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Single-atom catalysts (SACs), known for their high atomic utilization efficiency, are highly attractive for electrochemical CO 2 conversion. Nevertheless, it is struggling to use a single active site to overcome the linear scaling relationship among intermediates. Herein, an isolated diatomic Ni-Mn dual-sites catalyst was anchored on nitrogenated carbon, which exhibits remarkable electrocatalytic performance towards CO 2 reduction. The catalyst achieves CO Faradaic efficiency (FE CO ) over 90 % within the potential range of -0.6 to -1.4 V vs. reversible hydrogen electrode (RHE), and a nearly 100 % FE CO at a current density of 325 mA cm -2 in the flow cell. The Ni-Mn-NC also exhibits long-term stability, maintaining FE CO above 96 % for over 14 h. The density functional theory (DFT) studies further reveal that the synergistic effect of adjacent Ni-Mn centers effectively reduces the reaction barriers for the formation of *COOH and thus accelerates the reduction of CO 2 ., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier Inc. All rights reserved.)

Two unique 22-core sandwich {[Mn 6 Mo 6 O 37 ]Ln 3 [MnMo 6 O 24 ]} (Ln = La or Pr) units have been assembled, featuring an undisclosed {Mn 6 Mo 6 } cluster. This assembly is subsequently integrated into two three-dimensional polyoxometalate organic frameworks, which exhibit one-dimensional hydrophilic hexagonal channels formed by six intertwined 6 3 helical chains, leading to effective proton conduction primarily facilitated by an abundance of water molecules within the channels.

Lanthanide-containing polyoxometalate-based metal-organic frameworks (POMOFs) not only enjoy intriguing architectures but also have good application prospects as catalysts. Herein, three novel three-dimensional (3D) POMOFs with the formulas of {H[Ln 3 (2,6-pydc) 2 (H 2 O) 10 (MnMo 9 O 32 )]·2H 2 O} n (Ln = La( 1 ), Pr( 2 ), Nd( 3 )) have been synthesized based on Waugh-type [MnMo 9 O 32 ] 6- anions and pyridine-2,6-dicarboxylate (2,6-H 2 pydc). Compounds 1 - 3 are isomorphic, and there are two kinds of one-dimensional (1D) helical chains with opposite handedness staggered into two-dimensional (2D) layers. Interestingly, the coordinated L - and R -[MnMo 9 O 32 ] 6- anions are encapsulated in 1D chains with the same chirality and are further expanded into 3D structures. The catalytic tests indicate that compounds 1 - 3 exhibit high-efficiency heterogeneous catalytic activity in the oxidative desulfurization reaction for catalyzing the oxidation of sulfides to sulfoxides using tert -butyl hydrogen peroxide (TBHP) as the oxidant. Moreover, a series of control experiments have been conducted to investigate the influence of various parameters such as temperature, time, solvent, catalyst, and substrate on the reaction. Significantly, compound 2 , as an example, exhibits good reusability and structural stability in the oxidative desulfurization reaction. It is worth noting that investigations on the oxidative desulfurization of [MnMo 9 O 32 ] 6- anions are scarce. Moreover, their electrochemical properties are also explored.

Achieving long-term stable deep desulfurization at room temperature and recovering high value-added sulfone products is a challenge at present. Herein, a series of catalysts [C n mim] 5 VW 12 O 40 Br (C n VW 12 , 1-alkyl-3-methylimidazolium bromide tungstovanadate, n = 4, 8, 16) were presented for the room temperature catalytic oxidation of dibenzothiophene (DBT) and its derivatives. Factors affecting the reaction process, such as the amount of catalyst, oxidant, and temperature, were systematically discussed. C 16 VW 12 showed higher catalytic performance, and 100% conversion and selectivity could be achieved in 50 min with only 10 mg. The mechanism study showed that the hydroxyl radical was the active radical in the reaction. Benefiting from the "polarity strategy", the sulfone product accumulated after 23 cycles in a C 16 VW 12 system, and the yield and purity were about 84% and 100%, respectively.

