Modified polyoxometalate: a novel monocapped bi‐supporting and reduced α‐Keggin structure {PMo12O40[Cu(2,2′‐bpy)]}[Cu(2,2′‐bpy)(en)(H2O)]2

A novel modified polyoxometalate, {PMo₁₂O₄₀[Cu(2,2′‐bpy)]}[Cu(2,2′‐bpy)(en)(H₂O)]₂ [2,2′‐bpy is 2,2′‐bipyridyl (C₁₀H₈N₂) and en is ethylenediamine (C₂H₈N₂)], has been synthesized hydrothermally and structurally characterized by elemental analysis, TG, IR, XPS and single‐crystal X‐ray diffraction. The structural analysis reveals that the compound contains the reduced Keggin polyanion [PMo₁₂O₄₀]^6? as the parent unit, which is monocapped by [Cu(2,2′‐bpy)]²⁺ fragments via four bridging O atoms on an {Mo₄O₄} pit and bi‐supported by two [Cu(2,2′‐bpy)(en)(H₂O)]²⁺ coordination cations simultaneously. There exist strong intramolecular π–π stacking between the capping and supporting units, which play a stabilizing role during the crystallization of the compound. Adjacent POM clusters are further aggregated to form a three‐dimensional supramolecular network through noncovalent forces, hydrogen bonding and π–π stacking interactions. In addition, the photocatalytic properties were investigated in detail, and the results indicated that the compound can be used as a photocatalyst towards the decomposition of the organic pollutant methylene blue (MB).     

新颖的[CuI(dpq)2]+配合物阳离子修饰的砷钒酸盐[Cu(dpq)2]4[As8V14O42(H2O)]·2H2O的水热合成与结构表征

采用水热方法制备了一个新颖的[CuI(dpq)2]+配合物阳离子修饰的砷钒酸盐[Cu(dpq)2]4[As8V14O42(H2O)]·2H2O, X射线单晶衍射结果表明, 该化合物的结构是由4个[CuI(dpq)2]+阳离子和1个[As8V14O42(H2O)]4-簇阴离子以及2个结晶水组成的, 簇阴离子内部包含一个孤立的水分子.     

过渡金属配合物连接的多金属钒酸盐[Co(o-phen)]V2O6·H2O的水热合成和晶体结构

多金属氧酸盐 ( POMs)由于结构新奇 ,物理性能优异 ,在催化、医药、材料和光化学等领域有应用前景 ,而受到人们广泛关注 [1～ 8] .近年来 ,水热技术和有机指导剂的引入促进了 POMs的有机 -无机杂化材料如 [N( CH3) 4]5V18O4 6 [2 ]和 [V4 O10 ( phen) 2 ][3]等研究的迅速发展 .以上化合物多数仅以有机胺为抗衡离子或直接配位连接到无机骨架上 .而以过渡金属配合物为结构导向剂的合成策略 ,最近才引起人们的重视[9～ 11] .本文以钒酸盐 -过渡金属配合物作为研究体系 ,在水热条件下合成了一种未见文献报道的由新型过渡金属配合物连接的…     

新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征

金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1～6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域.     

Synthesis and Crystal Structures of the Molybdenum(II) Complexes with the N,N‐dimethylthiocarbamoyl Containing Ligand: Crystal Structures of β [Mo(CO)2{η2‐S2P(OEt)2}(η2‐SCNMe2)(PPh3)] and [Mo(CO)2(η3‐Tp)(η2‐SCNMe2)(PPh3)]

Reactions of the thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐SCNMe₂)(PPh₃)₂Cl] 1 , and ammonium diethyldithiophosphate, NH₄S₂P(OEt)₂, and potassium tris(pyrazoyl‐1‐yl)borate, KTp, in dichloromethane at room temperature yielded the seven coordinated diethyldithiophosphate thiocarbamoyl‐molybdenum complexe [Mo(CO)₂{η²‐S₂P(OEt)₂}(η²‐SCNMe₂)(PPh₃)] β‐3 , and tris(pyrazoyl‐1‐yl)borate thiocabamoyl‐molybdenum complex [Mo(CO)₂(η³‐Tp)(η²‐SCNMe₂)(PPh₃)] 4 , respectively. The geometry around the metal atom of compounds β‐3 and 4 are capped octahedrons. The α‐ and β‐isomers are defined to the dithio‐ligand and one of the carbonyl ligands in the trans position in former and two carbonyl ligands in the trans position in later. The thiocabamoyl and diethyldithiophosphate or tris(pyrazoyl‐1‐yl)borate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, or three nitrogen atoms, respectively. Complexes β‐3 and 4 are characterized by X‐ray diffraction analyses.     

