuclear lanthanide clusters, and pillared by diverse copper(i) halide motifs. The oxalate is introduced as a coligand to make the hook-like tetramer in compound 1 into compact butterfly-like tetramer in compounds 2 and 3 due to its size preference. [ABSTRACT FROM AUTHOR]

Four organic–inorganic hybrid monolacunary Keggin polyoxotungstate-based 3d–4f heterometallic derivatives [Cu(en)2(H2O)]2[Tb(α-HSiW11O39)(H2O)3]·12H2O (1), [Cu(en)2(H2O)]2[Eu(α-HGeW11O39) (H2O)3]·12H2O (2), Na2[Cu(en)2(H2O)]4[Sm(α-PW11O39)(CH3COO)(H2O)]2·10H2O (3) and [Cu(en)2 (H2O)]5[Cu(en)2][Tb(α-GeW11O39)(CH3COO)(H2O)]2·14H2O (4) (en = ethylenediamine) have been hydrothermally prepared and characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray single-crystal diffraction. 1 and 2 are isomorphic and exhibit the interesting one-dimensional chain arrangements built by monovacant-lanthanide substituted Keggin-type [Ln(α-HXW11O39)(H2O)3]4− (Ln = TbIII, EuIII; X = SiIV, GeIV) units via W–O–Ln–O–W bridges whereas 3 and 4 display typical organic–inorganic hybrid dimeric structures consisting of [(α-XW11O39)Ln(H2O)(η2,μ-1,1)-CH3COO]210/12− units modified by [Cu(en)2(H2O)]2+ fragments. To the best of our knowledge, 1 and 2 represent the rare 1D chain-like monovacant Keggin-type 3d–4f heterometallic polyoxotungstates containing both unusual 1 : 1 [Ln(α-XW11O39)]4/5− units and en ligands, whereas 3 and 4 represent the first monovacant Keggin-type phosphotungstates or germanotungstates containing both 3d–4f heterometals and mixed ligands of en and acetate. Furthermore, the variable-temperature magnetic susceptibilities of 1 and 3 have been investigated. [ABSTRACT FROM AUTHOR]

A polyoxometalate (POM) based on the assembly of [P5W30O110]15- ({P5W30}) units and copper ions, {(H5P5W30O110)2[(en)4Cu4(μ3-OH)3(μ-H2O)]2}[Cu(en)2]4[Cu(H2O)3] ·12H2O (en = ethylenediamine) ( 1), has been made under hydrothermal conditions and characterized by single-crystal X-ray diffraction (XRD), elemental analysis, IR spectroscopy, thermogravimetric analysis, and power XRD; saturated {P5W30} was used as the precursor to make the new POM. POM 1 is the first 3D {P5W30}-based POM linked by late transition metal copper complex ions, and it also features the rarely seen linkages of the saturated {P5W30} units and [Cu4(μ3-OH)3(μ-H2O)] ({Cu4}) clusters. In the structure of 1, the {P5W30} units and {Cu4} clusters are alternately linked to form dimeric units and are further connected by two kinds of [Cu(en)2]2+ complex bridges, which results in the 3D framework. [ABSTRACT FROM AUTHOR]

Two types of new polyoxometalates (POMs) based on circular P8W48 clusters with different tetralanthanide (Ln) clusters and octamanganese centers, [K(H2O)2]4[K4(μ-H2O)4(H2O)4]2{[Ln2(μ-OH)4(H2O) x]2(H24P8W48O184)} · yH2O [Ln = Nd ( 1), Sm ( 2), Tb ( 3)] and [K(H2O)2]4[K4(μ-H2O)8]2[K(H2O)]8{[Mn8(H2O)16](H4P8W48O184)} ·36H2O ( 4) have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetry (TG), and powder XRD. Compounds 1- 3 are the first series of Ln-containing P8W48-based POMs that use P2W12O4814- as the precursor; previously known P8W48-based POMs used P8W48O18440- as the precursor. In 4, eight manganese ions were incorporated. Owing to the different radii of the Ln and Mn ions, the four large Ln ions are divided into two {Ln2} clusters located on two sides of the cavity of the P8W48 wheel in 1- 3, but the eight small manganese ions in 4 only bond to the inside of the P8W48 wheel and do not form manganese clusters. The magnetic properties of 3 are discussed. [ABSTRACT FROM AUTHOR]