Two three-dimensional frameworks based on the {P 4 Mo 6 } unit, H(4,4'-bipy) 2 [Fe 4 (PO 4 )(H 2 O) 4 Na 6 ][Fe 6 (H 2 O) 4 ][(Mo 6 O 12 )(HPO 4 ) 3 (PO 4 )(OH) 3 ] 4 ·5H 2 O (4,4'-bipy = 4,4'-bipyridine) (1) and H 3 (C 12 H 14 N 2 ) 4 [Fe 4 (PO 4 )(H 2 O) 4 Na 4 ][Fe 2 (Mo 6 O 12 (HPO 4 ) 3 (PO 4 )(OH) 3 ) 4 ]·6H 2 O (2) were successfully synthesized by varying the solvent. The extended structures of the two compounds were formed by transition metal Fe(II) ions bridging the {P 4 Mo 6 }-based tetrameric clusters around [Na X Fe 4 (PO 4 )] ( X = 6 (1), or X = 4 (2)) core. The 4,4'-bipy molecules and in situ generated methyl viologen cations as templates induce the formation of two three-dimensional structures, an 8-connected bcu topology framework for 1 and a 4-connected 2-fold interpenetrating diamond-like topological network for 2, respectively. Additionally, multiform hydrogen bonds are found in the framework and also play an important role in stabilizing the structure. The proton conduction mechanism of the two compounds can be mainly classified as the Grotthuss mechanism; the proton conductivity values are 1.06 × 10 -3 S cm -1 for 1 and 3.13 × 10 -3 S cm -1 for 2 at 75 °C under 98% relative humidity. The visible-light photocatalytic activity was evaluated by photocatalytic decomposition of Cr(VI) and MB dye, and the removal ratios can reach 95.6% (1) and 82% (2) for Cr(VI), and 98% (1) and 99% (2) for MB.

Water-stable proton-conducting materials owning excellent performances at ambient temperatures are currently one of the crucial challenges. Herein, four water-stable three-dimensional polyoxometalate-based rare-earth organic frameworks have been successfully synthesized and formulated as H{Ln 4 (L) 2 (H 2 O) 21 [Zr 3 (OH) 3 (PW 9 O 34 ) 2 ]}·15H 2 O ( 1 - 3 ) (Ln = La ( 1 ), Ce ( 2 ), Pr ( 3 ); L = 3,5-pyridine dicarboxylic acid), which are the first examples of MOFs constructed by a zirconium sandwiched polyoxoanion. There are abundant coordinated water molecules functionalizing the Pr III centers, and simultaneously, plenty of lattice water molecules are fitted into the channel of the framework. A continuous H-bonding network is found between the architectures and plays an important role in stabilizing the structure. Benefiting from the consecutive H-bonding networks, compounds 1 - 3 showed high proton conductivities at ambient temperature (up to 1.05 × 10 -3 S·cm -1 under 98% RH) by a synergistic effect of the combined components.

Two unique polyoxometalate (POM)-encapsulated tubular materials with the formula K(H 2 O) 6 [M 6 (btp) 6 (H 2 O) 22 ](P 2 W 18 O 62 ) 3 (Hbtp) 5 (btp) 3 ·52H 2 O [M = Mn ( 1 ) and Co ( 2 ); btp = 2,6-bis(1,2,4-triazol-1-yl)pyridine] were designed and synthesized based on the Dawson POM and V-type btp ligand, as confirmed by IR, X-ray diffraction (XRD), and element analysis. Single-crystal XRD analyses of compound 1 show that two kinds of remarkable metal-organic supramolecular nanotubes, including trigonal and hexagonal nanotubes, are constructed along the c -axis direction via π···π-packing interactions between {Mn 3 (btp) 3 } rings and the btp ligands, of which [α-P 2 W 18 O 62 ] 6- anions are confined in channels, making the entire structure extraordinarily stable. Meanwhile, the coordinated [α-P 2 W 18 O 62 ] 6- anion within the hexagonal channel makes the channel highly hydrophilic and attracts a number of guest water molecules to fill in the free space, conducive to proton transport. Therefore, the single-crystal sample of 1 exhibits a high proton conductivity of 6.39 × 10 -3 S cm -1 along one-dimensional channels, 30 times higher than that of a pellet sample at 358 K and 98% relative humidity.