Two New Polyoxovanadate‐supported Transition Metal Complexes: [Zn(en)2][Zn(en)2(H2O)2][{Zn(en)(enMe)}As6V15O42(H2O)]·4H2O and [Zn2(enMe)2(en)3][{Zn(enMe)2}As6V15O42(H2O)]·4H2O

Two novel As‐V‐O cluster supported transition metal complexes, [Zn(en)₂][Zn(en)₂(H₂O)₂][{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 1 ) and [Zn₂(enMe)₂(en)₃][{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 2 ), have been hydrothermally synthesized. The single X‐ray diffraction studies reveal that both compounds consist of discrete noncentral polyoxoanions [{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]^4? or [{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]^4? cocrystallized with respective zinc coordination complexes. Interestingly, compounds 1 and 2 exhibit the first two polyoxovanadates containing As₈V₁₅O₄₂‐(H₂O)]^6? cluster decorated by only one transition metal complex. Crystal data: 1 , monoclinic, P2₁/n, a = 14.9037(4) Å, b = 18.1243(5) Å, c = 27.6103(7) Å, β = 105.376(6)°, Z = 4; 2 monoclinic, P2₁/n, a = 14.9786(7) Å, b = 33.0534(16) Å, c = 14.9811(5) Å, Z = 4.     

Hydrothermal Synthesis and Structure of a Novel Two-dimensional Complex:[Ni_(0.5)(H_2O)_(1.5){Ni(en)_2}_3V_(18)O_(42)(Cl)]3.5H_2O

1 INTRODUCTION The crystal engineering of inorganic-organic hybrid materials has generated significant interest in their new structural architectures and potential ap- plications in the fields of photochemistry, catalysis, electromagnetism and sorption[1…     

新型化合物[Ni(en)2V6O14]n的水热合成与晶体结构

金属 -氧簇合物在催化吸附、医药临床、能量存储和材料科学等方面的应用越来越受到关注 [1～ 3 ] .钒 -氧簇合物的结构新颖 ,在材料领域中具有广泛的应用前景 .采用水热合成技术 ,以简单的无机、有机起始原料在相对低温下制备金属 -氧簇合物晶体是近年来刚刚兴起的研究工作 [4 ] ,并且已经合成出一维链状化合物 Cu(prn) 2 V2 O6[5]、层状结构 Ni(C10 H8N2 ) 2 V3 O8.5[6]及三维网状结构 (H2 en Me)[Ni(en) 2 V12 O2 8][7] .我们采用水热技术合成了由 { V V 2 O7} n 单元层与桥配体 [Ni(en) 2 ]2 +构建的三维无机 -有机化合物 [Ni(en…     

Keggin型配合物（C12H9N2）3[PMo12O40]的水热合成及晶体结构

采用水热反应合成了有机-无机杂化的Keggin型配合物（C12H9N2）3[PMo12O40],并通过X-射线单晶衍射对其结构进行了分析。该配合物为正交晶系P212121空间群,晶胞参数为a=1.20800（1）nm,b=2.10108（4）nm,c=2.24234（5）nm。配合物包含了孤立的Keggin型[PMo1...     

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 ] ,     

The Interaction of α‐Hydroxycarboxylic Acids with Metal Ions: Lactic Acid (H2L1) and 2‐Methyllactic Acid (H2L2) with Cobalt(II) Crystal and Molecular Structures of [Co(HL1)2(H2O)2]·H2O and [Co(HL2)2(H2O)2]

The cobalt(II) complexes [Co(HL¹)₂(H₂O)₂]·H₂O) ( 1 ) and [Co(HL²)₂(H₂O)₂]( 2 ) [(HL¹)^‐ = (/plusmn;)‐lactate, (HL²)^‐ = 2‐Methyl‐lactate] were prepared and characterized structurally. The cobalt atom is in a distorted octahedral environment in both compounds. Both α‐hydroxycarboxylato ligands are O, O'‐bidentate chelating monoanions. The presence of a lattice water molecule in 1 makes its supramolecular organization different from that of 2 . The thermal behaviour of both compounds was also investigated.     

1D Polyoxometalate‐based Inorganic‐Organic Hybrid Derived from ß‐Octamolybdate — Synthesis and Crystal Structure of [CoII(2, 2′‐bipy)2]2[Mo8O26]

A polyoxometalate‐based inorganic–organic hybrid compound [Co^II(2, 2′‐bpy)₂]₂[Mo₈O₂₆] ( 1 ) was synthesized by hydrothermal methods and structurally characterized by IR spectrum, TG analysis and X‐ray diffraction. The compound crystallizes in the monoclinic system, space group P2₁/n, a = 10.0681(2), b = 16.4467(2), c = 15.7838(3) Å, β = 100.046(1)°, V = 2573.52(8) ų, Z = 2. The structure of 1 is built up from β‐[Mo₈O₂₆]^4? subunits covalently linked via [Co^II(2, 2′‐bpy)₂]²⁺ fragments into a infinite 1D {[Co^II(2, 2′‐bpy)₂]₂[Mo₈O₂₆]}_∞ polymer.     

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.     

