A three‐dimensional inorganic/organic hybrid material, [Ni2(4,4′‐bipy)3(H2O)2V4O12]·2.5H2O

The title compound, poly­[[[di­aqua(μ‐4,4′‐bipyridyl)­di­nickel(II)]‐bis(μ‐4,4′‐bipyridyl)‐di‐μ‐hexa­oxo­di­vana­date(2?)] 2.5‐hydrate], [Ni₂­(V₂O₆)₂­(C₁₀H₈N₂)₃­(H₂O)₂]·­2.5H₂O, has been prepared hydro­thermally and characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. The structure consists of [V₂O₆], [Ni­(4,4′‐bipy)₄O₂] and [Ni­(H₂O)₂­(4,4′‐bipy)₂O₂] polyhedra, and water of crystallization. The Ni atoms and one bipyridyl group lie on centres of symmetry.     

Synthesis,Characterization, and Luminescence of Two New Zinc(II) Coordination Polymers Constructed by 5‐(4‐Carboxybenzyloxy)Isophthalic Acid Ligand

Two coordination polymers, namely Zn(HL)(4,4′‐bpy)_1.5 ( 1 ), [Zn₃(L)₂(BIMB)₂] · 5H₂O ( 2 ) [H₃L = 5‐(4‐carboxybenzyloxy)isophthalic acid, 4,4′‐bpy = 4,4′‐bipyridine, BIMB = 1,4‐bis(1H‐imidazol‐1‐yl)benzene] were synthesized under hydrothermal conditions. Their structures are determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and thermogravimetric (TG) analyses. Complex 1 features a 2D 4‐connected network. Complex 2 is a 3D twofold interpenetrating (3,4,6)‐connected net. In addition, the luminescent properties for 1 and 2 were studied in the solid state at room temperature.     

Cube‐like 12‐MC‐4 and Offset Stacked 10‐MC‐3 Metallacrowns: Synthesis,Structure, and Magnetic Properties

Two complexes [Mn^III₄(naphthsao)₄(naphthsaoH)₄] ( 1 ) and [Fe^III₆O₂(naphthsao)₄(O₂CPh)₆] ( 2 ) [naphthsao = 1‐(1‐hydroxy‐naphthalen‐2‐yl)ethanone oxime] were obtained through the reactions of naphthsao ligand and MnCl₂ · 4H₂O or FeCl₃ · 6H₂O in the presence of triethylamine (Et₃N). Their structures were determined by X‐ray single crystal diffraction, elemental analysis, and IR spectra. Complex 1 displays 12‐MC‐4 metallacrown structural type with cube‐like configuration and 2 shows an offset stacked 10‐MC‐3 structural type with the ring connectivity containing Fe–O–C–O–Fe–O–N–Fe–O–N. Magnetic susceptibility measurement reveals the ferromagnetic interactions and field‐induced slow relaxation of the magnetization for 1 , whereas out‐of‐phase signal is not observed for 2 .     

A three‐dimensional cyanide‐bridged heterometallic coordination polymer: poly[[diacetonitrilediaqua[μ2‐3,6‐bis(pyridin‐2‐yl)‐1,2,4,5‐tetrazine‐κ4N1,N6:N3,N4]tetra‐μ‐cyanido‐tetracyanidodimanganese(II)molybdate(IV)] dihydrate]

A metal coordination polymer, {[Mn₂Mo(CN)₈(C₁₂H₈N₆)(CH₃CN)₂(H₂O)₂]·2H₂O}_n, has been synthesized by the reaction of Mn(ClO₄)₂·6H₂O with 3,6‐bis(pyridin‐2‐yl)‐1,2,4,5‐tetrazine (bptz) and (Bu₃N)₃[Mo(CN)₈] at room temperature. The polymer was characterized by IR spectroscopy, elemental analysis and X‐ray diffraction, and the magnetic properties were also investigated. The X‐ray diffraction analysis reveals that the compound is a new three‐dimensional coordination polymer with a PtS‐type network. Magnetic investigation shows antiferromagnetic coupling between adjacent Mn²⁺ cations.     