Four novel isopolymolybdate-based coordination polymers (CPs), constructed from 2,6-bis(1,2,4-triazol-1-yl)pyridine (btp), 1,3-bis(4 H -1,2,4-triazol-4-yl)benzene (btb), and 3,5-bis(1-imidazolium)pyridine (bip), have been synthesized under a hydrothermal method: {[Co(btp)(H 2 O) 2 (β-Mo 8 O 26 ) 0.5 ]·3H 2 O} n ( 1 ), [Ni(btp)(H 4 Mo 6 O 22 ) 0.5 ] n ( 2 ), [Co(btb)(H 2 O)(β-Mo 8 O 26 ) 0.5 ] n ( 3 ), and {[Co(Hbip) 2 (H 2 O) 2 (γ-Mo 8 O 26 )]·6H 2 O} n ( 4 ). Complex 1 exhibits one 3D framework with an unexpected 3-nodal 2,4,6-c net topology containing the 1D {β-Mo 8 O 26 } n chains, 6-connected Co II centers, and V-type coordinated btp ligands. The neighboring [Mo 6 O 22 ] 4- anions of complex 2 are bridged by the Ni II centers to build one 2D {Ni 2 (Mo 6 O 22 )} network, which is arranged into the 3D framework through the weak π···π stacking interactions. In compound 3 , one 3D framework is formed by the adjacent 1D {Co 2 (btp) 2 } n chains connected by {β-Mo 8 O 26 } n units, which demonstrates a rare 4,6-c fsc topology. In complex 4 , one 2D {Co(Hbip) 2 (γ-Mo 8 O 26 )} layer with a (4, 4) network is connected to one 3D hydrogen-bonding framework via N-H···O and O-H···O hydrogen bonds. Magnetic data indicate that complexes 1 and 4 exhibit antiferromagnetic behaviors, whereas complexes 2 and 3 reveal spin-canting magnetic behavior and metamagnetic behavior, respectively. In addition, the proton conductivity of complexes 3 and 4 was investigated, showing that compound 4 has good proton conductivity at 85 °C and a relative humidity of 98% RH.

Four novel three-dimensional interpenetrating frameworks based on {P 4 Mo 6 } units, H[C 12 H 14 N 2 ] 4 [TM 4 (PO 4 )(H 2 O) 4 Na 6 ][TM 2 (Mo 6 O 12 (HPO 4 ) 3 (PO 4 )(OH) 3 ) 4 ]·8H 2 O ( 1 , 2 ) and H[C 14 H 18 N 2 ] 4 [TM 4 (PO 4 )(H 2 O) 4 Na 6 ][TM 2 (Mo 6 O 12 (HPO 4 ) 3 (PO 4 )(OH) 3 ) 4 ]·8H 2 O ( 3 , 4 ) (TM = Co 2+ ( 1 , 3 ), Mn 2+ ( 2 , 4 )) were synthesized and characterized using infrared spectroscopy, elemental analyses, thermogravimetric analysis, and single-crystal X-ray diffraction. In situ generated methyl viologen (compounds 1 and 2 ) or ethyl viologen (compounds 3 and 4 ) cations function as templates to induce the generation of 2-fold interpenetrating structures in which the {P 4 Mo 6 } tetrameric clusters with [TM 4 (PO 4 )Na 6 ] (TM = Co 2+ ( 1 , 3 ) and Mn 2+ ( 2 , 4 )) as the core were bridged by transition metal ions. Compounds 1 - 4 possess high thermal stabilities and the decomposition temperature of the inorganic frameworks were all >500 °C. It is worth noting that the four compounds all exhibited the bifunctional catalytic performance that they not only had an excellent photocatalytic activity for the reduction of hexavalent chromium (Cr(VI)) under visible light irradiation but also showed a good electrocatalytic activity for the reduction reaction of hydrogen peroxide.