A New Polymer of Mixed‐Anions Complex [Pb(phen)(O2CCH3)(O2NO)]n (phen = 1,10‐phenanthroline)

The single crystal X‐ray data of a mixed anions complex of Pb^II with 1,10‐Phenantroline, [Pb(phen)(O₂CCH₃)‐ (O₂NO)], shows the complex to be polymeric as a result of acetate ligand bridging. The Pb atom has an asymmetrical eightfold coordination of two nitrogen atoms of the 1,10‐phenanthroline ligand and six oxygen atoms of the nitrate and acetate anions. The arrangement of the 1,10‐phenantroline ligand, acetate and nitrate anions suggest a gap in the coordination around the Pb^II ion, occupied possibly by a stereoactive lone pair of electrons on lead(II) where the coordination around the lead atoms is hemidirected. There is a π‐π stacking interaction between the parallel aromatic rings of an adjacent chain in the compound which might help to increase the ‘gap' in the coordination around the Pb^II ion.     

一种新颖的六帽Keggin型钼钒砷酸盐——(H3O)3[AsMo12O40(VO)6]·6H2O的水热合成和晶体结构

近年来,含有Keggin结构的杂多酸以其优异的结构可修饰性及其在催化、功能材料和医药等方面的潜在应用而引起人们广泛的研究兴趣.在这一领域中,众多过渡金属取代的Keggin型杂多化合物,尤其是含有钒和铝的多金属氧酸盐由于其独特的电磁特性及结构特点而倍受关注.但迄今为止,只有少数带帽Keggin型结构的杂多阴离子被报道.这些Keggin阴离子通常具有低的V/Mo.     

Hydrothermal synthesis and characterization of the tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate: {PW4W5V3O40(VO)3[Cu(en)2]}

A novel polyoxometalate [Cu(phen)₂]₃{PW₄^VIW₅^VV₃^IVO₄₀(V^IVO)₃[Cu(en)₂]}4H₂O 1 (en=ethylenediamine, phen=1,10-phenanthroline) has been synthesized hydrothermally and characterized by elemental analysis, IR, XPS, TG, EPR and single-crystal X-ray diffraction analysis. The crystal structure analysis shows that compound 1 contains a novel highly reduced tri-capped and mono-supported pseudo-Keggin-type heteropolyanion, {PW₄^VIW₅^VV₃^IVO₄₀(V^IVO)₃[Cu(en)₂]}⁶⁻, three [Cu(phen)₂]²⁺ cations and four lattice water molecules. They are further linked to form three-dimensional supramolecular networks through extensive hydrogen bonding and π–π stacking interactions. Interestingly, the water dimer and terminal oxygen of the cluster polyanion constitute a beautiful supramolecular helix chain. The heteropolyanion is the first example of tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate and the pH value is crucial for obtaining compound 1 in synthetic procedure.     

First Total Synthesis of N‐(3‐Guanidinopropyl)‐2‐(4‐hydroxyphenyl)‐2‐oxoacetamide

The first total synthesis of the α‐oxo amide‐based natural product, N‐(3‐guanidinopropyl)‐2‐(4‐hydroxyphenyl)‐2‐oxoacetamide ( 3 ), isolated from aqueous extracts of hydroid Campanularia sp., has been achieved. The α‐oxo amide 12 , prepared via the oxidative amidation of 1‐[4‐(benzyloxy)phenyl]‐2,2‐dibromoethanone ( 9a ) with 4‐{[(tert‐butyl)(dimethyl)silyl]oxy}butan‐1‐amine ( 10a ), has been used as the key intermediate in the total synthesis of 3 as HBr salt. On the way, an expeditious total synthesis of polyandrocarpamide C ( 2c ), isolated from marine ascidian Polyandrocarpa sp., was carried out in four steps.     

Hydroxo‐bridged Tetranuclear CuII Complexes: {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O and {[Cu(phen)(OH)]4(H2O)2}]Cl4 · 4 H2O

The blue tetranuclear Cu^II complexes {[Cu(bpy)(OH)]₄Cl₂}Cl₂ · 6 H₂O ( 1 ) and {[Cu(phen)(OH)]₄(H₂O)₂}Cl₄ · 4 H₂O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) ų, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) ų, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]₄Cl₂}²⁺ and {[Cu(phen)(OH)]₄(H₂O)₂}⁴⁺ complex cations formed by condensation of four elongated square pyramids CuN₂(OH)₂L^ap with the apical ligands L^ap = Cl, H₂O, OH. The resulting [Cu₄(μ₂‐OH)₂(μ₃‐OH)₂] core has the shape of a zigzag band of three Cu₂(OH)₂ squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl^– anions and H₂O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Cl^ap = 2.563; Cu–O^ap(OH) = 2.334–2.369 Å; Cu–O^ap(H₂O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χ_m(T‐θ) = 0.933 cm³ · mol^–1 · K with θ = –0.7 K).     

An Azelaato‐bridged Dinuclear Copper(II) Complex, [Cu2(phen)2(C9H14O4)2] · 6 H2O (phen = 1,10‐phenanthroline)

The title compound [Cu₂(phen)₂(C₉H₁₄O₄)₂] · 6 H₂O was prepared by the reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), azelaic acid and Na₂CO₃ in a CH₃OH/H₂O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR² = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu₂(phen)₂(C₉H₁₄O₄)₂] complexes and hydrogen bonded H₂O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands.