Assembly of Three Scandium-containing Heteropolytungstates Based on a Building-block Synthetic Strategy

Three novel scandium-containing heteropolytungstates[Sc₃(H₂O)₃NO₃(PW₉O₃₄)₂]^10-(1a),[Sc₈(H₂O)₂(GeW₉O₃₄)₂(GeW₆O₂₆)₂]^12-(2a) and[Sc₁₁(W₆O₁₀)₂(OH)₂(H₂O)₁₆(BiW₉O₃₃)₆]^27-(3a) were synthesized by reactions of Sc^III ions with trilacunary Keggin precursors,[A-α-XW₉O₃₄]^n-(X=P, Ge, n=9, 10) or[B-α-BiW₉O₃₃]^9-, in NaOAc/HOAc buffer solution under conventional synthetic condition, respectively. All the three compounds were characterized by means of single-crystal X-ray diffraction(XRD), Fourier transform-infrared(FTIR) spectroscopy ultraviolet-visible(UV-Vis) spectroscopy, elemental analysis, and thermogravimetric analysis. The aqueous solution stability of the sandwich polyanion[Sc₃(H₂O)₃NO₃(PW₉O₃₄)₂]^10- was also verified by electrospray ionization mass spectrometry(ESI-MS) due to its good solubility in water.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Four Coordination Polymers Assembled with a New Biscarboxyl-functionalized Schiff Base Ligand

Based on a new biscarboxyl-functionalized Schiff base ligand 1,2-cyclohexanediamino-N,N'-bis[3-methoxyl-5-(p-carboxyl-phenylazo)] salicylidene(H₄L), four polymers,[(CH₃)₂NH₂]₂·[Mn₃(L)₂(H₂O)₄]·2DMF(CP1),[Fe₂(L)(H₂O)(DMF)](CP2),[(CH₃)₂NH₂]·[Cu(HL)]·H₂O(CP3) and[Ni₂(L)(teta)]·2DMF·H₂O(CP4), have been synthesized(teta=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). In CP1, both of the internal[N₂O₂] pocket and the external carboxylate groups of L^4- anion are ligated by Mn²⁺ ions, and the structure displays a layer. In CP2, the Fe²⁺ cations are linked by L^4- anions to form a binuclear double chain. CP3 displays a[Cu₂(HL)₂] dimer. In CP4, the Ni²⁺ ions are connected by L^4- anions to form a chain. The structures are further linked by hydrogen bonds to form 2D or 3D supramolecular architectures, respectively. CP1 exhibits adsorption ability to three organic dyes.     

Hydrothermal Synthesis,Structure and Property of Transition Metal(Mn,Zn, Cd or Pb) Coordination Frameworks Using Quinoline-8-oxy-acetate Acid and Dicarboxylic Acid as Ligands

Five transition metal coordination compounds, [Mn₂(8-qoac)₂(bdc)(H₂O)₄](1)(8-qoacH=quinoline-8-oxy- acetate acid, H₂bdc=benzene-1,4-dicarboxylic acid), [Zn₄(8-qoac)₄(bdc)₂]_n(2), {[Cd₂(8-qoac)₂(Hip)₂(H₂O)₂]· (H₂O)₄}_n(3)(H₂ip=benzene-1,3-dicarboxylic acid), [Pb₃(8-qoac)₂(bdc)_1.5(H₂O)Cl]_n(4) and [Zn₂(8-qoac)(8-ql)(bdc)]_n (5)(8-Hql=8-hydroxyquinoline), were synthesized by hydrothermal syntheses of metal salts with benzenedicarboxy- lic acid and 8-qoacH. Compound 1 possesses a discrete dimer bridged by bdc^2- ligand. Compound 2 presents a 2D layer network constructed from bdc^2- linkers and 1D infinite ribbons, in which Zn(II) centers are bridged by 8-qoac^- with a tetradentate binding mode. Compound 3 displays a 1D zigzag chain, with adjacent chains further connected via extensive O-H···O hydrogen bonds to generate a 3D supramolecular structure. Compound 4 shows a 3D framework containing trinuclear lead secondary building units and bdc^2- linkers, in which a new coordination mode of 8-qoac^- ligand is observed. In compound 5, Zn(II) ions are simultaneously bridged by 8-qoac^-, 8-ql^- and bdc^2- ligands to form tetranuclear zinc units, which are further interlinked by bdc^2- linkers to yield a 2D wave-like layer. Based on intraligand(IL)(π-π^*) fluorescent emission, compounds 1―5 possess strong purple fluorescent emissions. In addition, the thermal stabilities of compounds 1―5 were studied.     