Two additive-induced isomeric aluminoborates, (CH3NH3)2(H2O)2[Al(B5O10)] (1) and (CH3NH3)(H2O)[Al(B5O10)] (2), have been obtained by using small methylamine molecules as structure directing agents (SDA) under solvothermal conditions and characterized by elemental analysis, IR, TGA, powder X-ray diffraction, single-crystal X-ray diffraction, NLO determination, UV-vis spectral investigation, electronic structure calculation and ion exchange. Different arrangements of B5O10units and AlO4tetrahedra results in two different structures with two pairs of helical channels along [100] and [010] directions, respectively. Interestingly, the two frameworks with noncentrosymmetric and chiral space groups separately exhibit the same diamond topologies and display good second harmonic generation efficiencies of about 2.0 times the value of KDP. [ABSTRACT FROM AUTHOR]

Two three-fold interpenetrated frameworks, [LnCuL4][Ln0.25Cu0.25L] (Ln = Dy 1, Er 2; HL = 4-(pyridin-4-yl)benzoic acid), have been made. Their structures contain two kinds of four-connected uniform nets: dia and mdf nets. The mdf net is a new chiral 86net with the long vertex symbol (81.83.84.84.84.84). [ABSTRACT FROM AUTHOR]

A new mixed alkali metal borate LiCs[B 5 O 8 (OH)]·H 2 O ( 1 ) has been made under solvothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, diffuse-reflectance spectroscopy, powder X-ray diffraction and thermogravimetric analysis, respectively. 1 crystallizes in the monoclinic space group P 2 1 / c , a = 10.1523(9) Å, b = 8.4516(6) Å, c = 12.2178(17) Å, β = 122.522(8)°, V = 883.93(14) Å 3 and Z = 4. 1 exhibits a novel fluctuant anionic [B 5 O 8 (OH)] n 2n − layers based on the unusual B 5 O 10 (OH) oxoboron clusters, showing a four-connected spl topology net with the Schläfli symbol of {4 4 ·6 2 }. The layers are further linked via the Li O Cs chains and H-bonds to form a new 3-D structure. The cutoff edge of 1 is below 190 nm and it has a band gap of 5.82 eV. [ABSTRACT FROM AUTHOR]

Two new organic–inorganic hybrid copper–lanthanide heterometallic polyoxometalates (POMs), [Cu(dap) 2 ] 3.5 [Cu(dap) 2 (H 2 O)] 3 [La( α -SiW 11 O 39 ) 2 ]·5H 2 O ( 1 ) and H[Cu(dap) 2 (H 2 O)][Cu(dap) 2 ] 4 [Eu( α -PW 11 O 39 ) 2 ]·13H 2 O ( 2 ) (dap = 1,2-diaminopropane), have been made under hydrothermal conditions and characterized by elemental analyses, IR spectra, XRD, thermogravimetric (TG) analyses and X-ray single-crystal diffraction. They both display interesting 2D organic-inorganic hybrid POMs containing 3d-4f cations and organic dap ligands. To the best of knowledge, 1 represents the first 2D Cu–Ln heterometallic silicotungstate assembled by [La( α -SiW 11 O 39 ) 2 ] 13 − dimers and [Cu(dap) 2 ] 2 + linkers, while 2 is a new 2D Cu-Eu heterometallic Keggin-type phosphotungstate with dap ligands. Furthermore, the variable-temperature magnetic susceptibility of 2 has been investigated. [ABSTRACT FROM AUTHOR]

