Two Zn(Ⅱ)/Cd(Ⅱ)Metal-organic Frameworks Constructed from 1,3,5-Benzenetricarboxylic Acid and 1,4-Bis(1-imidazolyl)benzene:Syntheses,Structures and Photoluminescent Properties

Two new d;metal-based metal-organic frameworks,{[Zn;（btc）;（bib）;（H;O）;]·2H;O};（1）and{[Cd;（btc）;（bib）;（H;O）;]·6H;O};（2）(btc=1,3,5-benzenetricarboxylate anion,bib=1,4-bis（1-imidazolyl）benzene)have been prepared under hydrothermal conditions by the reactions of d;metal oxides of ZnO and CdO with the aromatic polycarboxylic H;btc and the N-heterocyclic bib.The two products were characterized by single-crystal X-ray diffraction analysis,elemental analysis,thermogravimetric analysis（TGA）,and IR spectroscopy.Complexes 1 and 2 crystallize in monoclinic C2/c and triclinic P 1 space groups,respectively.1 shows a 3D framework,and the potential large voids of the 3D network lead to a 3-fold interpenetrating architecture.2 displays a 2D framework,and the adjacent 2D layers expand into a 3D supramulecular network via rich hydrogen bonds.Moreover,the luminescent properties of the two complexes are investigated in solid state.

Syntheses and Structures of Two Metal-organic Frameworks Constructed from Zn/Ni and 3-Formyl-4-(pyridin-4-yl)Benzoic Acid Ligand

Two metal-organic frameworks [（Zn0.5L）·（H2O）]n （1） and [（Ni0.5L）？（H2O）]n （2） constructed by the 3-formyl-4-（pyridin-4-yl） benzoic acid ligand （HL） were synthesized and characterized by single-crystal X-ray diffraction. 1 crystallizes in orthorhombic space group Pnna with a = 16.6152（8）, b = 12.6825（6）, c = 15.3908（8） A, V = 3243.2（3） ？3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F（000） = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ（I）. 2 is isostructural to 1, which also crystallizes in orthorhombic space group Pnna with a = 16.6152（8）, b = 12.6825（6）, c = 15.3908（8） ？, V = 3243.2（3） ？3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F（000） = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ（I）. Additionally, thermogravimetric analysis, FT-IR spectroscopy and powder X-ray diffraction were discussed.

Synthesis, Crystal Structure and Photoluminescent Property of Metal-Organic Frameworks with Mixed Carboxylate and Imidazole-Containing Ligands

Three new metal-organic frameworks （MOFs）, namely [Zn（tib）（PDC）] （1）, [Zn3（tib）2（CHDC）3]·8H20 （2） and [Zn3（tib）2（BTC）2]·4.95H20 （3） were synthesized by hydrothermal reactions of ZnC12 with 1,3,5-tris（l-imidazolyl）- benzene （tib） and different carboxylate ligands of 2,6-pyridinedicarboxylic acid （H2PDC）, 1,4-cyclohexanedicar- boxylic acid （H2CHDC） and 1,3,5-benzenetriacetic acid （H3BTC）, respectively. The complexes were characterized by 1R, thermogravimetric analysis, single crystal and powder X-ray diffractions. Complex 1 has a binuclear structure, in which one imidazole group of tib is free of coordination, while 2 has three-dimensional （3D） framework with the CHDC-Zn microcycles filled into the tib-Zn 3D net, and 3 is a 2-fold interpenetrating 3D framework with the interconnection of two one-dimensional （ID） chains formed by BTC-Zn and tib-Zn, respectively. The different structures of 1 3 are resulted from the distinct carboxylate ligands. In addition, complexes 1-3 show obvious emissions at room temperature in the solid state.

