Hydrothermal Synthesis,Structural Characterization and Proton-conducting Property of a 3-D Framework Based on Zr_3Na_3-Substituted Polyoxometalate Building Blocks

A novel Zr-substituted polyoxometalate(POM) H_2K_3[Na_6(H_2O)_9][Zr_3Na_3O_3(H_2O)_3-(GeW_9O_(34))_2]·12H_2O(1) has been made under hydrothermal conditions. 1 was characterized by infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are: H_(50)O_(95)Na_9K_3Ge_2Zr_3W(1)_8, hexagonal space group P63/mmc, a = 15.2251(6), b = 15.2251(6), c = 25.035(2) ?, V = 5025.7(6) ?~3, Z = 2, D_c = 3.716 mg/m~3, μ = 21.648 mm~(-1), F(000) = 4726, the final R = 0.0259 and w R = 0.0647 for 1487 observed reflections with I 2σ(I). Single-crystal X-ray structure analysis reveals that 1 exhibits a 3-dimensional framework structure based on Zr_3Na_3-substituted polyanions [Zr_3Na_3O_3(H_2O)3(GeW_9O_(34))_2]~(11-) and [Na_6(H_2O)_9]~(6+) clusters building blocks. UV-Vis spectrum indicates that 1 is a wide-gap semiconductor. In addition, the proton-conducting property of 1 was also investigated.     

A New 3-D Lanthanide Porphyrin: Synthesis,Structure and Photophysical Properties

A new lanthanide porphyrin, [Sm III(H3TPPSIII)]n·n H2O(1, H6 TPPS = tetra(4-sulfonatophenyl)porphyrin), has been synthesized through a hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the P4/mcc space group of tetragonal system: a = 15.3683(12), c = 9.895(2) A, V = 2337.0(5) A3, C44H29N4O13S4 Sm, Mr =1100.30, Z = 2, Dc = 1.564 g/cm3, S = 1.063, μ(Mo Kα) = 1.502 mm–1, F(000) = 1102, R = 0.0583 and w R = 0.1666. Compound 1 is characteristic of a three-dimensional(3-D) framework with a slightly distorted square-antiprism eight-coordinated Sm3+ ion. Fluorescent study revealed that compound 1exhibits an emission in the red region. The fluorescence quantum yield and lifetime of 1 were determined to be 3.5% and 9.1 ns, respectively. UV-vis absorption spectra were also investigated.     

Synthesis,Crystal Structure and Water Vapor Adsorption Property of a New Supramolecular Architecture

A new complex, [Cu(HL)(phen)(H_2O)]·4H_2O(1, H_3L·HCl = 5-((4-carboxypiperidin-1-yl)methyl)isophthalic acid hydrochloride, phen = 1,10-phenanthroline), 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/c with a = 14.5520(14), b = 12.6659(12), c = 15.5006(14) ?, β = 97.224(2)o, V = 2834.3(5) ?3, Z = 4, C27H33N3O11 Cu, Mr = 639.10, Dc = 1.498 g/cm~3, μ = 0.837 mm~(-1), S = 1.047, F(000) = 1332, the final R = 0.0423 and w R = 0.1118 for 18772 observed reflections(I 2σ(I)). The compound is a Cu(Ⅱ) centre mononuclear molecule in the asymmetric unit. The independent binuclear [Cu_2(HL)_2(phen)_2] units are bridged to form a three-dimensional(3D) supramolecular polymer by extensive hydrogen bonds and π-π non-covalent bonding interactions. Moreover, thermogravimetric(TG) analysis and gas adsorption property of 1 were also discussed.     

Synthesis,Structure and Photoelectric Property of a 3D Supramolecular Zinc Coordination Polymer

Using a rigid azo ligand 4-[(8-hydroxy-5-quinolinyl)azo]-benzoic acid(H2 L),a new supramolecular compound [Zn(L)(H_2O)_2]_n(1) has been solvothermally synthesized and structurally characterized by X-ray single-crystal diffraction,infrared spectrum,elemental analysis,power X-ray diffraction and thermal analysis.Compound 1 crystallizes in monoclinic,space group C2/c with a = 30.372(8),b = 11.415(3),c = 9.248(3) ?,β = 106.94(3)o,V = 3067.20(15) ?3,C_(16)H_(13)N_3O_5Zn,M_r = 392.66,Z = 8,D_c = 1.701 Mg/m~3; F(000) = 1600,μ = 1.636 mm~(-1),reflections collected:7290,reflections unique:2735,R_(int)= 0.0282,R = 0.0351,wR(all data) = 0.0919,GOOF on F~2 = 1.036.Compound 1 exhibits a one-dimensional(1 D) zig-zag chain structure connected into a three-dimensional(3D) supramolecular network through hydrogen bonding interactions.Fluorescent property and electrochemical property were detected on compound 1.     