Abstract: A new organic–inorganic hybrid zinc borate [Zn(dab)0.5(dab′)0.5(B4O6(OH)2)]·H2O has been hydrothermally synthesized by using 1,4-diaminobutane (dab) as the linkers and characterized by means of elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction, respectively. This compound crystallizes in the monoclinic space group P21/c, a =9.997(3) Å, b =8.371(3) Å, c =16.321(4) Å, β =111.7(1)°, V =1268.8(7) Å3, Z =4. The structure contains ZnO2N2 tetrahedra, 1,4-dab and B4O7(OH)2 clusters, which interconnect to form a new three-dimensional framework. [Copyright &y& Elsevier]

Abstract: Two di-cadmium-substituted vanadoarsenates, [Cd(enMe)3]2{α-[(enMe)2Cd2As8V12O40(0.5H2O)]}·5.5H2O (1, enMe=1,2-diaminopropane) and [Cd(enMe)2]2{β-[(enMe)2Cd2As8V12O40(0.5H2O)]} (2), were hydrothermally synthesized and characterized by elemental analyses, IR, TGA, UV–Vis, XRD, magnetic measurements and single crystal structural analyses. Crystal data for 1: monoclinic, P2(1)/c, a=15.040(9)Å, b=20.288(12)Å, c=27.873(17)Å, β=98.046(8)°, V=8421.3(19)Å3, Z=4; for 2: monoclinic, P2(1)/n, a=12.753(3)Å, b=19.334(5)Å, c=14.310(3)Å, β=99.984(3)°, V=3475.1(14)Å3, Z=2. X-ray diffraction analyses reveal that compounds 1 and 2 exhibit isolated and one-dimensional inorganic–organic hybrid structures, respectively. The former is the first di-cadmium-substituted vanadoarsenate derived from α-{As8V14O42} shell, while the latter is another kind of di-cadmium-substituted vanadoarsenate derived from β-{As8V14O42} shell. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interactions between VIV cations in 1 and 2. [Copyright &y& Elsevier]

Abstract: Three new cobalt borate compounds, [Co(DIEN)2][B5O6(OH)4]2 (DIEN=diethylenetriamine) (1), [B5O7(OH)3Co(TREN)] (TREN=tris(2-aminoethyl)amine) (2), and [Co2(TETA)3][B5O6(OH)4]4 (TETA=triethylenetetramine) (3) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, elemental analysis and thermogravimetry. The structures exhibit interesting 3D supramolecular hydrogen-bonded architectures, involving the similar borate polyanion [B5O6+ n (OH)4− n ](n+1)−( for 1 and 3, and for 2) and the templating transition metal complexes which are generated in situ under mild solvothermal conditions. Crystal data: 1, monoclinic, space group C2/m (No. 12), , , , , , ; 2, monoclinic, P21/c (No. 14), , , , , , ; 3, triclinic, space group P-1 (No. 2), , , , , , , , . [Copyright &y& Elsevier]

Abstract: A new lead borate, Pb[B8O11(OH)4], has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, FTIR, powder X-ray diffraction and thermogravimetric analysis. The compound crystallizes in the monoclinic system, space group P21 /n (No. 14), , , , , , and . The structure consists of layers of 9-membered borate rings enclosing Pb2+ cations. Adjacent borate layers are interconnected via ionic Pb–O bonds and hydrogen bonding to form a 3D supramolecular network. [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]

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]

A novel vanadium oxide, [Cu(phen)V4O10]∞ (1), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR, EPR spectroscopy and thermal analysis. The compound crystallizes in monoclinic structure of P21/m with a=7.4169(10) A˚, b=10.0460(13) A˚, c=11.0845(15) A˚, β=102.520(2)°, V=806.27(19) A˚3 and Z=2. [Copyright &y& Elsevier]

A new nonlinear optical crystal [Ca 2 B 5 O 9 ]·[H(OH) 2 ] ( 1 ) has been synthesized under hydrothermal condition. Compound 1 crystallizes in the monoclinic space group C2 with lattice constants a = 10.111(2) Å, b = 7.754(11) Å, c = 6.198(14) Å, β = 127.04(3)° and Z = 2. The fundamental building block ( FBB ) of 1 is a [B 5 O 12 ] unit with two BO 3 triangles and three BO 4 tetrahedra. 1 was characterized by single-crystal X-ray diffraction, IR and UV–Vis spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) respectively. Also, powder second harmonic generation (SHG) measurements indicate that 1 is phase matchable and displays a SHG response of about 3.5 times that of KDP (KH 2 PO 4 ). [ABSTRACT FROM AUTHOR]

