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Five new luminescent metal–organic frameworks (MOFs), [Cd(bdc)(dia)0.5(MeOH)](DMA)0.5 (1), [Cd2O(1,4-ndc)2(dia)2(H2O)]·DMA (2), [Cd(1,4-ndc)(dia)]·MeOH (3), [Cd(bpdc)(dia)0.5]·DMF (4), [Cd(bpdc) (dia)]·DEF (5) (dia = 9,10-bis(1H-imidazol-1-yl)anthracene), were obtained from solvothermal conditions and characterized by PXRD, IR, TG, and PL spectra. Single-crystal X-ray diffraction analyses showed that all compounds 1–5 display three-dimensional architectures with diverse topologies. Compound 1 was a 6-con pcu network based on dinuclear Cd cluster. Compound 2 features an eight-connected network constructed from a binuclear Cd cluster. Compound 3 presents a 3-fold interpenetrated four-connected dia topology. Compounds 4 and 5 exhibit a 3-fold interpenetrated six-connected pcu framework and a 3-fold interpenetrated four-connected dia net, respectively. Because compounds 3–5 have one-dimensional (1D) channels, the luminescence properties of 3–5 in different solvents were investigated systematically. Furthermor...

The reaction of Na2WO4 and Na2SeO3 in the presence of MnCl2 under moderately acidic conditions yielded two unprecedented tungstoselenites: dimeric K2Na10[K2⊂{MnSe4W23O85(H2O)6}]·29H2O (1) and trimeric wheel-shaped K2Na10[K2⊂{Mn3Se7W39O131(OH)20(H2O)2}]·60H2O (2). The assemblies of 1 and 2 are based upon the structure directing effects of SeIV heteroatoms for generating diverse well-defined vacancy selenotungstate precursors during the formation. The polyoxoanion of 1 contains two novel Wells–Dawson-type-like {Se2W11} fragments, which are constructed from novel {SeW4} and {SeW7} species derived from Wells–Dawson-type {α-Se2W14} fragments and one disorder of Mn/W center. The polyoxoanion of 2 exhibits a crown-type structure composed of a [Se6W38O120(OH)18(H2O)2]6– “host” (abbreviated as {Se6W38}) encapsulating SeO32–-modified Mn/W and two K+ “guests”. Remarkably, the crown {Se6W38} shell remains a new type of {Se2W12}-based trimeric aggregate in the polyoxometalates chemistry. The two compounds were charact...

Four novel high-dimensional metal–organic rotaxane frameworks (MORFs) were successfully fabricated by cucurbit[6]uril-based pseudorotaxanes ([PR43]) and rigid carboxylate ligands by adjusting the synthesis temperature and the length of ligands. Compound 1 represents a three periodic 2-fold interpenetrating dia network based on a binuclear {Cd2Cl4O4} second building unit (SBU). 2 and 3 are isostructural pcu networks constructed by binuclear and trinuclear cadmium clusters, respectively, while compound 4 is a two-dimensional layered network with a large grid 44.3 × 19.8 A2. Furthermore, their fluorescent properties in different solvents are investigated.

Four new architectures containing [Co2Mo10H4O38]6– polyoxoanion, [Ln(H2O)7][Ln(H2O)5][Co2Mo10H4O38]·5H2O (Ln = Gd 1; Tb 2), and (NH4)3[Ln(H2O)6][Co2Mo10H4O38]·6H2O (Ln = Gd 3; Tb 4) have been synthesized at different temperatures and characterized by elemental analysis, IR and Raman spectroscopy, TG analysis, powder X-ray diffraction and single crystal X-ray diffraction. Isostructural compounds 1 and 2 obtained at the higher temperature (85 °C), are built up of Evans–Showell-type polyoxoanions [Co2Mo10H4O38]6–, respectively, linked by Gd3+ or Tb3+ cations to form a 3D racemic framework with 1D zigzag channels. From the topological point of view, the 3D net is a rare binodal 4-connected SrAl2 (sra) topology. As far as we know, compounds 1 and 2 represent the first examples of 3D architectures based on Evans–Showell-type polyoxometalate. Interestingly, the stable 3D microporous compounds exhibit selective adsorption ability: adsorbing water and methanol, as well as excellent photocatalytic activity for orga...