The synthesis and lyotropic phase behaviour of some aquatetra(cyano)-dodecylaminoferrate(II) complexes

Some alkali and alkaline earth metal salts of the amphiphilic anion [Fe(CN)₄(H₂O)(C₁₂H₂₅NH₂)]^2- have been synthesized by reaction of [Fe(CN)₅NO]^3- with C₁₂H₂₅NH₂. Using optical microscopy, they have been shown to give a hexagonal (H₁) mesophase in water.     

Hydrothermal Synthesis,Structure and Properties of a New Phosphomolybdate Based on Novel [Co(H2O)4(HP2Mo5O23)]8- Anions and [H8(H2O)16]8+ Water Cluster Cations

A pure inorganic [P₂Mo₅O₂₃]^6- based cobalt complex [H₈(H₂O)₁₆][Co(H₂O)₄(HP₂Mo₅O₂₃)₂] with a sandglass-like shape was synthesized and characterized by means of single-crystal X-ray diffraction, powder X-ray diffraction(PXRD), infrared spectroscopy(IR), thermogravimetry/differential scanning calorimetry(TG/DSC), ultraviolet-visible spectroscopy(UV-Vis) and cyclic voltammogram(CV). Single-crystal X-ray diffraction analysis reveals that the asymmetric unit of compound 1 consists of a half cobalt ion, one [P₂Mo₅O₂₃]^6- anion, two coordinated water molecules and eight lattice water molecules. It is especially intriguing to note that two [P₂Mo₅O₂₃]^6- clusters are symmetrical about the Co ion, like a sandglass. And a chair-like water cluster with an unprecedented centrosymmetric [H₈(H₂O)₁₆]⁸⁺ can be observed in compound 1. Additionally, the electrochemical and catalytic properties of compound 1 were also investigated.     

Template-directed Synthesis of Three Metal Oxalates via 4-Connected Building Units

Three novel compounds, [Co（en）3]2[Zr2（C2O4）7]·2H20（HNU-2, en=ethylenediamine）, [Co（NH3）6]· [Ce（CzO4）3（H2O）]·H2O（HNU-3） and [Co（dien）2][Gd（C2On）3]·0.75H2O（HNU-4, dien=dethylenetriamine） were hydro- thermal synthesized based on the templates of [Co（en）3]C13, [C0（NH3）6]C13 and [Co（dien）2]C13, respectively. The Zr4＋ Ce3＋ and Gd3＋ cations are all coordinated by four oxalates to form [M（C2O4）n（H2O）n]m （M=Zr, Ce or Gd; n=0 or 1; m=4 or 5）, which are similar to [In（C2O4）4]5- in NKB-1, and can be regarded as 4-connected building units. The [M（C2O4）a（H2O）n]m units are connected via sharing the bis-bidentate bridging oxalate ligands to form binuclears in HNU-2 and 1D ＂zigzag＂ chains in HNU-3 and HNU-4. cular building units to design 3D open frameworks with It is suggested that these compounds could be used as mole- zeolite topologies.     

Extended structural materials constructed from sulfate-centered Preyssler-type polyoxometalate with excellent electrocatalytic property

The sulfate-centered Preyssler-type polyoxometalate was firstly used to construct inorganic-organic hybrid materials, which exhibits excellent electrocatalytic activity toward reduction of H₂O₂ and NO₂^-.     

Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

Abstract By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate （NH4）42·[MoI320372·（CH3COO）30（H2O）y2]·ca.300H2·ca. 10CH3COONH4（1） with tetramethylammonium bromide, a new derivative （NH4）26[TMA]16{MoI32O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca.189H2O（2, TMA=tetramethylammonium） was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy（FTIR）, UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear opti- cal（NLO） properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly- oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, （NH4hs（TBA）24{Mo132O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca. 173H2O（3, TBA=tetrabutylammonium） and （DODA）40（NH4）2[（H2O）nMo132O372（CH3COO）3o（H20）72]（4, DODA=dimethyldioctadecylammonium）, reveal that the third-order nonlinearity[x（3）] values of compounds 1, 2 and 3 in the DMF/H2O solution and compound 4 in chloro- form are almost the same, which indicates that the counter cations with different length of alkyl chains show ignora- ble impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[x（3）≈10 19 m2/V2] mainly come from the [MoI32O372（CH3COO）30（H2O）72]42 anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments（such as hydrophilic, hydrophobic, polar, apolar, etc.） can be achieved by simply varying cations to meet the demands in the design of diverse devices. Keywords Keplerate type polyoxometalate; Nonlinear optical property; Z-Scan technique; Self-defocusing; Reverse saturable absorption     

新的四帽Keggin结构的金属-氧簇合物[NiMo12O40H10{Ni(H2O)3}4]的水热合成与结构表征

多金属氧酸盐 (也称金属 -氧簇 )由于在催化、材料及医药等领域的应用日益广泛而备受关注 .近年来 ,一些新颖的非经典结构的化合物不断被合成出来 .如带二帽的 Keggin结构化合物 [V15O4 2 ]9- [1] ,[PV14 O4 2 ]9- [2 ] ,[As V14 O4 2 ]9- [3 ] ,[{ Mo8V7O4 2 } 2 ]14 - [4 ] ,     

萘磺酸型离子配合物的合成及其分子识别性能

常温反应条件下制备了4个基于乙二胺和1,5-萘二磺酸的配位化合物[M(en)(H_2O)_4]·1,5-nds·(H_2O)_2(M=Ni(1),Co(2),Cd(3),Cu(4),nds=1,5-萘二磺酸;en=乙二胺),并通过红外光谱、元素分析、X射线单晶衍射、X射线粉末衍射和热重分析等技术手段确定了其晶体结构。结构分析表明,该系列配合物属于同构体系,单斜晶系,C2/c空间群。以配合物1为例,其晶胞参数为a=1.69026(19)nm,b=1.01373(11)nm,c=1.3448(3)nm,α=90°,β=120.2650°,γ=90°,V=1.9901(5)nm~3,Z=4,Dc=1.713 g/cm~3,F(000)=1072,R_1=0.0326,wR_2=0.0867。该系列配合物的中心金属为六配位模式,与来自乙二胺的2个N原子和4个H_2O中的氧原子配位。游离水与磺酸氧和配位水之间存在着丰富的氢键作用,构筑成三维的网络结构。测定了以Cd为中心金属配合物3的荧光光谱,发现其在对于甲醇的小分子识别性能方面具有应用前景。     

Two New Borates Built by Different Types of {B9} Cluster Units

Two new belt-like borates Na₄[B₉O₁₄(OH)₃]·0.5H₂O(1) and Na₅[B₉O₁₄(OH)₄](2) have been synthesized under solvothermal conditions. Both compounds contain unprecedented B₉O₁₆(OH)_n^(n+5)-[n=3(1), 4(2)] clusters, which are constructed from four B₃O₃ rings via three BO₄ tetrahedra. Compound 1 exhibits a rare 1D belt with two types of 8-membered ring(MR) windows based on B₉O₁₆(OH)₃^8- clusters. Compound 2 features two different 1D belts built by different B₉O₁₆(OH)₄^9- units, which is first discovered in borate family. UV-Vis diffuse reflectance spectra reveal that compounds 1 and 2 have the cut-off edges below 190 nm, indicating that they may have potential application in deep UV(DUV) region.     