四个对苯酚四唑硫酮金属(II)配合物的合成和晶体结构

四唑酸(–CN4H)与羧酸(–COOH)具有相似的酸性。对苯酚四唑硫酮(H2L)可以作为单齿(–S或–N)或双齿(–N, N或–N, S)配体与金属离子配位形成配位化合物。合成了4个以H2L为配体的金属(II)配合物：Co(HL)2(Py)2(H2O)2 (1), [Mn(HL)2(H2O)4]·2H2O (2), Mn(HL)2(Phen)2 (3), and [Zn(HL)2(Phen)2]·0.5H2O·1.5CH3OH (4),并用X−射线单晶衍射法测定了晶体结构。晶体结构分析表明,在这些配合物中所有的中心金属原子均呈现六配位的八面体构型。在配合物1和2中,HL–配体以氧原子与中心金属原子配位,而在配合物3和4中HL–配体则以硫原子与中心金属原子配位。     

Synthesis and crystal structure of 2‐amino‐3‐hydroxypyridinium dioxido(pyridine‐2,6‐dicarboxylato‐κ3O2,N,O6)vanadate(V) and its conversion to nanostructured V2O5

2‐Amino‐3‐hydroxypyridinium dioxido(pyridine‐2,6‐dicarboxylato‐κ³O²,N,O⁶)vanadate(V), (C₅H₇N₂O)[V(C₇H₃NO₄)O₂] or [H(amino‐3‐OH‐py)][VO₂(dipic)], (I), was prepared by the reaction of VCl₃ with dipicolinic acid (dipicH₂) and 2‐amino‐3‐hydroxypyridine (amino‐3‐OH‐py) in water. The compound was characterized by elemental analysis, IR spectroscopy and X‐ray structure analysis, and consists of an anionic [VO₂(dipic)]⁻ complex and an H(amino‐3‐OH‐py)⁺ counter‐cation. The V^V ion is five‐coordinated by one O,N,O′‐tridentate dipic dianionic ligand and by two oxide ligands. Thermal decomposition of (I) in the presence of polyethylene glycol led to the formation of nanoparticles of V₂O₅. Powder X‐ray diffraction (PXRD) and scanning electron microscopy (SEM) were used to characterize the structure and morphology of the synthesized powder.     

一个新颖的由Zn配合物修饰的Keggin型钴钨酸盐：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O

通过水热合成技术,一个新颖的基于Zn配合物修饰的Keggin型钴钨酸的有机-无机杂化化合物：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O已经被合成,化合物通过红外光谱、热重分析和单晶X-射线衍射进行了表征。单晶X-射线衍射的结果显示标题化合物是由一个单支撑的{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2}6-多阴离子,三个[Zn(2,2’-bipy)3]2+阳离子和一个水分子构成。有趣的是[Zn(1)(2,2’-bipy)3]2+阳离子通过氢键连接在一起形成螺旋链。另外标题化合物在空气中是稳定的,并且在室温下显示了强的荧光。     

Syntheses,Structures, and Catalytic Activities of Copper(I) Complexes with the Ligand 2(4,5‐Diphenyl‐1H‐imidazol‐2‐yl)­pyridine

Two copper(I) complexes of compositions [Cu(HL)I]₂ · EtOH ( 1 ) and [Cu(HL)₃]I · MeOH ( 2 ) were synthesized via the reactions of HL [HL = 2(4,5‐diphenyl‐1H‐imidazol‐2‐yl)pyridine] and CuI in EtOH and MeOH, respectively, under solvothermal conditions. The complexes were characterized by X‐ray single crystal diffraction, IR spectroscopy, and elemental analysis. Compounds 1 and 2 are catalytically active towards ketalization reaction, giving various ketals under mild conditions.     