Six new coordination polymers, (Me2NH2)[In(L)]·DMF (1), (Me2NH2)2[In2(L)2]·(DMF)3·(H2O)2 (2), (Me2NH2)4[Cd2(L)2]·(DMF)2 (3), (Et2NH2)2[Cd(L)]·H2O (4), (Et2NH2)3[Cd2(L)2]·(DEF)2·(H2O)4 (5), (Et2NH2)3[Cd2(L)2]·(EtNH2)2·(H2O)2 (6) have been prepared based on a newly designed flexible tetracarboxylate ligand of H4L {H4L = 5-[bis(3-carboxybenzyl)amino]isophthalic acid; DMF = N,N-dimethylformamide; DEF = N,N-diethylformamide}. Compounds 1–6 possess very similar two-dimensional framework structures with (4,4)-net topology. These compounds comprise two groups of conformational supramolecular isomers, owing to identical compositions of the frameworks but different conformations of ligands. It is worth noting that as much as seven pairs of stereoisomers of ligands have been found in these compounds, which demonstrated that the introduction of multiple single bonds has greatly expanded the flexibility of the ligand. The photoluminescent properties of compounds 1–6 have also been investigated where the emission of th...

A new compound based on the Wells–Dawson polyoxometalate, Ag7(bbi)5(OH)(P2W18O62) (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (1), has been hydrothermally synthesized and characterized by the normal physical methods and single-crystal X-ray diffraction. Compound 1 represents the first interpenetrating framework based on the Wells–Dawson POMs. The AgI···AgI interactions are crucial in the formation of the two individual motifs: in the first interpenetrating motif, the supported {Ag2}2+ dimers and the P2W18 polyanions form an infinite inorganic chain, then the Ag+ monomers and bbi ligands extend the chain to form a three-dimensional framework. The second motif is constructed by the Ag–bbi meso-helix chains which are stitched by the unsupported Ag7···Ag7 dimers to form a two-dimensional layer with huge loops. The electrochemical study exhibits that compound 1 could be used as electrocatalyst in the electrical reductions of bromate. In addition, compound 1 shows a photocatalytic action for degradation of RhB.

A new 3D chiral metal–organic framework [Co2(BTT)(OH)(H2O)5]·5CH3OH·6DMA (1) has been synthesized using an achiral tritopic bridging ligand, 1,3,5-tris(2H-tetrazol-5-yl)benzene (H3BTT). 1 possesses a (10,3)-a net containing large helical channels of 17.43 A and exhibits a high solvent-accessible volume (calculated 79%). The N2 adsorption and magnetic properties for 1 have been examined.

With the use of a flexible N-donor ligand 1,3-bis(4-pyridyl)propane (bpp), a new porous framework with Wells-Dawson clusters as nodes and Ni2+ ions as linkers, [Ni(bpp)(H2O)2]3[P2W18O62]·∼24H2O (1), has been successfully obtained. Topological analysis indicates that 1 possesses a perovskite structure. As a porous framework, 1 displays adsorption behavior toward H2O and CH3OH.

Six binary metal−organic compounds, namely, [Cd(L)2] (1), α-[Cd(L)2(H2O)] (2), β-[Cd(L)2(H2O)] (3a and 3b), γ-[Cd(L)2(H2O)] (4), and [Cd(L)2(H2O)2] (5), where HL = 4-(pyridin-3-ylmethoxy)benzoic acid, have been synthesized under hydrothermal conditions. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. The structure of 1 is a two-dimensional (2D) → 2D 3-fold parallel interpenetrating network with (4,4) grid. Compounds 2, 3, and 4 are supramolecular isomers formed by Cd(II) cations, L− ligand, and water molecule, showing a 2D → 2D 2-fold parallel interpenetrating (4,4) network for 2, single (4,4) network for 3a and 3b, and (66) topological net for 4 through using different reaction materials. Compounds 3a and 3b show chiral structures by spontaneous resolution using an achiral ligand. In compound 5, Cd(II) cations are linked by L− ligands to form an infinite chain. Comparing these s...

