A novel Wells–Dawson polyoxometalate-based metal–organic framework constructed from the uncommon in-situ transformed bi(triazole) ligand and azo anion

A novel Wells–Dawson polyoxometalate (POM)-based metal–organic framework (MOF) constructed from bi(triazole) ligand and azo anion, namely, [Ag₁₃(L)₆(N₂)(HP₂W₁₈O₆₂)] (1) (HL = 4-(1 H-1,2,4-triazol-3-yl)-2 H-1,2,4-triazolyl) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectra, PXRD analysis. In compound 1, the rigid bi(triazole) ligands connected Ag^I ions to construct a 2D metal–organic layer, which was further extended by azo anions forming a 3D framework. The Wells–Dawson type [P₂W₁₈O₆₂]^6 − anion as a multidentate inorganic ligand coordinated with the Ag^I ions, consolidating the 3D MOF. The L ligands and azo anions were in-situ transformed from a bi(triazole) derivative, which has never been observed in previous reports. In addition, the electrocatalytic and photocatalytic properties of compound 1 have been investigated.     

LiBa1.5[B5O8(OH)3]: A new 1-D metal borate chain constructed from B5O9(OH)36 − cluster units

A new mixed metal borate LiBa_1.5[B₅O₈(OH)₃] (1) has been hydrothermally synthesized and structurally characterized by FT-IR spectroscopy, powder X-ray diffraction, single crystal X-ray diffraction, and thermogravimetric analysis, respectively. 1 crystallizes in the monoclinic system, space group C2/c, a = 11.2839(7) Å, b = 7.3974(4) Å, c = 20.7151(13) Å, β = 103.392(6)°, V = 1682.10(17) ų and Z = 8. The structure consists of infinite one-dimensional (1-D) borate chains constructed from B₅O₉(OH)₃^6 − cluster units. These BO chains are further linked by the Ba^2 + and Li⁺ cations to form a 3-D framework.     

A novel 12-tungstovanadate and 3d–4d heterometallic complex hybrid compound [V1W12O40][VO2Ag(phen)3]2

A novel organic–inorganic hybrid compounds containing 12-tungstovanadate and 3d–4d heterometallic complex, [V₁W₁₂O₄₀][VO₂Ag(phen)₃]₂ (1), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction and IR analysis. The complex is an uncommon bisupporting polyoxometalate derivative in which the saturated Keggin type polyoxoanions are covalently linked by bimetallic complex [VO₂Ag(phen)₃]²⁺. The neighboring Ag⁺ and V⁵⁺ cations are bridged by the oxo atom forming heterometallic cations with the Ag–V distances of 3.556(2) Å in [VO₂Ag(phen)₃]²⁺ cations. Furthermore, the title compound shows good photocatalytic activity for reduction of Rhodamine B (RB) in a liquid–solid system.     

A novel organic-inorganic hybrid polyoxometalate-based 3D framework constructed by organo-functionalized [As2W21O72(mal)2]18 − units and Ce3 + ions

A novel organic-inorganic hybrid polyoxometalate-based 3D framework K₅H₄{Ce₃(H₂O)₉[As₂W₂₁O₇₂(mal)₂]}·20H₂O (1) (mal = malic acid) has been synthesized by the metastable precursor [As₂W₁₉O₆₇(H₂O)]^14 −, which was further characterized by IR spectrum, thermogravimetric analysis (TGA), and X-ray single-crystal diffraction. Structural analysis revealed that 1 consists of the organo-functionalized [As₂W₂₁O₇₂(mal)₂]^18 − units linked together by the Ce^3 + ions resulting in 3D network-like architecture. Magnetic property studies indicate that obvious antiferromagnetic interactions exist in three Ce^3 + ions.     

One novel near-infrared ytterbium metal–organic framework based on an unprecedented [Yb6(μ2-OH)2(μ3-OH)6]10 + cluster

A novel ytterbium metal–organic framework based on an unprecedented [Yb₆(μ₂-OH)₂(μ₃-OH)₆]^10 + cluster has been obtained and characterized, which shows a rare (3,12)-connected {3².4}₂{3⁸.4²².5²⁴.6¹⁰.7²} topological net and strong near-infrared luminescent emission.     

Hydrothermal synthesis and structural characterization: a novel α-Keggin unit supported zinc-bipyridyl complex [Zn(2,2′-bipy)3]2[ZnW12O40Zn(2,2′-bipy)2] · H2O

The hydrothermal reaction of Na₂WO₄ · 2H₂O, ZnCl₂, Zn(Ac)₂ · 2H₂O, 2,2^′-bipyridine, and H₂O gives rise to a novel Keggin unit supported zinc-bipyridyl complex [Zn(2,2^′-bipy)₃]₂[ZnW₁₂O₄₀Zn(2,2^′-bipy)₂] · H₂O consisting of a novel heteropolyanion [ZnW₁₂O₄₀Zn(2,2^′-bipy)₂]⁴⁺ in which the Keggin anion [ZnW₁₂O₄₀]⁶⁻ acts as a bidentate ligand towards the transition metal cation Zn²⁺ through a terminal oxygen and a bridging oxygen from the same WO₆ octahedron.     