Diamond‐ and Graphite‐Like Octacyanometalate‐Based Polymers Induced by Metal Ions

By using cyclohexane‐1,2‐diamine (chxn), Ni(ClO₄)₂ ? 6H₂O and Na₃[Mo(CN)₈] ? 4H₂O, a 3D diamond‐like polymer {[Ni^II(chxn)₂]₂[Mo^IV(CN)₈] ? 8H₂O}_n ( 1 ) was synthesised, whereas the reaction of chxn and Cu(ClO₄)₂ ? 6H₂O with Na₃[M^V(CN)₈] ? 4H₂O (M=Mo, W) afforded two isomorphous graphite‐like complexes {[Cu^II(chxn)₂]₃[Mo^V(CN)₈]₂ ? 2H₂O}_n ( 2 ) and {[Cu^II(chxn)₂]₃[W^V(CN)₈]₂ ? 2H₂O}_n ( 3 ). When the same synthetic procedure was employed, but replacing Na₃[Mo(CN)₈] ? 4H₂O by (Bu₃NH)₃[Mo(CN)₈] ? 4H₂O (Bu₃N=tributylamine), {[Cu^II(chxn)₂Mo^IV(CN)₈][Cu^II(chxn)₂] ? 2H₂O}_n ( 4 ) was obtained. Single‐crystal X‐ray diffraction analyses showed that the framework of 4 is similar to 2 and 3 , except that a discrete [Cu(chxn)₂]²⁺ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond‐ or graphite‐like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [Mo^IV(CN)₈] bridges mediate very weak antiferromagnetic coupling between the Ni^II ions in 1 , but lead to the paramagnetic behaviour in 4 because [Mo^IV(CN)₈] weakly coordinates to the Cu^II ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the Cu^II and W^V/Mo^V ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the W^V and Cu^II ions than between the Mo^V and Cu^II ions.     

Coordination Chemistry of Homoleptic Actinide(IV)–Thiocyanate Complexes

The synthesis, X‐ray crystal structure, vibrational and optical spectroscopy for the eight‐coordinate thiocyanate compounds, [Et₄N]₄[Pu^IV(NCS)₈], [Et₄N]₄[Th^IV(NCS)₈], and [Et₄N]₄[Ce^III(NCS)₇(H₂O)] are reported. Thiocyanate was found to rapidly reduce plutonium to Pu^III in acidic solutions (pH<1) in the presence of NCS^?. The optical spectrum of [Et₄N][SCN] containing Pu^III solution was indistinguishable from that of aquated Pu^III suggesting that inner‐sphere complexation with [Et₄N][SCN] does not occur in water. However, upon concentration, the homoleptic thiocyanate complex [Et₄N]₄[Pu^IV(NCS)₈] was crystallized when a large excess of [Et₄N][NCS] was present. This compound, along with its U^IV analogue, maintains inner‐sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand‐to‐metal charge‐transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced An^IV–NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu.     

一个二维Honeycomb-like聚合簇合物 (Et4N)3{[MoS4Cu2(m-CN)]2(m’-CN)}·2MeCN的合成和晶体结构

采用一个预制的簇合物(Et₄N)₂[MoS₄(CuCN)₂]·H₂O(1)和HAc在MeCN中混合反应，生成了一个有趣的二维聚合簇合物(Et₄N)₃{[MoS₄Cu₂(m-CN)]₂(m’-CN)}·2MeCN (2)。通过元素分析，红外光谱及单晶X-射线衍射分析对簇合物2进行了表征。在2的结构中，前驱体1中的MoS₄Cu₂簇核得到了保留，并且此簇核作为三重连接点通过单一氰桥和其他相同的簇核相连，形成一个阴离子型的2D (6,3)（蜂窝状）网络。由预制的簇合物1通过醋酸诱导形成的超分子2表明这种简单的合成方法有可能应用到许多其他相关的体系。     