One Dimensional Iron Molybdophosphate Anionic Chains with Different Structural Arrangements Reflecting a Flexibility Character

Structural comparison of a new compound[(bpp)₃H₆]Fe₂^IIIFe₂^IIMo₂₄^V(H₂PO₄)₈(HPO₄)₄(PO₄)₄O₄₈(OH)₁₂· (H₂O)₄·2H₂O(1)[bpp=1,3-di(4-pyridyl)propane] with our previously reported two compounds[(bpy)₃Fe^II]₃· Fe₂^IIIFe₂^IIMo₂₄^V(H₂PO₄)₈(HPO₄)₄(PO₄)₄O₄₈(OH)₁₂(H₂O)₄·12H₂O(2) and[(bpy)₃Fe^II]₂Fe^IIFe^IIIMo₁₂^V(H₂PO₄)₂(H_2-xPO₄)·(H_1+xPO₄)(HPO₄)₂(PO₄)₂O₂₄(OH)₆(H₂O)₂·9H₂O(x=0―1)(3)(bpy=2,2'-bipyridine), which all exhibit one-dimensional mixed-valence iron molybdophosphate anionic chains constructed by alternating connection of Fe^III ions and magic[Fe^II(Mo₆P₄O₃₁)₂] units, reveals that the non-hydrogen atomic ratios of Mo:Fe:P:O within the polymeric anionic chains are the same for all the three compounds, while the polymeric anionic chains of the different compounds bear different numbers of negative charges. And therefore there exist different numbers of counter cations per {Fe₂^III[Fe₂^II(P₁₆Mo₂₄^VO₁₂₄)]} unit found in the titled compounds. It discloses that not only are the spatial assembling of counter cations and polymeric inorganic chains of three compounds quite different, but also the O―Fe^III―O bond angles and Fe^III―O bond lengths of the three different inorganic chains exhibit small differences. What is more important is that such small changes in bond length and bond angle in the assemblage of Fe^III―O bonds lead to the considerable fluctuations of inorganic chains in their structural conformation within the three compounds, reflecting an interesting phenomenon of “flexibility" in the pure inorganic one dimensional mixed-valence iron molybdophosphate chains.     

铜配合物修饰的Dawson型钨磷酸盐的合成、晶体结构和催化性能

在水热条件下,Cu(Ⅱ)-H₂biim配合物与Dawson型钨磷酸盐构筑了1个无机-有机杂化化合物[Cu(H₂biim)₂(H₂O)][{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]·11H₂O(1)(H₂biim=2,2'-联咪唑)。 通过单晶X射线衍射、红外光谱(IR)、X射线粉末衍射(XRD)、元素分析、电化学分析等技术手段对其进行了表征。 结构分析表明,在化合物1分子中,[P₂W₁₈O₆₂]^6-单元作为双齿配体与2个Cu²⁺离子配位形成双支撑的杂多阴离子[{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]^2-,在其外部有1个游离的[Cu(H₂biim)₂(H₂O)]²⁺ 和11个H₂O分子。 H₂biim分子与杂多阴离子/H₂O分子间存在氢键,通过氢键、静电和π-π堆积作用,进一步构成具有3D结构的晶体材料。 该晶体化合物对H₂O₂和NaNO₂的还原具有良好的电催化作用;同时,作为酸催化剂用于合成环己酮乙二醇缩酮反应,催化活性高,可重复使用。     

铁氰根桥联的一维链状大环配位聚合物的合成及结构

配位聚合物的合成、结构和性质研究近年来引起了人们极大的兴趣 ,已成为配位化学最活跃的研究领域之一 .由于 [Fe( CN) 6 ]3- 和 [Fe( CN) 6 ]4- 离子本身具有丰富的配位特性 ,可与金属离子及其配合物形成一维链状、二维网状和三维立体结构的配位聚合物 [1～ 5] ,铁氰根和亚铁氰根桥联的配位聚合物的研究成为其中的研究热点之一 .此外 ,铁氰根和亚铁氰根桥联的配位聚合物具有较高的铁磁相变温度[6～ 8] ,是一类具有较好应用前景的分子磁体 .但是 ,以金属大环配合物作为结构单元与 [Fe( CN) 6 ]3-和 [Fe( CN) 6 ]4-离子形成的配位聚合物…     