化合物[Co(2,2'-bpy)2H2O]12[Mo12V6O42(VO4)][Mo8V8O40(VO4)]3·8H2O的水热合成与晶体结构

用中温水热法合成出一种新的α-Keggin结构化合物[Co(2,2'-bpy)2H2O]12[Mo12V6O42(VO4)][Mo8V8O40(VO4)]3·8H2O,并对其进行了元素分析、IR谱、TGA及X-射线单晶衍射等系列表征.该簇合物属三斜晶系,空间群P-1,a=1.57287(2)nm,b=2.46159(3)nm,c=0.52347(3)nm,α=76.6220(3)°,β=92.078°,γ=79.9390(4) °,V=9.1934(2)nm3,Z=2,Dc=4.642 g·cm-3,μ=4.642mm-1,F(000)=12420,R1=0.0751,wR2=0.1964.化合物中基本构筑单元为三种具有α-Keggin结构的聚阴离子簇,簇与簇之间通过配位阳离子[Co(2,2'-bpy)2H2O]2+桥连成三维结构.化合物中包含少见的六帽α-Keggin结构簇单元.并且在同一晶胞中同时存在聚阳离子和聚阴离子.     

A luminescent novel octanuclear silver(I) cluster framework with potential Cr2O72 − sensing

An unique and novel octanuclear silver(I) cluster compound, [Ag₈(ADC)₄]_n (1) (H₂ADC = 1,3-adamantanedicarboxylic acid), has been synthesized and characterized. Compound 1 exhibits significant Ag–Ag interactions to form 2D infinite silver layers with multiple unsaturated Ag atoms. Moreover, Luminescent investigations show that 1 can exhibit highly selective response to Cr₂O₇^2 − through luminescence quenching effect in aqueous solution, which make its good candidate as luminescent sensor.     

A novel paradodecatungstate-B compound decorated by transition metal copper,Na2Cu5(H2O)24(OH)2[H2W12O42]·10H2O: Synthesis,structure and antitumor activities

A new paradodecatungstate-B compound decorated by transition metal copper, Na₂Cu₅(H₂O)₂₄(OH)₂[H₂W₁₂O₄₂]·10H₂O (1), has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray diffraction, IR spectrum, elemental analysis and TGA. The compound crystallizes in the triclinic P-1 space group with a = 10.7140(8) Å, b = 12.9476(9) Å, c = 13.6696(10) Å, α = 73.56°, β = 75.73°, γ = 67.69°, V = 1661.8(2) ų and Z = 1. In compound 1, polyanion of [H₂W₁₂O₄₂]^10 − acts as a dodecadentate ligand that links copper and sodium cations, forming a remarkable three-dimensional framework. The experiment of antitumor activities in vitro shows that the title compound exhibits remarkable inhibitory actions on human cervical carcinoma HeLa cells, ovarian carcinoma SKOV-3 cells, hepatoma HepG2 cells and neuroblastoma SHY5Y cells.     

Synthesis and Crystal Structure of an One-dimensiornal Silver(Ⅰ)Sulfonate Complex [Ag2 (2-Pyr) ( H2O)4 ]L2

由Ag2 CO3、2,5-二氯-4-氨基苯磺酸(HL)和2-甲基吡嗪(2-Pyr)反应,得了一种新型磺酸银配合物[Ag2(2-Pyr)( H2O)4]L2(1),通过元素分析、红外光谱和X-单晶衍射等对配合物的结构进行了表征.结果表明:1属单斜晶系,空间群P21/c,晶胞参数a＝0.92748(19),b=0.77156(15),c＝2.0044(4) nm,β=91.34(3)°,V＝ 1.4340(5) nm3,Z＝2,F(000)＝850,Dc＝ 1.999 g/cm3,R＝0.0867,wR2＝0.1717 [I＞2σ(I)].配合物中银离子被2-Pyr配体和配位水分子连接成一维的链状结构,进一步通过分子间氢键作用扩展为三维的超分子结构.并且得出了第二配体(2-Pyr)的存在使磺酸银化合物的结构发生了根本的改变.     