Synthesis,Crystal Structure and Band Structure of Tb3Co4Sn（13）

A new intermetallic compound,Tb3Co4Sn13,has been synthesized by solid-state reaction of the corresponding pure elements in a welded tantalum tube at high temperature.Its crystal structure was established by single-crystal X-ray diffraction.Tb3Co4Sn13 crystallizes in cubic,space group Pm3n(No.223) with a = 9.5072(2) ,V = 859.33(3) 3,Z = 2,Mr = 2255.45,Dc = 8.717 g/cm3,μ = 34.369 mm-1,F(000) = 1906,and the final R = 0.0140 and wR = 0.0312 for 199 observed reflections with I > 2σ(I).The structure of Tb3Co4Sn13 belongs to the Yb3Rh4Sn13 type.It is isostructural with RE3Co4Sn13(RE = La,Ce),featuring a 3D [Co4Sn12] framework based on [CoSn6] trigonal prisms.The [CoSn6] trigonal prisms are interconnected via corner-sharing and Sn-Sn bonds to form a 3D [Co4Sn12] framework.The other Sn and Tb atoms are located in the spacers of the 3D framework.Band structure calculations indicate that Tb3Co4Sn13 is metallic.     

Hydrothermal Syntheses and Structural Characterization of Two 3-D Supramolecular Networks Constructed from Tetra-CoII Sandwiched Polyoxometalates

Two Co₄-substituted sandwich-type polyoxometalates (H₂en)₉[Co₄(H₂O)₂(PW₉O₃₄)₂]{[Co(H₂O)₄][Co₄(H₂O)₂(PW₉O₃₄)₂]}·18H₂O (1) and (H₂en)₅[Co₄(H₂O)₂(H₃GeW₉O₃₄)₂]{[Co(H₂O)₄]₂[Co₄(H₂O)₂(H₂GeW₉O₃₄)₂]}·16H₂O (2) (en = ethylenediamine) have been hydrothermally synthesized and characterized by IR spectra, elemental analyses, thermogravimetric analyses, powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal structure analysis reveals that the molecules of 1 and 2 contain two Co₄-substituted sandwich-type polyoxoanions. This type of a molecular unit containing double polyoxoanions is very rare. From the viewpoint of supramolecular chemistry, the sandwich-type polyoxoanions in 1 and 2 can be further extended to 3-D frameworks via extensive hydrogen-bonding interactions.     

Copper(II) Supramolecular Complex: Synthesis,Crystal Structure,and Electrochemical Property

A novel complex {Cu(Bobb)₂](pic)₂}₂ [pic = picrate anion, Bobb = 1,3‐bis(1‐benzylbenzimidazol‐2‐yl)‐2‐oxopropane] was synthesized and characterized by means of elemental analyses and electrical conductivity. The crystal structure of the copper complex has been determined by single‐crystal X‐ray diffraction. A study of the electrochemistry of the title compound was carried out by using cyclic voltammetry. It revealed that the copper complex exhibits a quasi‐reversible redox process. The X‐ray structure of the above complex shows that the unit cell consists of two centrosymmetric, crystallographically independent molecules, in which the copper(II) ions have the same coordination environment and should be described as distorted octahedron. The complex is formed of { ··· Cu(2) ··· Cu(1) ··· Cu(1) ··· }_∞ supramolecular configuration by π ··· π stacking interactions between the benzimidazole rings. The complex was also identified by IR and electronic spectroscopy.     

Synthesis,Structure and Fluorescent Property of a New Isolated Zn_6Co_9 Heteronuclear Cluster Constructed by Four Kinds of Ligands

A novel zero-dimensional heteronuclear cluster based on N-(phosphonomethyl)imino-diacetic acid(H4PMIDA) and Phen(1,10-phenanthroline), [Zn_6Co_9(PMIDA)_6(Phen)_6(NO_3)_4(H_2O)6]· 2NO_3·16H_2O, has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, thermal analysis, and single-crystal X-ray diffraction. The isolated 15-nuclearity cluster [Zn_6Co_9(PMIDA)_6(Phen)_6(NO_3)_4(H_2O)6]~(2+) was constructed by four kinds of ligands, and its charges are balanced by NO–3. Each isolated cluster is further extended into a 3D supramolecular network through π···π interaction and C–H···O hydrogen bonds. Moreover, the solid-state fluorescent property of this complex has also been investigated at room temperature.     

A 3-D Supramolecular Framework with Open Channels Constructed from Lanthanide Ions and Mixed Ligands

A 3-D supramolecular framework, [Er（pybz）2（Hnds）（H2O）2]·H2O （1, Hpybz = 4- pyridin-4-yl-benzoic acid, H2nds = naphthalene-1,5-disulfonic acid）, based on lanthanide ions and mixed ligands has been hydrothermally synthesized. The structure was determined by single-crystal X-ray diffraction and further characterized by IR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.849（2）, b = 22.526（5）, c = 17.167（4） A, β =105.461（4）° and V = 3670.9（2） A^3. In 1, two seven-coordinated Er^3＋ ions are bridged by two pybz^- ligands to form a dimeric [Er2（COO）2] unit, which is further orderly linked by carboxyl of pybz^-ligand to obtain a 1-D chain running along the a axis. Interestingly, significant H-bonding and π-π stacking interactions link the neighboring parallel chains leading to a 3-D supramolecular network structure which displays 1-D rhombus open channels （17.2A× 22.5A）.     

Synthesis, Crystal Structure and Photoluminescent Property of a 3D Hydrogen-bonded Supramolecular Compound with Large Channels

The title compound, [Pd（2,2′-bipy）2]（Haadip）2·4H2O, was synthesized via the hydrothermal reaction of PdCl2 with 5-aminodiacetic isophthalic acid （H4adip） in an acetic acid water solution. It was characterized by elemental analysis and infrared spectrum. Crystal data for C44H44N6O20Pd： monoclinic, space group P21/n, a = 11.0674（2）, b = 9.9716（2）, c= 20.5770（3）A, β = 92.7300（3）°, V = 2268.29（7）A^3, Z = 2, Mr = 1083.25, Dc = 1.586 g/cm^3, F（000） = 1112,μ = 0.499 mm^-1, 2（MoKa） = 0.71073 A, T = 293（2） K, 2θmax = 51.38°, GOOF = 1.067, R = 0.0268 and wR = 0.0710 for 3770 reflections with 1 〉 2σ（I）. X-ray diffraction studies reveal that the title compound has an interesting 3D microporous architecture via hydrogen bonds with the cations located inside the channel.     

A 2-Fold Interpenetrated Framework Assembled from Pyridine-3-carboxylate Ligand and Transition Metal:Synthesis,Structure and Photoluminescent Property

A novel cadmium（Ⅱ） coordination polymer [Cd2（3-pa）4（4,4＇-bpy）（H2O）].3.08H2O 1 has been synthesized by pyridine-3-carboxylate （3-pall） and CdO with exo-bidentate rigid dipyridyl ligand 4,4＇-bipyridine （4,4＇-bpy） by using a hydrothermal method, its structure was determined by single-crystal X-ray diffraction and its luminescent property was also documented. Complex 1 crystallizes in orthorhombic space group Pbcn with a = 21.4074（14）, b = 27.1119（18）, c = 12.3879（8） A, V = 7189.9（8） A3, Z = 8, C34H32.16Cd2N6O12.08, Mr= 942.85, Dc = 1.742 g/cms, p = 1.255 mm-1 and F（000） = 3766. The structure was solved by direct methods and refined to R = 0.0353 and wR = 0.0891 for 6278 observed reflections （I 〉 2σ（I））. The most prominent structural feature is the mutual interpenetration of two identical 3-D open frameworks via filling the large void space, which gives a 2-fold interpenetrating architecture during the self-assembly process.     

A Convenient Synthesis of 3-Behzyl, 3-Benzyl-4-Substituted Coumarins and Their Benzo Derivatives

It is reported in the literature that alkylation of simple (unsubstituted) phosphorane with alkyl halide in ethyl acetate leads to equimolar mixture of alkylated phosphorane and salt of the unsubstituted phosphorane. Here we report exclusive formation of alkylated phosphorane from its salt from benzyl bromide in chloroform. This alkylated phosphorane (2) on reaction with 2-hydroxy carbony1 compounds (1a-1) provide E-ethyl Oc-benzyl cinnamates in high yields which on thermal cyclisation gave 3-benzylf 3-benzyl-4-substituted and benzocoumarins. Thus this method can be used conveniently to synthesise above compounds in good yields.     