Conductive metal-organic frameworks: Recent advances in electrochemical energy-related applications and perspectives

Metal-organic frameworks(MOFs),typically constructed with metallic nodes and organic linkers,have influenced the development of modular solid materials.Their adjustable molecular structure provides a remarkable variety of MOF-based solid-state structures towards diverse applications.However,the low conductivity of traditional MOFs extremely hinders their applications in electronic and electrochemical devices.The emerging conductive MOFs,generally possessing twodimensional layered structures,are endowed with both the structural merits of common MOFs and exceptional electronic/ionic conductivities.Besides,the selection and optimization of ligands and metal centers,as well as synthetic methods enormously affects the intrinsic conductivity of conductive MOFs.The distinctive crystal structures and superb conductivity promise their appealing applications in electrochemical energy-related fields.In the review,we mainly summarize representative crystal features,conducting mechanisms and recent advances in rational design and synthesis of conductive MOFs,along with their versatile applications as electrodes for electrochemical capacitors and rechargeable batteries,and as catalysts towards electrocatalysis.Finally,the involved challenges and future trends/prospects of the conductive MOFs for electrochemical energyrelated applications are further proposed.

Two New Metal-organic Frameworks Constructed from 3,4,5-Substituted-1,2,4-Triazole Ligands

Two new complexes,[Zn（L1）2（SCN）2]·H2O（1,L1 = 3,5-dimethyl-4-p-tolyl-4H1,2,4-triazole and [Cd3（L2）6（SCN）6]（2,L2 = 3,5-dimethyl-4-phenyl-4H-1,2,4-triazole）,have been hydrothermally prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in monoclinic,space group P21 /n with a = 11.246（13）,b = 9.640（11）,c = 26.13（3）,β = 100.97（3）,V = 1108.5（3） 3,Z = 4,C24 H28 N8 OS2 Zn,Mr = 572.02,Dc = 1.366 g/cm3,μ = 1.065 mm-1,S = 0.992,F（000） = 1184,the final R = 0.0602 and wR = 0.1700 for 2925 observed reflections（I 2σ（I））.Complex 2 crystallizes in triclinic,space group P1 with a = 11.6669（3）,b = 12.0957（2）,c = 14.3674（3）,α = 105.380（3）,β = 91.020（2）,γ = 92.4100（10）o,V = 1952.30（7）3,Z = 1,C66H66N24S6Cd3,Mr = 1725.08,Dc = 1.467 g/cm3,μ = 1.025 mm-1,S = 1.037,F（000） = 870,the final R = 0.0336 and wR = 0.0946 for 7819 observed reflections（I 2σ（I））.In the title complexes,complex 1 is a mononuclear molecule where the centre Zn（II） coordinates to two 3,4,5-substituted 1,2,4-triazole ligands（L1） and two terminal SCN-anions in a tetrahedral environment while six-coordinated centre Cd（II） atoms with octahedral geometry in complex 2 are bridged by virtue of substituted 1,2,4-triazole（L2） in N1,N2-bridging mode and μ2-N,N-SCN-anions into a trinuclear molecule.

A 2D Layer Copper(Ⅱ) Coordination Polymer with 3-Nitrophthalic Acid: Synthesis, Crystal Structure and Copper 3-Nitrophthalate Metal-organic Framework-graphene Oxide Nanocomposite

A 2D layer Cu(Ⅱ) coordination polymer [Cu(npth)(H_(2)O)]n(1) was crystallized from a mixture of 3-nitrophthalic acid and Cu(OAc)_(2)·H_(2)O in water under room temperature and structurally characterized by single-crystal X-ray diffraction, FT-IR and TGA. Compound 1 was applied to make a nanocomposite with graphene oxide(GO). A highly dispersible and stable nanocomposite of Cu(npth)-GO was successfully synthesized by a simple ultrasonication method. SEM, TEM, UV-vis, FT-IR and TGA were used to characterize the morphology and structure of the prepared composite. In accordance with the characterization results, we suspected that the binding mechanism of Cu(npth) and GO was assigned to be the cooperative interaction of Cu–O coordination, π-π stacking and hydrogen bonding.