Synthesis and crystal structure of an Ag20 cluster incorporating in situ generated bipodal [ArP(OEt)S2]− and tripodal [ArPOS2]2− ligands (Ar = 4-methoxyphenyl)

The ultrasonic reaction of Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,3-dithiadiphosphetane-2,4-disulfide, LR) with Ag(OAc) and Ph₃P (triphenylphosphane) gave an Ag₂₀ cluster {[Ag₂₀(ArP(OEt)S₂)₆(ArPOS₂)₆(Ph₃P)₈]·2(OAc)·8(H₂O)·(CHCl₃)} (1) (Ar = 4-methoxyphenyl). The core of this cluster is an Ag-based propeller comprised of one triangle central axis and three distorted rectangle leaves. The bipodal and tripodal P/S-containing ligands were generated from in situ P–S bond cleavage and P–O bond formation process.     

First two-dimensional framework material constructed from bicapped Keggin structure clusters: [Cu(en)2(H2O)]{[PMoVI8VIV6O42Cu(en)2][Cu0.5(en)]3} · 5.5H2O

The hydrothermal reaction of CuCl₂ · 2H₂O, Na₂MoO₄ · 2H₂O, NH₄VO₃, ethylenediamine (en) and H₃PO₄ yields a novel two-dimensional open-framework material. The extended structure consists of a network of {PMo₈V₆O₄₂ [Cu(en)₂]}⁵⁻ cages, with each cage connected to three other neighboring units via [Cu(en)₂]²⁺ bridging groups.     

A new ring-shaped Cr-containing tungstophosphate based on [H2P2W12O48]12−

A new Cr-containing tungstophosphate [(Cr(H₂O)₂)₃(H₂P₂W₁₂O₄₈)₃]^27 − (1a) was prepared via simple, one-pot reaction method, which was isolated as hydrated potassium salt, K₄[H₂₃(Cr(H₂O)₂)₃(H₂P₂W₁₂O₄₈)₃]·34H₂O (1). Compound 1 was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, elemental analyses, thermal analysis, electrochemistry and electrospray ionization mass spectrometry. Polyoxoanion 1a is composed of three {P₂W₁₂} subunits linked by three {Cr(H₂O)₂} bridges alternately, forming a ring in a corner-sharing mode. Moreover, variable temperature magnetic susceptibility indicates that 1 shows antiferromagnetic behavior.     

A tetranuclear oxomolybdenum(V) complex with bridging squarate ligands, [MoV4O8(OH)2(H2O)2(C4O4)2]2−

The new tetranuclear polyoxomolybdate(V) ion [Mo^V₄O₈(OH)₂(H₂O)₂(C₄O₄)₂]²⁻ has been obtained in one step by the reaction of sodium molybdate, hydrazine and squaric acid in water and crystallized as a potassium salt. The structure has been solved by single-crystal X-ray diffraction showing the location of the hydroxo and water molecule ligands.     

超分子化合物(C12N2H9)2(C12N2H8)[SW12O40]的合成与结构表征

利用水热法合成了超分子化合物（C12N2H9）2（C12N2H8）[SW12O40],通过元素分析和X射线单晶衍射确定了其晶体结构,该晶体为正交晶系,P2（1）2（1）2（1）空间群,晶胞参数为a=12．0168（3）A^。,b=21．0534（6）A^。,c=22．5820（6）A^。,V=5713．1（3）A^。^3,α=β=γ=90°,Z=4,Dc=3．977mg·m^-3,并通过IR和XRD进行了结构表征,采用热重分析研究了晶体的热稳定性。该化合物由邻菲罗林和Keggin结构[SW12O40]^2-阴离子组成,以氢键自组装成超分子结构化合物。     

Synthesis and nanostructure of [Mo(C6H4O2)3]·2(C4H8N2O) and the synthesis from 1,2-PDA to (C4H8N2O)

Continuing our work on the synthesis of MoO₂L₂ and MoO₃L_AL_B that show excellent anti-cancer activities in vitro, the MoL₃ have been synthesized by the solvothermal reaction of Na₂MoO₄ with catechols and 1,2-DPA in the mixed solvent of MeCN/MeOH. X-ray diffraction revealed that Mo in chiral octahedral geometry coordinate with three catechol ligands formed three five-membered rings, and the [Mo(C₆H₄O₂)₃] are linked by hydrogen bonds Mo(OC₆H₄)O…H–N(C₄H₈O)N–H…O(C₆H₄O)Mo through the by-product (C₄H₈N₂O) that are formed by one 1,2-DPA with one CO₂ on the catalysis of Mo-complex. Also, we have disassembled bulk crystal into nano-aggregates, and under TEM mono-lamella morphology of nanostructures was observed, which agrees well with the previous conclusion that the morphologies of the nano-aggregates are associated with the quantum motifs in their crystal lattices. [Mo(C₆H₄O₂)₃] have also been characterized by UV–vis spectra, cyclic voltammogram and thermogravimetric analysis.