Synthesis and Crystal Structure of an Interpentateing 3-D Framework Constructed from Mixed Ligands

A novel organic-inorganic hybrid compound constructed from mixed ligands, Co3（SIP）2（bipy）4（H2O）6·6.5H2O （H3SIP = 5-sulfoisophthalic acid, bipy = 4,4′-bipyridyl）, has been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group P212121 with a = 11.395（2）, b = 19.395（4）, c = 30.675（6） A^°, Mr = 1513.05, V= 6779（2） A^°^3, Dc= 1.482 g/cm^3, F（000） = 3120, μ = 0.873 mm^-1, Z= 4, the final R = 0.0439 and wR = 0.119 for 13421 observed reflections with I〉 2σ（I）. The structure of the compound presents a 3-D framework containing Co-bipy 1-D chain and 2-D bilayer motifs and carboxylate spacers, and the connection of 1-D chain and 2-D bilayer motifs by carboxylate ligand results in the final open framework with twofold interpenetration net. A probe reaction of the oxidation of benzaldehyde with H2O2 using the title compound as catalyst was carded out in a liquid-solid system, showing that the compound has high oxidative catalytic activity to the reaction.     

6位取代的2-甲基-3-乙氧羰基-4-喹啉酮的微波合成及晶体结构

用微波技术在无溶剂条件下合成了4个6-位取代的2-甲基-3-乙氧羰基-4-喹啉酮类化合物,其结构经红外光谱和元素分析表征,并用X-射线衍射法测定了取代基为甲氧基的标题化合物的晶体结构,其晶体属单斜晶系,P21/n空间群,a=0.67780(14)nm,b=O.68990(14)nm,c=2.7329(6)nm,β=92.34(3).,V=1.2769(5)nm3,Z=4,M r=261.27,D c=1.359g/cm3,μ=0.100mm-1,S=1.097.F(000)=552,最终偏离因子为R1=0.087,wR2=0.200.分子间氢键N-H…O和π-π堆积作用使该化合物分子形成稳定的三维结构.     

1-D Open-channeled 3-D Supramolecular Frameworks Built with 2,3-Dihydroxybutanedioic Acid (H4dhbd) and 2,2':6,2"-Terpyridine (tpy)

The complex [Cu2(H2dhbd)2(tpy)2]·CH3OH·4H2O1 (H4dhbd=2,3-dihydroxybutane-dioic acid, tpy=2,2":6',2"-terpyddine) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space groups P1 with a=8.6859(17), b=11.223(2), c=12.275(2)A,α=112.454(3), β=98.435(3),γ=105.593(3)°, V=1022.5(3) A3, Z=1, C38H42Cu2N6.O18, Mr=997.86, Dc=1.621 g/cm3,μ=1.127 mm-1, F(000)=514, T=293(2) K, the final R=0.0539 and wR=0.1394 for 3550 observed reflections with 1 >20(1). In the dinuclear unit, two CuⅡ atoms are bridged by two H2dhbd chelate anions, forming a 14-membered ring, in which the distance of Cu…Cu atoms is 7.0526(12)A. Adjacent dinuclear units are constituted through π-π interactions and C-H…O hydrogen-bonding interactions, fashioning the final 3-D supramolecular framework with 1-D open channels. Variable-temperature magnetic susceptibility measurement indicates the presence of weak antiferromagnetic exchange interactions between CuⅡ ions.     

Synthesis and Polymerization of Some New Bis-Triazolinediones: A Stability Study of 4-Substituted Triazolinediones

Three new bis-triazolinediones, 3,3′-dimethyl-4,4′-bis-[3,5-dioxo-1,2,4-triazoline-4-yl]biphenyl, t-1,4-bis-[3,5-dioxo-1,2,4-triazoline-4-yl]methyl cyclohexane, and 4,4′-bis-[3,5-dioxo-1,2,4-triazoline-4-yl] phenyl ether, were synthesized from their corresponding bis-amines or bis-isocyanates. The compounds were identified by their quantitative ene reaction with 2,3-dimethyl-2-butene. The high degree of reactivity of the triazoline moiety makes solvent selection for reaction media rather difficult. This fact prompted a study of rates of reaction with a variety of polar and nonpolar solvents, including halogenated aliphatics, aromatics, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF). The compounds exhibited reasonable stability in the halogenated solvents, as well as in the aliphatic and aromatic hydrocarbons, but they underwent reaction with THF and DMF. The structure of the reaction product of N-phenyl-1,2,4-triazoline-3,5-dione in DMF solution was determined, and a mechanism for product formation was proposed. Two of the bis- triazolinediones were polymerized via a base-catalyzed condensation mechanism which eliminates N₂ from the triazolinedione ring.     