A New 3-Fold Interpenetrating 3D Zn(Ⅱ) Metal-organic Framework: Synthesis,Structure and Luminescent Property

A new Zn（Ⅱ） coordination polymer,namely {[Zn_（1.5）（1,3,5-btc^（3-））（dtb）（H_2O）]（H_2O）_2}_n（1）（1,3,5-H_3btc = 1,3,5-benzenetricarboxylic acid,dtb = 1,3-di-（1,2,4-triazole-4-yl）benzene）,has been hydrothermally synthesized and structurally characterized. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic C2/c space group with a = 33.811（12）,b = 8.406（2）,c = 17.296（4） ？,β = 120.593（2）°,V = 4232（2） ？~3,Z = 4,Mr = 1142.88,Dc = 1.794 Mg/m^3,μ = 1.783 mm^（-1）,F（000） = 2320,the final R = 0.0338 and wR = 0.0827 for 3043 observed reflections with I 〉 2σ（I）. Compound 1 exhibits 1D Zn（Ⅱ）-carboxylate chains,which are connected into a 3D porous framework with large channels by dtb,and then three identical 3D networks are interpenetrated with each other. In addition,the luminescence property of the complex has also been investigated.

Controlling structural topology of metal-organic frameworks with a desymmetric 4-connected ligand through the design of metal-containing nodes

Two new metal-organic frameworks（MOFs）,[Cu2（H_2O）_2（BCPIA）]（BUT-20）and（Me_2NH_2）[In（BCPIA）]（BUT-21）were designed and synthesized through the solvothermal reaction between a newly created desymmetric 4-connected ligand,5-（2,6-bis（4-carboxyphenyl）pyridin-4-yl）isophthalic acid（H_4BCPIA）and Cu（NO_3）2 2.5H_2O or In（NO_3）_3·5H_2O,respectively,and characterized by single-crystal and powder Xray diffraction,thermogravimetric analysis,infrared spectroscopy,and elemental analysis.The two MOFs have three-dimensional structures,in which both the BCPIA 4 ligand and metal-containing entities,Cu_2（COO）_4（H_2O）_2 and In（COO）_4 act as 4-connected nodes.However,different linkage configurations of the two metal-containing nodes,quadrilateral Cu_2_TD_2（COO）_4（H_2O）_2and tetrahedral In（COO）_4,lead to distinct structural networks of BUT-20 and 21,with Nbo and Unc topologies,respectively.

Assembly of Two Isostructural Metal-organic Frameworks Based on Hetero-N,O Donor Ligand for Detecting Nitro Explosives

Two isostructural metal-organic frameworks,[NO3][M3(H2O)3O(TBA)3]-2DMF-6H2O(1 and 2)[M=In and Fe, H2TBA=4-(1H-tetrazol-5-yl)-benzoic acid], have been successfully synthesized. Compounds 1 and 2 have three-dimensional structures bridged via the typical 6-connected tri-nuclear cluster units M3O(COO)6 and linear linker H2TBA. The whole 3D framework possesses a 6-connected acs topology. Notably, by the fluorescence technique, compound 1 can detect nitro explosives through fluorescence quenching effect, especially for 2,4,6-trinitrophenol(TNP, Ksv=3.64×10^4 L/mol). Furthermore, the fluorescence spectrum red shifts as the number of NO2 group increases. Based on the aforementioned consideration, compound 1 can be considered as a potential luminescent probe for the detection of TNP.