Seven coordination polymers constructed from structurally related ligands, namely, [Cd2(ODPT)(L1)(H2O)2]·H2O (1), [Cd2(ODPT)(L2)(H2O)2] (2), [Zn2(BPTC)(L3)]·(H2O)3 (3), [Cd(m-BDC)(L4)] (4), [CdL5] (5), [CdL6]·H2O (6), and [ZnL6]·H2O (7) (H4ODPT = 4,4′-oxidiphthalic acid, H4BPTC = 3,3′,4,4′-benzophenone tetracarboxylate ligand, H2m-BDC = 1,4-benzenedicarboxylate acid, L1 = 1,4-di(1H-benzo[d]imidazol-2-yl)butane, L2 = bis((1H-benzo[d]imidazol-2-yl)methyl)amine, L3 = 1,4-bis(1-(pyridin-4-ylmethyl)-1H-benzo[d]imidazol-2-yl)butane, L4 = bis((1-(pyridin-4-ylmethyl)-1H-benzo[d]imidazol-2-yl)methyl)amine, H2L5 = 4,4′-(2,2′-(butane-1,4-diyl)bis(1H-benzo[d]imidazole-2,1-diyl))bis(methylene)dibenzoic acid, and H2L6 = 2,2′-(2,2′-azanediylbis(methylene)bis(1H-benzo[d]imidazole-2,1-diyl))diacetic acid) have been synthesized under hydrothermal conditions. Their structures have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (...

Three inorganic−organic hybrids based on polyoxometalate (POM), [Cu6(bbtz)6(HPM12O40)]·2H2O (M = Mo, 1; W, 2) and [Cu6(trz)2(bbtz)2(SiW12O40)] (3) (trz = 1-H-1,2,4-triazole, bbtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), were synthesized under hydrothermal conditions, and structurally characterized. Through the use of the flexible ligand bbtz, isostructural compounds 1 and 2 with interpenetrating structures were obtained. In compound 1, ladder-like chains exist, in which the PMo12 anions act as “middle rails”. These chains are linked by wave-like [Cu(bbtz)]nn+ lines to construct a three-dimensional (3D) framework. Two such frameworks penetrate each other to construct a 2-fold interpenetrating structure. By introducing the rigid ligand trz, compound 3 with an un-interpenetrating structure is obtained. In compound 3, two-dimensional (2D) (63)2 metal organic framework (MOF) layers exist, which are linked by Keggin anions to construct a 3D (44·62)(63)2 framework. The differences between these compounds sho...

Reactions of hexavacant polyoxotungstate [H2P2W12O48]12− ({P2W12}) with transition-metal and lanthanide-metal cations assisted with organic molecules (tartrate or dimethylammonium chloride) lead to the isolation of two polyoxotungstates: K3Na8[K3⊂{GdMn(H2O)10}{HMnGd2(Tart)O2(H2O)15}{P6W42O151(H2O)7}]·44H2O (1) and K3Na10[K3⊂{GdCo(H2O)11}2{P6W41O148(H2O)7}]·43H2O (2). Single-crystal X-ray diffraction analyses reveal that both 1 and 2 contain a crown-type polyoxoanion shell [{WO(H2O)}3(P2W12O48)3]30− ({P6W39}), which consists of three {P2W12} units connected by three {WO(H2O)} linkers. Compound 1 has a two-dimensional porous framework constructed from 3d-4f cluster-containing {P6W39} aggregates and mixed 3d and 4f linkers. Compound 2 exhibits a one-dimensional chain-like structure composed of di-Co-containing {P6W39} aggregates and {Gd(H2O)7}3+ bridging units. Magnetic studies of compounds 1 and 2 indicate that antiferromagnetic interactions exist in these two compounds.

