Heterodinuclear Ruthenium(II) Complexes of the Bridging Ligand 1,6,7,12‐Tetraazaperylene with Iron(II), Cobalt(II), Nickel(II), as well as Palladium(II) and Platinum(II)

The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12‐tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)‐pyridinophane (L‐N₄Me₂) ligand, yielding complexes of the general formula [(L‐N₄Me₂)Ru(µ‐tape)M(L‐N₄Me₂)](ClO₄)₂(PF₆)₂ with M = Fe {[ 2 ](ClO₄)₂(PF₆)₂}, Co {[ 3 ](ClO₄)₂(PF₆)₂}, and Ni {[ 4 ](ClO₄)₂(PF₆)₂}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)‐ and platinum(II)‐dichloride [(bpy)₂Ru(μ‐tape)PdCl₂](PF₆)₂ {[ 5 ](PF₆)₂} and [(dmbpy)₂Ru(μ‐tape)PtCl₂](PF₆)₂ {[ 6 ](PF₆)₂}, respectively were also prepared. The molecular structures of the complex cations [ 2 ]⁴⁺ and [ 4 ]⁴⁺ were discussed on the basis of the X‐ray structures of [ 2 ](ClO₄)₄ · MeCN and [ 4 ](ClO₄)₄ · MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono‐ and homodinuclear ruthenium(II) complexes of the tape bridging ligand.     

1,2-环己二胺缩邻香兰素单核与四核镱稀土配合物的近红外性质

通过配体1,2-环己二胺缩邻香兰素（H₂L）和不同的镱盐反应,合成了4个镱稀土配合物[Yb（H₂L）₂]（ClO₄）₃·2CH₃OH·H₂O（1）,[Yb₄（L）₄（NO₃）₂（H₂O）₂]（PF₆）₂·4CH₃CN（2）,[Yb₄（L）₄（H₂O）₂Cl₂]（PF₆）₂·2CH₂Cl₂·2H₂O（3）和[Yb₄（L）₄（NO₃）₂（H₂O）₂][Yb（NO₃）₃（H₂O）₂（CH₃OH）]（NO₃）₂ ·4CH₂Cl₂·6CH₃OH（4）。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。     

Hydrothermal synthesis,crystal structure and antibacterial studies of nickel(II) and manganese(II) complexes with ciprofloxacin

Hydrothermal treatments of ciprofloxacin with Ni(NO₃)₂·6H₂O and Mn(ClO₄)₂·6H₂O yield two metal complexes: [Ni(H-cip)₂(H₂O)₂](NO₃)₂·2H₂O (1) and [Mn(H-cip)₂(H₂O)₂] (ClO₄)₂·2H₂O (2), confirmed by elemental analysis, IR and single crystal X-ray diffraction analyses. Complexes 1 and 2 were screened for antibacterial activity against Staphylococcus aureas, E. coli, Pseudomonas aeruginos and Candidaalbicans.     

Coordination compounds of cobalt(II), nickel(II), and copper(II) with 4-(3-hydroxyphenyl)-1,2,4-triazole: Synthesis and study

New Co(II), Ni(II), and Cu(II) complexes with 4-(3-hydroxyphenyl)-1,2,4-triazole (L) with the compositions [Co₃L₆(H₂O)₅(C₂H₅OH)](NO₃)₆ · 2H₂O · C₂H₅OH (I), [Ni₃L₆(H₂O)₆](NO₃)₆ · 2H₂O (II), and [M₃L₆(H₂O)₆](ClO₄)₆ · nH₂O (M = Co2⁺, n = 2 (III); Ni²⁺, n = 2 (IV); Cu²⁺, n = 0 (V)) are synthesized. The complexes are studied by X-ray structure analysis, X-ray diffraction analysis, UV and IR spectroscopy, and the statistical magnetic susceptibility method. All compounds have the linear trinuclear structure. Ligand L is coordinated to the metal ions by the N(1) and N(2) atoms of the heterocycle according to the bidentate bridging mode. In all compounds the coordination polyhedron of the metal atom is a distorted octahedron. The molecular and crystal structures of compound I, [Co₃L₆(H₂O)₆](ClO₄)₆ · 8C₂H₅OH (IIIa), and [Ni₃L₆(H₂O)₆](ClO₄)₆ · 8C₂H₅OH (IVa) are determined.     