A novel octanuclear heterometallic {Ni 6 WNi}-substituted Keggin-type phosphotungstate [Ni(H 2 O)(en) 2 ][WO 4 ]{[Ni 6 (OH) 3 (H 2 O) 2 (en) 3 (Im) 2 ](B-α-PW 9 O 34 )}·2H 2 O ( 1 ) with mixed organic ligands of en and Im (en = ethylenediamine, Im = Imidazole) has been hydrothermally synthesized and structurally characterized by IR spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Notably, 1 is an interesting spoon-shaped monomeric polyoxometalate consisting of mixed organic ligands and unprecedented octanuclear heterometallic {Ni 6 WNi} cores where the WO 4 tetrahedron is linked to the triangular {[Ni 6 (OH) 3 (H 2 O) 2 (en) 3 (Im) 2 ](B-α-PW 9 O 34 )} clusters and [Ni(H 2 O)(en) 2 ] 2 + cations through Ni–O t –W linkages. Magnetic susceptibility measurements indicate ferromagnetic coupling within 1 . [ABSTRACT FROM AUTHOR]

An open-framework borate [Zn(H 2 O) 4 ][B 6 O 10 ] with acentric structure, has been successfully obtained for the first time under solvothermal conditions. It has been characterized by powder and single crystal X-ray diffraction, IR spectroscopy, diffuse-reflectance spectroscopy and thermogravimetric (TG) analyses, respectively. It crystallizes in the orthorhombic system, space group Pna 2 1 , a = 11.3140(6) Å, b = 11.8995(7) Å, c = 8.6140(5) Å and Z = 4. In the structure, the alternative connections between [B 3 O 7 ] units give rise to an unprecedented 3D borate framework with 11- and 10-MR channels, in which the [Zn(H 2 O) 4 ] 2+ complexes are located. It has a cut-off edge below 200 nm and exhibits second harmonic generation (SHG) efficiency approximately 0.4 times that of KH 2 PO 4 (KDP). [ABSTRACT FROM AUTHOR]

Abstract: A novel 2-D hexa-CuII substituted sandwich-type polyoxotungstate [Cu(H2O)4][Cu(dien)(H2O)2]2[Cu(dien)(H2O)]2[Cu6(en)2(H2O)2(B-α-HGeW9O34)2][Cu6(Hdien)2(H2O)2(B-α-HGeW9O34)2]·24 H2O (1, en=ethylenediamine, dien=diethylenetriamine) has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. 1 represents the first 2-D inorganic–organic hybrid sandwich-type germanotungstate constructed by two kinds of hexa-CuII substituted sandwich-type POM hybrid units accompanying the mixed organoamine components in the structure. The TGA curve of 1 displays two continuous weight loss stages. [Copyright &y& Elsevier]

A new noncentrosymmetric aluminoborate (H2TETA)[Al(B5O10)] (1), has been solvothermally synthesized by using triethylenetetramine (TETA) as the structure-directing agent. Single-crystal X-ray diffraction analysis reveals that the compound crystallizes in the orthorhombic space group Pna21 with unit cell parameters a =12.9696(9) Å, b =17.0035(8) Å, c =7.3660(5) Å, V =1624.41(18) Å3 and Z =4. Its structure consists of AlO4 tetrahedra and B5O10 clusters and possesses 8-, 11- and 14-ring channels with sra topology. Second-harmonic generation (SHG) measurements on the powder samples reveal that 1 exhibits moderate SHG signals approximately 1.5 times that of KH2PO4 (KDP). [ABSTRACT FROM AUTHOR]