Reactions of Ph3SnCl or Ph3SnOH with the alkylarsonic acids, RAsO3H2, where R = n-propyl, n-butyl, benzyl, and 4-NO2-benzyl, have led to two types of tin oxo clusters: [Sn3Cl3(μ3-O)(R′O)3]2(RAsO3)4 [R = n-Bu, R′ = Et (1); R = n-Pr, R′ = Et (2); R = Bz, R′ = Et (3); R = n-Pr, R′ = Me (4), and R = 4-NO2−Bz, R′ = Et (5)] and [(PhSn)3(RAsO3)3(μ3-O)(OH)(R′O)2]2Sn [R = n-Pr, R′ = Et (6) and R = 4-NO2-Bz, R′ = Et (7)]. Two types of structural units, [Sn3(μ3-O)(μ2-OR′)3] for compounds 1−5 and [Sn3(μ3-O)(μ2-OR′)2] for compounds 6 and 7, were obtained by subtle changes of the organotin precursors. For the first time, hydrogen-bonding interactions such as C−H···Cl, C−H···O, and C−H···π were investigated in the crystal structures of tin alkylarsonate clusters (2−7). The cumulative effects of these weak interactions result in one-, two-, and three-dimensional suparmolecular architectures of 2−7.

Two novel hybrid compounds, [Cu2(Phen)4Cl][Cu2(Phen)3(H2O)Cl][P2W18O62]·H2O (1) and [Cu7(Phen)7(H2O)4Cl8] [P2W18O62]·6H2O (2) (Phen = 1,10-phenanthroline), containing multinuclear CuII complex cations, have been obtained in hydrothermal conditions and characterized by IR, elemental, thermogravimetric, magnetic, electrochemical and single-crystal X-ray diffraction analyses. The main structural feature to these two compounds is the presence of different copper−Phen complex moieties which compose new multinuclear copper−Phen complexes linked by a Cu−Cl bond. The binuclear cations [Cu2(Phen)4Cl]3+ and [Cu2(Phen)3(H2O)Cl]3+ of 1 indicate a special chiral arrangement. The 2 contains a heptanuclear copper chain [Cu7(phen)7(H2O)4Cl8]6+ formed by a one-Cl bridge and a two-Cl bridge. Magnetic studies prove that Cu−Cl−Cu angles result in different magnetic behaviors in 1 and 2. Furthermore, a compound 2-modiffied carbon paste electrode (2-CPE) displays good electrocatalytic activity toward the reduction of nitrite.

Two novel α-Keggin anion-based coordination polymers with argentophilic {Ag3}3+/{Ag4}4+ clusters, [{Ag3(bpy)4}{PMo12O40}]·2H2O (1), [{Ag(bpy)}2{Ag4(bpy)6}{PMo11VO40}][{Ag(bpy)}2{PMo11VO40}] (2), have been hydrothemally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. The crystal data for these are the following: C40H36Ag3Mo12N8O42P (1), triclinic P1, a = 10.5245(19) A, b = 12.058(2) A, c = 13.530(2) A, α = 87.015(2)°, β = 72.146(2)°, γ = 86.563(2)°, Z = 1; C100H80Ag8Mo22N20O80P2V2 (2), triclinic P1, a = 13.3603(15) A, b = 16.3035(18) A, c = 16.7523(19) A, α = 89.896(2)°, β = 84.000(2)°, γ = 88.066(2)°, Z = 1. Polymer 1 consists of an infinite zigzag one-dimensional (1D) chain constructed from [Ag3(bpy)4]3+ clusters and [PMo12O40]3− anions. Polymer 2 consists of isolated bisupporting [{Ag(bpy)}2{PMo11VO40}]2− anions and infinite 1D cationic chains [{Ag(bpy)}2{Ag4(bpy)6}{PMo11VO40}]2+ constructed from [{Ag(bpy)}2{PMo11V...