3-取代苯氧甲基-4-氨基-1,2,4-三唑-5-硫酮席夫碱的合成、结构表征和生物活性研究

以醋酸为反应溶剂和催化剂,用自制的4-氨基-4,5-二氢-3-取代苯氧甲基-1,2,4-三唑-5-硫酮与4-氟苯甲醛反应合成了5个4-氨基-4,5-二氢-3-取代苯氧甲基-1,2,4-三唑-5-硫酮席夫碱化合物,通过1HNMR、IR和元素分析对所有化合物进行了结构表征.初步生物活性测试结果表明所有化合物具有优良的杀菌活性,并对席夫碱结构与活性的关系进行了探讨.     

3',5'-二溴-3-甲氧基-4-羟基偶氮苯合成、晶体结构与异构化性能

以4-氨基硝基苯为原料,通过溴代、重氮化去氨基、硝基还原和重氮偶合反应合成了3’,5’-二溴-3-甲氧基-4-羟基偶氮苯,并通过物理掺杂方法制备了3’,5’-二溴-3-甲氧基-4-羟基偶氮苯-聚甲基丙烯酸甲酯(PMMA)薄膜。利用元素分析、红外光谱、质谱、核磁共振和X射线单晶衍射等技术手段对标题化合物结构进行了表征。晶体结构分析表明,标题化合物晶体属于单斜晶系,C2/c空间群,晶胞参数为a=1.6182(3)nm,b=0.81847(16)nm,c=2.1945(4)nm,β=102.819(2)°,V=2.8342(10)nm3,Z=8,Dc=1.809 g/cm3,μ=5.719 mm-1,F(000)=1504,R1=0.0366,ωR2=0.0764,化合物分子呈反式平面构型,分子间存在的氢键和苯环π-π堆积作用使得其沿b轴方向形成了一维无限链状结构。用紫外-可见光谱对标题化合物在有机溶剂、聚合物中光致反-顺异构化反应和热回复异构化反应的速率常数进行了定量测试,异构化反应的速率常数的数量级为10-1~10-2min-1。     

Synthesis,Structure,and Spectroscopic Studies of a Chiral Supramolecular Complex with Excellent Semiconductor Property

A novel chiral copper(Ⅱ) complex with racemic 1,2-diaminocyclohexane and iodide,[Cu(Ⅱ)(1,2-diaminocyclohexane)_3](I)_2·3H_2O(1) has been synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analysis,infrared spectroscopy,Raman spectroscopy and thermogravimetric analysis. In complex 1,the CuⅡ ion was coordinated by six nitrogen atoms of three 1,2-diaminocyclohexane molecules. The structure of complex 1 can be described as a supramolecular 3D-like structure which was formed by intermolecular hydrogen-bonding interactions between mononuclear molecules,uncoordinated water molecules and two iodide anions. UV-vis absorption spectrum and surface photovoltage properties of complex 1 have also been studied.     

Hydrothermal Synthesis and Crystal Structure of a New 3-D Open-framework Zincophosphate

An open-framework zincophosphate, [C4N3H16][Zn4.5（PO4）4] 1, has been hydro- thermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in the tetragonal space group P4 with a = 14.512（5）, c = 8.914（3）A, V = 1877.3（11）A3, C4H16NaO16P4Zn4.50, Mr = 780 24： Z = 4, Dc = 2.761 g/cm^3,μ= 6.103 mm^-1, F（000） = 1536, T = 298（2） K, R = 0.0416 and wR = 0.0816. In the structure, ZnO4 and PO4 tetrahedra are linked to each other, forming four-membered rings which are connected variably to form two secondary building units （SBUs）. The SBUs are connected so as to generate two chains along the c axis, which are further linked together alternatively via common oxygen atoms （Zn-O-P） giving rise to 8-ring-channels in the [001] direction, and the protonated guest diethylenetriamine （DETA） molecules sit in the middle of these channels. Other characterizations are also described by elemental analysis, thermal analysis and IR and fluorescent spectra.