Copper(II) and Cadmium(II) Complexes Based on N,N‐Bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine Ligand: Syntheses,Structures, Magnetic,and Luminescent Properties

The reaction of the aryl‐oxide ligand H₂L [H₂L = N,N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine] with CuSO₄ · 5H₂O, CuCl₂ · 2H₂O, CuBr₂, CdCl₂ · 2.5H₂O, and Cd(OAc)₂ · 2H₂O, respectively, under hydrothermal conditions gave the complexes [Cu(H₂L¹)₂] · SO₄ · 3CH₃OH ( 1 ), [Cu₂(H₂L²)₂Cl₄] ( 2 ), [Cu₂(H₂L²)₂Br₄] ( 3 ), [Cd₂(HL)₂Cl₂] ( 4 ), and [Cd₂(L)₂(CH₃COOH)₂] · H₂L ( 5 ), where H₂L¹ [H₂L¹ = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H₂L² [H₂L² = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission.     

Syntheses,Structures and Magnetic Behaviours of two Mixed‐Metal Inorganic‐Organic Hybrid Frameworks with N‐(Phosphonomethyl)iminodiacetate

Two mixed‐metal‐center inorganic‐organic hybrid frameworks incorporating N‐(Phosphonomethyl)iminodiacetate(H₄pmida), [Zn₂V₂O₂(pmida)₂(H₂O)₁₀]·H₂O ( 1 ) and [Zn₂V₂O₂(pmida)₂(H₂O)₁₂]·2H₂O ( 2 ), were synthesized by hydrothermal reactions and characterized by elemental analysis, IR spectra, UV‐Vis spectra and single crystal X‐ray analysis. In complex 1 , the centrosymmetric dimeric [V₂O₂(pmida)₂]^4– unit connected to neighboring Zn²⁺ through the phosphonate group, while 2 the [V₂O₂(pmida)₂]^4– unit uncoordinated with the Zn²⁺ in the presence of NaOH. Magnetic measurements in the range 2‐300 K have shown weak antiferromagnetic interaction between the adjacent vanadium ions in complexes.     

Synthesis and Magnetic Properties of Two New Cobalt Complexes Constructed by Semirigid V‐shaped 5‐(4‐Carboxyphenoxy)‐pyridine‐2‐carboxylic Acid

Two cobalt complexes, [Co₃(L)₂(CH₃OH)₂(μ₃‐OH)₂] ( 1 ) and [Co(L)(bpe)_0.5] · H₂O ( 2 ) [H₂L = 5‐(4‐carboxyphenoxy)‐pyridine‐2‐carboxylic acid; bpe = 1, 2‐bis(4‐pyridyl)ethylene] were synthesized and fully characterized by elemental analyses, IR spectroscopy, single‐crystal X‐ray diffraction, thermogravimetric analysis (TGA), and magnetic analysis. Complex 1 has a two‐dimensional (2D) structure with puckered Co–O–Co chains, and 2 displays a three‐dimensional (3D) network containing one‐dimensional rectangular channels with dimensions of 9.24 × 13.84 Å. In complex 1 , variable‐temperature magnetic susceptibility measurements indicate antiferromagnetic interactions between cobalt magnetic centers.     

Zweikernige Palladium(II)‐, Platin(II)‐ und Iridium(III)‐Komplexe von Bis[imidazol‐4‐yl]alkanen