Synthesis, Structure, and Magnetic Properties of a New 2D Cobalt(Ⅱ) Metal-organic Framework

Rational design of magnetic materials with desired magnetic properties has attracted wide interest in recent decades. Herein, we present a new 2D cobalt（II） metal-organic framework, namely [Co（MQ）2（V2O6）2]n·4nH2O 1, which was hydrothermally synthesized by the reaction of Co（NO3）2·4H2O, N-methyl-4,4′-bipyridinium（MQ＋） chlorine salt and NH4VO3. Single-crystal X-ray diffraction analysis reveals that 1 crystallizes in C2/c space group with a = 16.290（5）, b = 7.815（2）, c = 25.297（7） A, β = 108.459（5）°, V = 3054.8（15） A3, Z = 4, Dc = 1.890 g/cm3, μ = 1.791 mm-1, F（000） = 1748, the final R = 0.0444 and wR = 0.1208 with I 〉 2σ（I）. The individual Co（II） is connected and well separated by diamagnetic [V2O6]2-linkers. Magnetic measurements confirm that 1 exhibits ferrimagnetic interactions.

Syntheses,Structures of A Cobalt(Ⅱ) Metal-organic Framework Based on 2,6-di(2',4'-dicarboxylphenyl) pyridine and 4,4'-bis(imidazol-1-ylmethyl) biphenyl-ligands

[Objectives]The paper was to synthesize and describe a new 3D structure of a mew metal organic framework,and to provide new materials for the study of interdisciplinary.[Methods]A mixture of H_(4)L=2,6-di(2,4-dicarboxylphenyl)pyridine,bimb=4,4-bis(imidazole-1-ylmethyl)biphenyl,Co(NO_(3))_(2)·6H_(2)O were added to the solution of DMF∶H_(2)O=4∶2 and heated at 433 K for 4 d.[Results]Purple block crystals of the Co-compound were obtained(yield 83.6%,based on Co).[Conclusions]The crystal data are obtained as follows:C_(51)H_(36)Co_(2)N_(7)O_(9),Triclinic,P-1,a=9.916(8),b=15.926(14),c=15.945(13),α=113.913(13)°,β=93.929(9)°,γ=95.033(3)°,V=2278(3)A^(3),Z=2,R=0.0803(6446),wR_(2)=0.2106(10370),T=296 K.

Metal-Anion Coordination and Linker-Anion Hydrogen Bonding in the Construction of Metal-Organic Frameworks from Bipyrazole

Two new two-dimensional frameworks based on packing of square grids, Cu（Me4bpz）2（NO3）2 （1） and Zn（Me4bpz）（SO4） （2） （Me4bpz=3,Y,5,5＇-tetramethyl-4,4＇-bipyrazole）, have been synthesized by mild solvothermal method. In addition to the major metal-organic linker coordination, they allow us to study how the metal-inorganic anion coordination and organic linker-inorganic anion hydrogen bonding affect the resulting structures during the framework assembly.

A One-dimensional Metal-organic Framework of Eu(Ⅲ) from Triazine-based Flexible Polycarboxylate and Bidentate Nitrogen Donor Ligand

A new Eu（III） complex from 2,2＇-bipyridine（2,2＇-bipy） and 1,3,5-triazine-2-4,6-tri（L-alanine）（H3L）, {[Eu（L）（2,2＇-bipy）]（H2O）}n（1）, has been synthesized and characterized. The X-ray structure analysis reveals that 1 is an infinite one-dimensional chain-like coordination polymer consisting of dinuclear lanthanide building blocks. The 1D chains are further assembled into a 2D supramolecular architecture through π···π interaction among chains. Crystal data for 1： Eu C22H25N8O7, triclinic, space group P1, a = 11.3965（1）, b = 11.5112（6）, c = 12.0404（1）A, α = 61.970（11）, β = 86.698（15）, γ = 65.254（12）°, V = 1247.0（2） A3 and Z = 2. Solid-state photoluminescence property of 1 was investigated, which exhibited remarkable red luminescence emissions with high quantum yield up to 37%.

Metal-ion Interactions with Sugars:Crystal Structure of Bis(4-dehydro-L-arabinose) Calcium Methanol Bishydrate

The crystal structure of the metal-organic frame Ca（C5H9O5）2·CH3OH·2H2O（1） has been synthesized and characterized.Complex 1 belongs to a tetragonal P43212 space group.In complex 1,the sugar moiety shows a beta-L configuration of pyranose form.The calcium（Ⅱ） is eight-coordinated,binding to four such sugar moieties,via O（1）,O（2） of two molecules and O（3）,O（4） of the other two,with the 4-hydroxy group being deprotonated.The water and methanol molecules are not coordinated to the calcium ion.

Two Novel Zn(Ⅱ)-biphenyl-3,4,5-tricarboxylate Coordination Polymers:Syntheses,Crystal Structures and Luminescence Properties

Two novel Zn（II）-organic frameworks [（CH3）2NH2][Zn（BPT）]＇0.5DMF （1） and [Zn2（HBPT）2（1,4-bis）] （2） （H3BPT = biphenyl-3,4,5-tricarboxylic acid, 1,4-his = 1,4-bis（1H- imidazol-1-yl）butane） have been synthesized under solvothermal conditions, and characterized by IR spectroscopy, powder X-ray diffractions （PXRD） and single-crystal X-ray diffractions. Complex l displays a rtl rutile 3,6-connected network with {4.62}2{42.610.83} topology, while with the 1,4-his secondary ligand being introduced into the assembly, a different structure 2 has been obtained. Compound 2 forms a 2D layered framework through linking by both BPT and 1,4-bis ligands, which is further stacked via hydrogen-bonding interactions to a three-dimensional supramolecular architecture. Furthermore, thermal analyses （TGA） and photoluminescent properties of I and 2 are also investigated in detail.

Synthesis and Structure of a POMs-based 3D Zeolike Ionic Crystal,{[Co(dpdo)_2(H_2O)_2(CH_3CN)]_2(SiMo_(12)O_(40))(H_2O)_2}_n

A POMs-based 3D zeolike ionic crystal 1, {[Co（dpdo）2（CH3CN）（H2O）2]2（SiMo12O40）- （HEO）2}n （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, was constructed via self-assembly by embedding Keggintype [SiMo12O40]^4- polyanions within the intercrystalline voids as pillars and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 11.430（3）, b = 12.242（3）, c = 14.279（3）A, α = 106.196（4）,β = 94.316（4）, γ = 98.294（3）°, V = 1884.5（7）A^3 Z = 1, C44H50N10O54CoEMo12Si, Mr = 2880.17, Dc = 2.538 g/cm^3, p = 2.484 mm^-1,F（000） = 1388, the final R = 0.0383 and wR = 0.1096 for 7753 observed reflections with I 〉 2σ（I）. Flack factor is 0.22（3）. Compound 1 is a pillar-layered framework with the [SiMo12O40]^4- anions linearly located on the square voids between the 2D bilayers which are formed by the dpdo ligands and cobalt（II） ions.

Synthesis and Characterization of a Water-stable Metal-organic Framework Based on Mixed Ligands

A new water-stable metal-organic framework,[Cu_2（bdc）_2（tpt）_3]·2H_2O（1,H_2 bdc = terephthalic acid,tpt = 2,4,6-tri（4-pyridinyl）-1,3,5-triazine）,has been synthesized and characterized by elemental analysis,infrared（IR） spectrum,thermogravimetric analysis（TGA）,powder X-ray diffraction（PXRD） and single-crystal X-ray diffraction. Compund 1 crystalizes in monoclinic,space group C2/c with a = 30.147（5）,b = 11.0548（17）,c = 20.867（4） ？,β = 115.035（2）o,C_（70）H_（48）Cu_2N_（18）O_（10）,Mr = 1428.34,V = 6301.0（18） ？~3,Z = 8,D_c = 1.506 g/cm^3,μ = 0.754 mm^（–1）,F（000） = 2928,GOOF = 1.058,λ（MoK α） = 0.71073 ？,the final R = 0.0387 and wR = 0.1091 for 6230 observed reflections with I 〉 2σ（I）. In compound 1,the half metallacycles [Cu_2（tpt）_3] are linked by the bdc2-ligands to form a 1D bent ladder-like chain featured with a nano-sized channel,and these chains link each other via intermolecular hydrogen bonds and π-π stacking interactions to form a 3D supramolecular architecture with the voids filled with free water molecules. In addition,the water stability of 1 was investigated by PXRD patterns,which indicate that compound 1 keeps its structural integrity in boiling water for at least three days.