Through tuning the spacer length of flexible bis(triazole) ligands, three Keggin anion-based coordination polymers with different dimensionalities, [Cu4(H2O)4(bte)2(HPMoVI10MoV2O40)]·2H2O (1) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane), [Cu(btb)][Cu2(btb)2(PMo12O40)] (2) (btb = 1,4-bis(1,2,4-triazol-1-y1)butane), and [Cu5(btx)4(PMoVI10MoV2O40)] (3) (btx = 1,6-bis(1,2,4-triazol-1-y1)hexane), were synthesized and structurally characterized. Compound 1 exhibits a ladder-like chain, in which the polyoxometalate (POM) anions act as the “middle rails” of the ladder. The bte ligand with shortest spacer length acts as not only the bridging linker but also the chelator, which terminates the dimensional extension. Compound 2 exhibits a 2D POM-based framework, containing POM/Cu/btb grid-like layers. In compound 3, there exist three sets of (123)(121)2 2D Cu-btx frameworks to generate a 3-fold interpenetrating structure, into which the hexadentate POM anions are inserted to construct a 3D structure. The structural anal...

Six coordination polymers constructed from three structurally related ligands, 1,2-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene (L1), 1,3-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene (L2), and 1,4-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene (L3) have been synthesized: [Zn2(ODPT)(L1)0.5(H2O)]·3H2O (1), [Zn2(ODPT)(L2)(H2O)2]·3H2O (2), [Zn2(ODPT)L3(H2O)]·6H2O (3), [Cd2(ODPT)(L1)0.5(H2O)]·4H2O (4), [Cd(H2ODPT)(L2)]·2H2O (5), and [Cd1.5(HODPT)(L3)0.5] (6), where H4ODPT is 4,4′-oxidiphthalic acid. Their structures have been determined by single crystal X-ray diffraction analyses. All compounds are also characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. Compound 1 exhibits a two-dimensional (2D) layer structure with tetra-nuclear zinc clusters as building units, and intermolecular π···π stacking interactions link these sheets to a three-dimensional (3D) supramolecular structure. Compound 2 shows infinite chains and is extended into a 2D supramolecular sheet by intermolecular h...

Seven coordination polymers, namely [Zn(BPTC)0.5(L1)0.5(H2O)] (1), [Zn2(BPTC)(L2)]·H2O (2), [Zn2(BPTC)(L3)2]·3H2O (3), [Zn2.5(BPTC)(L4)(OH)(H2O)] (4), [Zn2(BPTC)(L5)(H2O)2]·3H2O (5), [Cd2(BPTC)(L5)(H2O)]·H2O (6), and [Cd(BPTC)0.5(L6)]·H2O (7), where L1 = 4,4′-bis(imidazol-1-ylmethyl)bibenzene, L2 = 4,4′-bis(imidazol-1-ylmethyl)benzene, L3 = 1,4-bis(imidazol-1-yl)butane, L4 = 1,4-bis(2-ethyl-imidazol-1-yl)butane, L5 = 1,3-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene, L6 = 1,2-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene, and BPTC = 3,3′,4,4′-benzophenone tetracarboxylate ligand, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. The structure of 1 exhibits a (4,6)-connected network with a (44·62)(44·610·8) topology formed by L1 ligands connecting BPTC−Zn sheets. The structure of 2 is a chiral 3D network in which there exists a Zn−O...