Dinuclear Palladium(II), Platinum(II), and Iridium(III) Complexes of Bis[imidazol‐4‐yl]alkanes The reaction of bis(1,1′‐triphenylmethyl‐imidazol‐4‐yl) alkanes ((CH₂)_n bridged imidazoles L(CH₂)_nL, n = 3–6) with chloro bridged complexes [R₃P(Cl)M(μ‐Cl)M(Cl)PR₃] (M = Pd, Pt; R = Et, Pr, Bu) affords the dinuclear compounds [Cl₂(R₃P)M–L(CH₂)_nL–M(PR₃)Cl₂] 1 – 17 . The structures of [Cl₂(Et₃P)Pd–L(CH₂)₃L–Pd(PEt₃)Cl₂] ( 1 ), [Cl₂(Bu₃P)Pd–L(CH₂)₄L–Pd(PBu₃)Cl₂] ( 10 ), [Cl₂(Et₃P)Pd–L(CH₂)₅L–Pd(PEt₃)Cl₂] ( 3 ), [Cl₂(Et₃P)Pt–L(CH₂)₃L–Pt(PEt₃)Cl₂] ( 13 ) with trans Cl–M–Cl groups were determined by X‐ray diffraction. Similarly the complexes [Cl₂(Cp*)Ir–L(CH₂)_nL–Ir(Cp*)Cl₂] (n = 4–6) are obtained from [Cp*(Cl)Ir(μ‐Cl)₂Ir(Cl)Cp*] and the methylene bridged bis(imidazoles).     

New Rh(III) complexes of 5‐methyl‐5‐(pyridyl)‐2,4‐imidazolidenedione: Synthesis,X‐ray structure,electrochemical study and catalytic behaviour for hydrogenation of ketones

We describe the reaction of anion [RhCl₆]³⁻ with a series of hydantoin ligands (HL1, HL2 and HL3 = 5‐methyl‐5‐(2‐, 3‐ and 4‐pyridyl)‐2,4‐imidazolidenedione, respectively). Based on spectroscopic, cyclic voltammetric, elemental and MS analyses, the complexes have the general formula K[RhCl₂(L1)₂] ( 1 ), cis ‐ and trans ‐K[RhCl₄(HL2)₂] ( 2a and 2b ) and cis ‐ and trans ‐K[RhCl₄(HL3)₂] ( 3a and 3b ). Complexes 2a , 2b , 3a and 3b were characterized successfully using infrared, ¹H NMR and ¹³C NMR spectral analyses. Dissolution of complex 1 in dimethylsulfoxide (DMSO) led to elimination of one KL1 ligand and coordination of two DMSO molecules as ligands and transformation of this complex to cis ‐ and trans ‐[RhCl₂L1(DMSO)₂] ( 1a and 1b ). Recrystallization led to separation and isolation of crystals of 1a from the initial mixture. X‐ray analysis results showed that this complex was crystallized as solvated complex cis ‐[RhCl₂L1(DMSO)₂]DMSO. The catalytic activity of these complexes was then evaluated for the hydrogenation of various ketones.     

Coordinative Behaviour of Tridentate NS2‐Donor Ligands with Cadmium: Synthesis and Crystal Structures of New Complexes

The reaction of cadmium salts with various amounts of the tridentate NS₂‐chelating ligands 1‐(2‐mercapto‐acetophenone)‐4‐triphenylmethylthiosemicarbazone (H₂L¹) and 1‐(5‐mercapto‐3‐methyl‐1‐phenylpyrazole‐4‐carboxaldehyde)‐4‐triphenyl‐methylthiosemicarbazone (H₂L²) in the presence of bases like N‐methylimidazole (N–MeIm), pyridine (py) or triethylamine (Et₃N) provided a series of novel mono‐, di‐, tri‐ and heptanuclear cadmium complexes. They are of the general formulas [CdL¹(N–MeIm)]₂ ( 1 ), [CdL¹(py)]₂ ( 2 ), [CdL²(N–MeIm)]₂ ( 3 ), [CdL²(py)₃] · 0.25 C₆H₁₄ · 0.5 py ( 4 ), [Et₃NH]₂[Cd₃L ] · 7 MeOH ( 5 ), [Et₃NH]₂[Cd₃L ] ( 6 ) and [Et₃NH]₂[Cd₇L ] · 14 MeOH ( 7 ). The compounds were characterized by elemental analysis, IR‐ and ¹H‐NMR‐spectroscopy. Single‐crystal X‐ray structure analyses are reported for the complexes 2 , 4 , 5 and 7 . While 2 has a dimeric structure where each cadmium ion is pentacoordinated in a N₂S₃‐environment, 4 consists of a monomeric cadmium center with distorted octahedral N₄S₂‐coordination. The complexes 5 and 7 exhibit new structural types for tri‐ and heptanuclear cadmium compounds. It is shown that sulfur bridging might proceed via arylthiolates, iminothiolates or even both functions of the ligand. Aggregation is influenced by various factors like solvents, counterions and ligand properties.     