The largest antimonomolybdate monomer, [Sb 8 Mo VI 13 Mo V 5 O 66 ] 5- ( 1- Sb 8 Mo 18 ), has been isolated and displays a new breakthrough of polyoxometalates (POMs) with an ionothermal synthesis strategy. 1-Sb 8 Mo 18 features the first hexanuclear sandwich-type polymolybdate (POMo) with an unexpected metal ring {Sb 6 O 12 } to make its debut in Sb clusters. Furthermore, 1-Sb 8 Mo 18 exhibits a prominent catalytic activity for reducing nitrobenzene to aniline with excellent sustainability.

A novel three-dimensional metal-organic framework [Ni 3 (BTC) 2 (bpp) 2 (H 2 O)]·3H 2 O (1) based on mixed ligands H 3 BTC (1,2,4-benzenetricarboxylic acid) and bpp (1,3-bis(4-pyridyl)propane) was obtained under hydrothermal conditions. Crystal structure analysis reveals that 1 is a framework based on cage-like Ni 8 (COO) 12 units. Furthermore, long-range magnetic ordering is observed at low temperature.

A cobalt-1,4-naphthalenedicarboxylic acid system in a systematic series of ionic liquids with different alkyl chain lengths of imidazolium cations governed the construction of four MOFs with regular changes of secondary building units (SBUs).

Geminal dicationic ionic liquids with different alkyl spacer lengths regularly tune four MOF structures of two structure types in the Ni(Ac)2-1,4-H2NDC system, which in turn bring about the magnetic properties divided into antiferromagnetic and ferromagnetic couplings consistent with the structures.

Two polyoxometalate-based inorganic-organic hybrid compounds constructed from silver(I)-L species and saturated Keggin type polyoxoanion, [Ag2L2(1)]2(SiMo12O40)·1.5DMF·0.5CH3OH⋅H2O 1 and [{Ag4L2(2)(DMF)5}(SiMo12O40)] 2 (L(1) = phenyl 2-pyridyl ketone azine, L(2) = 3-phenyltriazolo[1,5-a]pyridine), have been synthesized and structurally characterized by IR, UV, elemental analysis, XRPD and complete single crystal structure analyses, where the ligands L(1) and L(2) are bis-bidentate and tridentate azines synthesized with the same materials under different conditions. The structure of 1 exhibits a dinuclear double-helicate with [SiMo12O40](4)(-) anions as counter ions, where all of the Ag centers coordinate to bis-bidentate chelating ligands. Compound 2 displays a two-dimensional sheet formed by the Ag-organic infinite chains and the [SiMo12O40](4)(-) alternately arranged in a "rail-like" fashion. The luminescent properties of 1 and 2 in the solid state were investigated., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A new Co(I) one-dimensional coordination polymer [Co(SCN)(ql)]n (ql=quinoline) (1) has been synthesized and characterized by IR, elemental analysis, TG technique and X-ray crystallography. Co(I) atom has a distorted trigonal pyramidal N2S2 (1) environment with two S atoms and one N atom from three μ-1,1,3-thiocyanate bridge ligands and one N atom from ql ligand. Two S atoms from two μ-1,1,3-SCN- bridging ligands bridge two centers to obtain bimetallic 4-membered ring. Adjacent 4-membered rings are linked by a pair of μ-1,1,3-SCN- bridging ligands to form a 1D stair-case like chain. The luminescent properties and magnetic properties of the polymer 1 were investigated in the solid state., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Two polyoxometalate-based coordination polymers {[Mn2(dpdo)4(H2O)6](GeMo12O40)(H2O)4}n (1) and {[Mn2(dpdo)4(H2O)6](GeW12O40)(H2O)3}n (2) (dpdo=4,4'-bipyridine-N,N'-dioxide) have been synthesized and characterized by IR, elemental analysis, XRPD, TG technique and X-ray crystallography. The polymers 1 and 2 are basically isostructural and feature a 3D supramolecular framework decorated with Keggin-type polyanion clusters based on one-dimension polymeric chains, which formed through the coordination interaction of Mn(II) and dpdo. The luminescent properties of the polymers were investigated in the solid state at room temperature., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A new dicoumarol-based compound (C6H4)[CH2NHCO(C9O2H4)N(C2H5)2]21 was synthesized and characterized by IR, UV spectroscopy and single-crystal X-ray diffraction analysis. The structure of 1 exhibits a transoid formation with the two coumarin-containing arms sited on the two sides of the center benzene ring. In the crystal packing the molecule further interact with each other and form a three-dimensional framework through π-π stacking interactions and multiform hydrogen bonds. The compound 1 shows the main emission peak at 540 nm corresponding to the green hue in the solid state. The fluorescence recognition behaviors for various metal ions were investigated and 1 exhibits a highly fluorescence-quenching selectivity for Fe(III) ion in the mixed CH3CN-H2O solvent., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A series of 3D homochiral manganese-lanthanide frameworks have been synthesized based on chiral camphoric acid. In the heterometallic features, D-camphoric acids are unprecedentedly embedded in three coordination modes.

Two new two-dimensional coordination polymers [Cd(3)L(2)(SCN)(6)](n) (1) and [CdLI(2)](n) (2) have been synthesized and characterized by IR spectroscopy, elemental analysis, TG technique, XRPD and complete single crystal structure analysis, where L is 4-(pyridine-2-yl)methyleneamino-1,2,4-trizaole. Asymmetrical Schiff-base ligand L with five- and six-membered N-containing heterocyclic rings acts as a tridentate bridging ligand to bind two Cd(II) centers through one terminal N(triazolyl) and one pyridylimine chelate unit in 1 and 2. For polymer 1, tridentate bridging ligands link Cd-(1,3-μ-SCN(-)) 1D inorganic chains to form a 2D layer network. The existence of C-H···π and π-π stacking interactions between 2D hybrid layers further gives rise to a 3D supramolecular network. In comparison with 1, polymer 2 shows a 2D layer network containing hexanuclear macrometallacyclic units. The 2D layers are staggered together through the combination of C-H···π and π-π stacking interactions and forming a 3D supramolecular structure. The luminescent properties of the polymers 1 and 2 were investigated in the solid state at room temperature., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A 2D Wells-Dawson-based silver(I) coordination polymer was achieved based on silver-Schiff base building blocks and [P(2)Mo(18)O(62)](6-) clusters using AgNO(3), N,N'-bis(furan-2-ylmethylene)hydrazine and Keggin [PMo(12)O(40)](3-) as original materials at room temperature. It is structurally characterized by IR spectroscopy, (31)P NMR, XRPD, thermogravimetric (TG) analyses and X-ray crystallography. The structure of 1 exhibits a novel crystalline 2D coordination polymer constructed by the coordination interaction between the Wells-Dawson polyoxoanion [P(2)Mo(18)O(62)](6-) and Ag-L species. The luminescent property of 1 in the solid state is investigated.

Two new one-dimensional coordination polymers {[CdL(2)(H(2)O)(2)](NO(3))(2)(H(2)O)(6)}(n) (1) and {[CdLI(2)](H(2)O)(CH(3)OH)}(n) (2) have been synthesized and characterized by IR, elemental analysis, TG technique, XRPD and complete single crystal structure analyses, where L is bis(pyridin-4-ylmethylene)biphenyl-2,2'-dicarbohydrazide. The Cd(II) atom has a distorted octahedral coordination geometry with N(4)O(2) donors from four ligands and two water molecules in 1 and a distorted tetrahedral coordination geometry with NOI(2) donors from two ligands and two I(-) anions in 2, respectively. Polymer 1 shows a 1D framework structure containing bimetallic 42-membered quadrangular ring units. The adjacent 1D chains are interacted forming a 3D supramolecular network structure through multiform hydrogen bond interactions. In comparison with 1, polymer 2 is a new rampart-type chain and each chain is interacted with each other through hydrogen bond interactions to lead a 2D layer. The luminescent properties of the polymers 1 and 2 were investigated in the solid state at room temperature., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A novel copper(II) inorganic-organic hybrid compound [CuL(DMF)(CH(3)OH)](2)(PMo(V)Mo(VI)(11)O(40))·2DMF (L=phenyl 2-pyridyl ketone azine) 1 has been synthesized and characterized by IR, UV, elemental analysis and X-ray crystallography. Cu(II) atom has a distorted square pyramidal environment interconnecting with N(3)O(2) donor set. In solid-state there are three types of C-H···π interactions between adjacent [CuL(DMF)(CH(3)OH)](2+), which generate a two-dimensional (2D) layer. Adjacent 2D layers form porous channels in which polyoxoanions as templates are filled. Simultaneously, the oxygen atoms of polyoxoanion as electron acceptors feather multiple intermolecular hydrogen bonds, through which giving rise to a 3D supramolecular network. The luminescent properties of the compound 1 were investigated in the solid state and in aqueous solution at room temperature, respectively., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Two one-dimensional d(10)-metal coordination polymers {[AgL(H(2)O)](2)[AgL(NO(3))](2)(NO(3))(2)L(H(2)O)(2)}(n) (1) and [ZnLCl(2)](n) (2) (L=N,N'-bis-(1-pyridin-4-yl-ethylidene)-hydrazine) have been synthesized and characterized by IR, elemental analysis, TG technique, XRPD and X-ray crystallography. Polymer 1 contains two types of 1D Ag-double-chain units. Ag(1)-double-chain unit is formed by linking two adjacent Ag(1)-L-chains through face-to-face π⋯π interactions, while Ag(2)-double-chain unit is formed through the combination of coordinating NO(3)(-) anions bridging interactions and π⋯π interactions between two adjacent Ag(2)-L-chains. Free ligands interact with the adjacent Ag(1)-double-chain units and Ag(2)-double-chain units to form a 3D supramolecular structure through multiform hydrogen bonds. For polymer 2, each ligand acts as a bis-monodentate bridging ligand to bind adjacent Zn(II) centers forming a one-dimensional chain structure. Furthermore, 1D chain is held together with its neighboring ones via CH⋯π interactions. The luminescent properties of the polymers 1 and 2 were investigated in the solid state at room temperature., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Two new one-dimension copper(II) coordination polymers [CuL(2)(NCS)(2)](n) (1) and [CuL(2)(NO(3))(2)](n) (2) (L=(C(5)H(4)N)C(CH(3))=N-N=(CH(3))C(C(5)H(4)N)) have been synthesized and characterized by IR, elemental analysis, TG technique and X-ray crystallography. Each Cu(II) atom has a distorted octahedral N(6) (1) or N(4)O(2) (2) environment with four pyridyl N atoms from four ligands and two N atoms from two NCS(-) anions for polymer 1 or two O atoms from two NO(3)(-) anions for polymer 2, respectively. A pair of bis-monodentate bridging ligands links two Cu(II) centers to form one dimension chain structure containing bimetallic 22-membered macrometallacyclic rings. 1D chain is held together with its neighboring ones via C-H⋯S hydrogen bonds for 1 and C-H⋯O hydrogen bonds, C-H⋯π interactions for 2 to form a 3D supramolecular structure, respectively. The luminescent properties of the polymers 1 and 2 were investigated in the solid state at room temperature., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Two new copper(II) complexes Cu(NCS)2(4-Bzpy)2 (1) and Cu(NO3)2(4-Bzpy)4 (2) (4-Bzpy=4-benzoylpyridine) have been synthesized and characterized by IR, UV, elemental analysis and X-ray crystallography. Cu(II) atom has a square planar environment for 1 and an distorted octahedral environment for 2, respectively. In solid state there are C-H⋯π interactions and C-H⋯S hydrogen bonds between adjacent molecules in complex 1. The molecule of complex 2 is further connected by multiform π-π interactions, C-H⋯π interactions and C-H⋯O hydrogen bonds to form a three-dimensional supramolecular structure. The luminescent properties of the complexes 1 and 2 were both investigated in H2O solution and in solid state at room temperature, respectively., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A new inorganic-organic hybrid compound [FTMA](2)[Co(NCS)(4)] (FTMA = ferrocenylmethyltrimethylammonium cation) has been synthesized and characterized by IR, UV, elemental analysis and X-ray crystallography. Co(II) atom has a distorted tetrahedral environment with four N atoms of four NCS(-) anions. In the solid state there are C-H⋯π interactions between adjacent ferrocenyl cations, which generate one-dimensional (1-D) supramolecular chain, and C-H⋯S hydrogen bonds between [FTMA](+) cations and cobalt thiocyanate anions. The title compound shows strong purple fluorescence emission in the solid state at room temperature., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A new inorganic-organic hybrid compound [O2NBzQL]4[Cd(SCN)4(NCS)2] (O2NBzQL=1-(4'-NO2-benzyl)quinolinium cation) has been synthesized and characterized by IR, UV, elemental analysis and X-ray crystallography. Cd(II) atom has an distorted octahedral environment with an N4S2 donor set. In solid state there are three types of face-to-face π-π interactions between adjacent cations and multiform C-H⋯S and C-H⋯N hydrogen bonds between [O2NBzQL]+ cations and cadmium thiocyanate anions. The luminescent properties of the title compound were both investigated in H2O solution and in solid state at room temperature, respectively., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The polyoxometalate-based 1D coordination polymer [[Cu(DMF)₆][PMo(V)Mo(VI)₁₁O₄₀Cu(DMF)₄]·DMF1 was synthesized and characterized by IR, UV spectroscopy and single-crystal X-ray diffraction analysis. Each Cu(II) center has a distorted octahedral coordination geometry. Cu(1) center interconnects with two [PMo(V)Mo(VI)₁₁O₄₀]⁴⁻ anion subunits and each [PMo(V)Mo(VI)(11)O(40)]⁴⁻ polyoxoanion acts as a didentate ligand to link two Cu centers through two terminal oxygen atoms to form a one-dimensional chain structure. The luminescent properties of 1 in the solution and in the solid state were investigated, respectively., (Copyright © 2010 Elsevier B.V. All rights reserved.)