By introducing different long rigid ligands into polyoxometalate (POM) systems, four novel inorganic–organic hybrids containing multitrack Cu−N coordination polymeric chain-modified POMs, {[Cu(4,4′-bipy)]3[HGeMo12O40]}·0.5H2O (1), [Cu(4,4′-bipy)]{[Cu(4,4′-bipy)]2[W6O19]}·4H2O (2) (bipy = bipyridine), [Cu(bpe)]{[Cu(bpe)]2[GeMo12O40(VO)2]} (3) (bpe = bis(4-pyridyl)ethylene), and [Cu2(phnz)3]2[SiW12O40] (4) (phnz = phenazine), have been hydrothermally synthesized and characterized by routine physical methods. The crystal structures of 1–4 have been established by single crystal X-ray diffraction. Compound 1 exhibits a tritrack Cu−N chain-modified Keggin POM 1D structure. Compound 2 represents the first example of a 2D framework constructed from a Lindquist polyoxoanion modified by double bitrack Cu−N chains via its terminal oxygen and bridge oxygen atoms. The rail-like 1D structure of compound 3 is formed from Keggin clusters modified by double monotrack Cu−N chains. Compound 4 shows a pseudo-1D structure of...

Two novel multi-Ni-substituted polyoxometalates K12[(SiW8O31)2Ni7(H2O)4(OH)6]·23H2O (1) and K6Na18[H2{Ni5(H2O)5(OH)3(x-SiW9O34)(β-SiW8O31)}2]·39H2O (2) have been successfully synthesized by routine synthetic reactions in aqueous solution. Single-crystal X-ray analysis was carried out on the two compounds (1 and 2), which both crystallize in the triclinic system. For 1, space group P1, a = 11.442(2) A, b = 11.905(2) A, c = 17.169(3) A, α = 107.62(3)°, β = 91.67(3)°, γ = 102.37(3)°, V = 2166.1(8) A3, Z = 1. For 2, space group P1, a = 18.435(4) A, b = 25.095(5) A, c = 25.095(5) A, α = 81.44(3)°, β = 73.87(3)°, γ = 85.31(3)°, V = 9624(3) A3, Z = 2. Compound 1 represents the first example of the double-cubane Ni7O8-cluster-substituted polyoxometalates, and the [β-SiW8O31] unit in 1 was scarcely reported previously. Compound 2 exhibits a novel asymmetric dimeric structure, consisting of [β-Ni3SiW9O37(H2O)3] and [γ-SiW8Ni2O34(H2O)2] units linked by three μ3-OH groups. In the [β-Ni3SiW9O37(H2O)3] half unit, thi...

Three novel porous coordination polymers based on lead(II) and isonicotinic acid N-oxide, [Pb(INO)2]2·7H2O (1), [Pb(INO)2]·nH2O (2), and [Pb4(OH)4(INO)4]·nH2O (3) (HINO = isonicotinic acid N-oxide), have been synthesized and characterized through single-crystal X-ray diffraction. Compound 1 features a most remarkable and unique three-dimensional (3D) framework with two distinct kinds of channels showing different sizes and shapes, which are occupied by two kinds of water clusters, according to the size and shape of the channels. Compound 2 possesses a 3D framework built up from one-dimensional (1D) Pb−O chains and INO ligands with 1D rectangular channels, in which lattice water molecules are located. The structure of 3 consists of [Pb4(OH)4]4+ cluster inorganic building blocks, which connect with μ4-INO ligands through oxygen atoms from N-oxide moieties and carboxylate groups of INO to form 8.7 × 8.7 A2 rhombic channels running along the c-axis. In addition, the photoluminescence properties of coordinatio...

A (3,12)-connected 3D metal-organic framework has been synthesized based on octanuclear zinc clusters as 12-connected nodes and flexible carboxylate ligands as 3-connected nodes, and it represents the highest connected binodal network topology presently known for metal-organic frameworks.

A (4,8)-connected metal-organic framework has been constructed using an asymmetrical ligand based on dinuclear cadmium clusters as eight-connected nodes and mononuclear cadmium atoms as four-connected nodes, and it represents the flu topology network.