C‐O Bond Cleavage of Diethyl Ether and Tetrahydrofurane by [(dpp‐BIAN)AlI(Et2O)] [dpp‐BIAN = 1,2‐bis[(2,6‐di‐iso‐propylphenyl)‐imino]acenaphthene]

At elevated temperatures, the aluminum complex [(dpp‐BIAN)AlI(Et₂O)] ( 1 ) splits the C‐O bonds of diethyl ether and tetrahydrofurane yielding the dimeric alkoxides [(dpp‐BIAN)AlOEt]₂ ( 2 ) and [(dpp‐BIAN)AlO(CH₂)₄I]₂ ( 3 ), respectively. Already at ambient temperatures, a cleavage of the C‐O bond of THF is to observe in the reaction of 1 with CpNa in THF as confirmed by the formation of [(dpp‐BIAN)AlO(CH₂)₄C₅H₅]₂ ( 4a ) and [(dpp‐BIAN)Al{O(CH₂)₄C₅H₅}(THF)] ( 4b ) in a molar ratio of 1:2. The reaction of 1 with t‐BuOK affords the monomeric alkoxide [(dpp‐BIAN)AlO‐t‐Bu(Et₂O)] ( 5 ). Compounds 2 , 3 , and 4a/b were characterized by elemental analyses and IR spectra. Additionally, the structures of 2 and 3 were determined by single crystal X‐ray diffraction.     

Counterion‐Directed Assembly of Praseodymium(III) Compounds based on the Flexible Ligand 5‐Aminotetrazole‐1‐propionic Acid (Hatzp)

Different kinds of counterions (such as NO₃^–, ClO₄^–, and Cl^–) play a special role in controlling the framework of coordination compounds. Using this strategy, 5‐aminotetrazole‐1‐propionic acid (Hatzp) was selected to react with praseodymium(III) nitrate or perchlorate in the same solvent system, producing two different coordination compounds, [Pr₂(atzp)₄(H₂O)₈] · 2NO₃ · 2H₂O ( 1 ) and [Pr₂(atzp)₆(H₂O)₂] · H₂O ( 2 ). These compounds were structurally characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. X‐ray diffraction analysis revealed that compound 1 displays a dinuclear structure, whereas 2 shows a one dimensional zigzag chain framework. Furthermore, the luminescence properties of compounds 1 and 2 were investigated at room temperature in the solid state.     

A novel alkaline earth strontium(II) coordination polymer: poly[hexaaquatetrakis(μ5‐pyridine‐2,6‐dicarboxylato)bis(μ4‐pyridine‐2,6‐dicarboxylato)(μ7‐sulfato)heptastrontium(II)]

The title compound, [Sr₇(C₇H₃NO₄)₆(SO₄)(H₂O)₆]_n, has been synthesized by an ionothermal method using the ionic liquid 1‐ethyl‐3‐methylimidazolium ([Emim]Br) as solvent, and characterized by elemental analysis, energy‐dispersive X‐ray spectroscopy, IR and single‐crystal X‐ray diffraction. The structure of the compound can be viewed as a three‐dimensional coordination polymer composed of Sr²⁺ cations, pyridine‐2,6‐dicarboxylate anions, sulfate anions and water molecules. The compound not only exhibits a three‐dimensional structure with a unique coordination mode of the sulfate anion, but also features the first example of a heptanuclear strontium(II) coordination polymer. The structure is further stabilized by O—H...O hydrogen bonds and π–π stacking interactions.