Abstract: A novel Cu–azido complex modified hexa-CuII substituted sandwich-type phosphotungstate [Cu(en)2]{[Cu2(en)2(μ-1,1-N3)2(H2O)]2[Cu6(en)2(H2O)2(B-α-PW9O34)2]}·6H2O (1) (en=ethylene-diamine) has been prepared under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. 1 displays a beautiful 1-D chain architecture constructed from sandwich-type [Cu2(en)2(μ-1,1-N3)2(H2O)]2[Cu6(en)2(H2O)2(B-α-PW9O34)2]2− units and [Cu(en)2]2+ linkers. To our knowledge, 1 represents the first hexa-CuII sandwiched phosphotungstate with supporting Cu–azido complexes. [Copyright &y& Elsevier]

A new mixed metal borate LiBa1.5[B5O8(OH)3] (1) has been hydrothermally synthesized and structurally characterized by FT-IR spectroscopy, powder X-ray diffraction, single crystal X-ray diffraction, and thermogravimetric analysis, respectively. 1 crystallizes in the monoclinic system, space group C2/c, a =11.2839(7) Å, b =7.3974(4) Å, c =20.7151(13) Å, β =103.392(6)°, V =1682.10(17) Å3 and Z =8. The structure consists of infinite one-dimensional (1-D) borate chains constructed from B5O9(OH)3 6− cluster units. These B O chains are further linked by the Ba2+ and Li+ cations to form a 3-D framework. [ABSTRACT FROM AUTHOR]

Abstract: A series of new polyoxometalates based on [Ni6(μ3-OH)3(H2O)6(en)3(B-α-PW9O34)] (en=ethylenediamine) clusters capped by different tripodal alcohol ligands have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray diffraction, respectively. The experimental results indicate that the tripodal alcohol ligands can substitute three hydroxyl groups located on the axial positions of the Ni6 cluster to form new polyoxometalates with different substituted modes. [Copyright &y& Elsevier]

Five aluminoborates Al[B5O10]∙H2dab∙2H2O (1), [Al(B4O9)(BO)] ∙ H2en (2), [Al(B4O9)(BO)]∙H2dap (3), K2Al[B5O10]∙4H2O (4), and (NH4)2Al[B5O10] ∙ 4H2O (5) have been synthesized under hydrothermal conditions and characterized by means of elemental analysis, IR, TG analysis, MAS NMR, UV-vis and fluorescence spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, and NLO determination. The structure 1 comprises of A1O4 tetrahedra and B5O10 clusters and contains 12-, 11-, and 8-MR 3D-intersecting channels with a CrB4 topological net. Structures 2 and 3 are both constructed from the same AlB5O13 clusters and exhibit a six-connected framework with 41263 topology. Structures 4 and 5 are isomorphous and are composed of AlO4 tetrahedra and B5O10 clusters that possess odd 11-MR channels and 8-MR helical channels. Structures 2-5 crystallized in an acentric structure and presented good SHG properties. UV-vis spectral investigation indicates that they are wide-band-gap semiconductors. The electronic structure calculations for the compounds also have been performed. [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: Two inorganic–organic hybrid solids, Zn2(phen)(HPO3)2 (1) and Zn(phen)(HPO3) (2), have been synthesized under solvothermal conditions in the presence of 1,10-phenanthroline (phen) ligands. Their structures were determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectra. Compound 1 crystallizes in the triclnic system, space group P-1, , , , , , , , . Compound 2 is monoclinic, , , , , , , . Both structures consist of 1D chains constructed from strictly alternating ZnO4 and HPO3 polyhedra through sharing vertices. The chains are further decorated by Zn-centered complex architectures, [Zn(phen)]2+ for 1 and [Zn(phen)2]2+ for 2. The 2D and 3D supramolecular arrays for 1 and 2 are stably stacked via strong π–π interactions of the phen groups, respectively. [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]

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 compound [Zn(H2O)4]2[H2As6V15O42(H2O)]·2H2O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) A˚, c=33.970(7) A˚, γ=120°, V=4278.8(12) A˚3, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H2As6V15O42(H2O)]4− anions and [Zn(H2O)4]2+ cations linked through hydrogen bonds into a network. The [H2As6V15O42(H2O)]6− cluster consists of 15 VO5 square pyramids linked by three As2O5 handle-like units. [Copyright &y& Elsevier]