A novel Cd(II) coordination polymer [Cd(SCN)(2)(hmt)(1/2)(H(2)O)](2).H(2)O (hmt=hexamethylenetetramine) has been synthesized and characterized by IR, elemental analysis, TG technique and X-ray crystallography. Cd(II) atom has an distorted octahedral environment with an N(3)S(2)O donor set. Every six Cd(II) centers are linked by hmt and thiocyanato bridges to form a planar 2D coordination polymer containing hexagonal metallocyclic rings [Cd(6)(SCN)(8)(hmt)(2)]. A 2D layer structure is held together with its neighboring ones via a set of hydrogen-bonding interactions to form a 3D supramolecular structure. The luminescent properties of the title complex in the solid state were investigated.

A two-dimensional porous framework, which was formed from neutral discrete hexanuclear copper clusters via self-assembly, exhibited highly selective absorption of aromatic molecules in water with special fluorescent response.

Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.

A nonplanar metallacrown [Ni-N-N]12 was achieved using a pentadente ligand, salicylaldehyde 2-pyridinecarboxylhydrazone (H2L) via a new modular self-assembly approach. The special bridging models of the ligand forced the macrocycle to form in a specific size with the wavelike conformation.

A new enantiomeric interpenetrating 3D nets with chiral helical coordination silver(i) polymer was achieved via self-assembly using the new ligand modular approach, in which the special helical conformation of the ligand provided the opportunity to translate chirality from one metal center to others.

A 3-D porous zeolite-like metal-organic framework surviving guest removal is assembled from a well-defined tetrahedral Fe(4)L(6) cavity by the cooperativity of hydrogen bonds and [small pi]-[small pi] stacking.