Synthesis,Structure and Luminescent Property of a Zn(Ⅱ)Complex with Mixed Multi-N Donor and 2,5-Dihydroxy-terephthalic Acid Ligands

A new complex, [Zn2（HL）2（2,5-OH-pbda）]n（1, L = 1-（1 H-imidazol-4-yl）-4-（4 Htetrazol-5-yl）benzene（H2L） and 2,5-OH-H2 pbda = 2,5-dihydroxy-terephthalic acid）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/n with a = 8.8101（10）, b = 17.105（2）, c = 9.4014（11）A, β = 105.704（2）o, V = 1363.9（3） A3, Z = 4, C（14）H9N6O3Zn, Mr = 374.64, Dc = 1.824 g/cm3, μ = 1.831 mm^（-1）, S = 1.042, F（000） = 756, the final R = 0.0309 and w R = 0.1003 for 3130 observed reflections（I 2σ（I））. The H2L ligand was deprotonated to be an HL-anion, and coordinated with Zn^（2＋） to form two-dimensional（2D） Zn2（HL^-）2^（2＋） sheets, which were pillared by the 2,5-OH-pbda2-ligands to form a three-dimensional（3D） dmc net with Point（Schlafli） symbol of（4·82）（4·85）. The large vacancy of the dmc net is filled via mutual interpenetration of another independent framework, leading to the formation of a 2-fold interpenetrating architecture. Solid state luminescent property of 1 has been investigated.

A 2D Metal-Organic Framework Based on 9-（Pyridin-4-yl）-9H- carbazole-3,6-dicarboxylic Acid： Synthesis, Structure and Properties

A metal-organic framework （MOF） formulated as [Cd2（μ3-L）2（DMF）4]·H2O （CdL） [H2L=9-（pyridin-4-yl）- 9H-carbazole-3,6-dicarboxylic acid, DMF=N,N-dimethylformamide] was synthesized under solvothermal condition. Crystal structural analysis reveals that CalL features the layered 2D framework with L2- ligands as 3-connected nodes. The compound CdL emits blue-violet light with the narrow emission peak and the emission maximum at 414 nm upon excitation at the maximum excitation wavelength of 340 nm. The compound CalL has a similar emission spectrum curve to the free H2L ligand that indicates the emission of compound CdL should be originated from the coordinated L2 ligands.

Structure and Properties of a Cd(Ⅱ)Metal-organic Framework Based on a Newly Designed Heterotopic Tripodal N-Donor Ligand

In this paper,a Cd(Ⅱ)metal-organic framework(MOF),Cd-DIBT(HDIBT=5-(3?,5?-di(1 Himidazol-1-yl)-[1,1?-biphenyl]-4-yl)-1 H-tetrazole),has been constructed based on a newly designed heterotopic tripodal ligand containing both imidazolyl and pyrazolyl groups.The Cd-DIBT exhibits a new three-dimensional(3,3,9)-connected trinodal network topology with point symbol of(42·6)(43)2(48·615·812·10)(namely scnu)based on binuclear secondary building blocks(SBUs).Staggered 1 D channels were observed in such framework and was estimated to have 5487?^(3)potential solvent area(56%).The stability study reveals that the framework is unstable and easily transforms into amorphous MOF after the removal of guest molecules.In addition,the Cd-DIBT shows a ligand-centered luminescence.