SO_4~(2-)功能化处理对Fe_2O_3催化剂上氨选择性催化还原NO_x性能的促进机理研究

采用沉淀法制备了Fe(OH)_3和Fe_2O_3。通过硫酸化处理得到SO_4~(2-)/Fe(OH)_3和SO_4~(2-)/Fe_2O_3两种催化剂,并将其应用于氨选择性催化还原NO_x(NH_3-SCR)反应,研究了SO_4~(2-)功能化处理对Fe_2O_3催化剂上NH_3-SCR脱硝性能的促进机理。结果表明,与纯的Fe_2O_3相比,硫酸化处理得到的催化剂上SCR活性得到显著提升;其中,SO_4~(2-)/Fe(OH)_3表现出更加优异的催化性能,在250-450℃时NO_x转化率高于80%,且具有优异的稳定性和抗H_2O+SO_2性能。XRD、Raman、TG、FT-IR、H_2-TPR、NH_3-TPD和in situ DRIFTS等表征结果显示,硫酸功能化处理能抑制Fe_2O_3的晶粒生长,同时SO_4~(2-)与Fe~(3+)结合形成硫酸盐复合物,提高了催化剂表面酸性位点的数量和酸强度,抑制了Fe_2O_3上的氨氧化反应,从而提高了其脱硝催化性能。     

类水滑石[CdxMg6-xAl2(OH)16]2+[S·2H2O]2-的合成与表征

用中温水热法合成了类水滑石[Cd_xMg_6-xAl₂(OH)₁₆]²⁺[S·2H₂O]^2-,探讨了pH值、投入Cd²⁺离子的量以及硫化时间等条件对合成的影响,并用XRD、FT-IR、DTA-TG等手段进行了表征,找出了合成层间嵌入S^2-离子的含Cd类水滑石的最佳条件。     

铈(Ⅳ)与焦磷酸盐的配位作用

考察了在焦磷酸盐水溶液中用O₃氧化Ce(Ⅲ),生成的Ce(Ⅳ)与P₂O₇^4-的作用情况,并对不同条件下所得的固体进行了研究。     

Multi-functional Photoelectric Sensor Based on a Three-fold Interpenetrated Cd(II) Coordination Polymer for Sensitively Detecting Different Ions

Athree-fold interpenetrated cadmium coordination polymer[Cd₃(BTC)₂(H₂O)₉]·2H₂O(CP 1)(H₃BTC=1,3,5-benzenetricar-boxylic acid) was selected and synthesized to investigate its photoelectric properties. CP 1 showed excellent sensitivity for Cr₂O₇^2- and Fe³⁺, low limit of detection(LOD:0.39 µmol/L for Cr₂O₇^2- and 1.72 µmol/L for Fe³⁺) and stability as electrochemical sensor. More importantly, fluorescence sensing studies indicated that CP 1 exhibits sensing activity for Fe³⁺, Fe²⁺, and MnO₄^- with good cyclic stability and selectivity. Low LOD and high-sensitivity capability of CP 1 make it a potential multifunctional photoelectric sensor.     

Two New Alkaline Metal Borates with Supramolecular Framework Constructed from 1D {B5}/{B6} Helical Chains

Two new alkaline metal borates containing 1D{B5}/{B6}oxoboron helical chains,namely Na0.5[B5O8(OH)2]0.5[B5O6(OH)2]0.5·0.5H3O(1)and NaKCs[B6O9(OH)3](2)were synthesized under solvothermal conditions.Compound 1 contains the interesting alternative left-and right-handed helical{[B5O8(OH)2][B5O6(OH)2]}2-({B5}-1 and{B5}-2)1D chains and compound 2 possesses the similar[B6O11(OH)3]7-({B6})chains.Their 1D chains are further assembled into 2D layers and 3D supramolecular frameworks through O-H…O hydrogen bonds.In addition,the UV cutoff edge of compounds 1 and 2 is both below 190 nm.