1，2-环己二胺缩邻香兰素单核与四核镱稀土配合物的近红外性质

通过配体1,2-环己二胺缩邻香兰素（H2L）和不同的镱盐反应,合成了4个镱稀土配合物[Yb（H₂L）₂]（ClO₄）₃·2CH₃OH·H₂O（1）,[Yb₄（L）₄（NO₃）₂（H₂O）₂]（PF₆）₂·4CH₃CN（2）,[Yb₄（L）₄（H₂O）₂Cl2]（PF₆）₂·2CH₂Cl₂·2H₂O（3）和[Yb₄（L）₄（NO₃）₂（H₂O）₂][Yb（NO₃）₃（H₂O）₂（CH₃OH）]（NO₃）₂·4CH₂Cl₂·6CH₃OH（4）。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。     

Synthesis,vibrational spectra,and structure of 4′-(4″-benzo-15-crown-5)oxy-2,2′:6′,2″-terpyridine (L) and its transition metal complexes. Extraction and ion-selective properties of L

Complexes of Co(II), Ni(II), Zn(II), and Cu(II) perchlorates and hexafluorophosphates with 4′-(4″-benzo-15-crown-5)oxy-2,2′:6′,2″-terpyridine (L) [M(L)₂](ClO₄)₂ · 3H₂O and [M(L)₂](PF₆)₂ · 2H₂O were synthesized. The spectral criteria of ligand coordination through the terpyridine nitrogen atoms were established. An assumption concerning the benzo-15-crown-5 conformation in the ligand molecule in the synthesized complexes was made. The extraction and ion-selective properties of L were studied.     

Synthesis and study of cobalt(II), nickel(II), and copper(II) complexes with 4-(4-hydroxyphenyl)-1,2,4-triazole

New complexes of Co(II), Ni(II), and Cu(II) nitrates, chlorides, and perchlorates with 4-(4-hydroxyphenyl)-1,2,4-triazole (L) were obtained and examined by single-crystal X-ray diffraction, X-ray powder diffraction, and electronic absorption and IR spectroscopy. The cations of all the complexes have linear trinuclear structures. Ligand L is coordinated to the metal ions in a bidentate bridging fashion through the N(1) and N(2) atoms of the heterocycle. The coordination polyhedron of the metal atoms is a distorted octahedron. The molecular and crystal structures of the complexes [Co₃L₆(H₂O)₆](ClO₄)₆ · 3C₂H₅OH · 3.75H₂O and [M₃L₆(H₂O)₆](ClO₄)₆ · 6H₂O (M = Cu²⁺ and Ni²⁺) were determined.     

2‐Amino‐5‐(2‐pyridyl)‐thiadiazole as Bidentate Ligand

The amino substituted bidentate chelating ligand 2‐amino‐5‐(2‐pyridyl)‐1,3,4‐thiadiazole (H₂ L ) was used to prepare 3:1‐type coordination compounds of iron(II), cobalt(II) and nickel(II). In the iron(II) perchlorate complex [Fe^II(H₂ L )₃](ClO₄)₂·0.6MeOH·0.9H₂O a 1:1 mixture of mer and fac isomers is present whereas [Fe^II(H₂ L )₃](BF₄)₂·MeOH·H₂O, [Co^II(H₂ L )₃](ClO₄)₂·2H₂O and [Ni^II(H₂ L )₃](ClO₄)₂·MeOH·H₂O feature merely mer derivatives. Moessbauer spectroscopy and variable temperature magnetic measurements revealed the [Fe^II(H₂ L )₃]²⁺ complex core to exist in the low‐spin state, whereas the [Co^II(H₂ L )₃]²⁺ complex core resides in its high‐spin state, even at very low temperatures.     

Synthesis and characterization of TCNQ derivatives of Ni(II) and Cu(II) with pyrazole-based ligands

Reactions between nickel(II) and copper(II) salts [M(L) _n ](ClO₄)₂ [L: 2-(pyrazole-1-ylmethyl)pyridine; n = 3 for Ni(II) and n = 2 for Ni(II) and Cu(II)] and LiTCNQ or mixture of LiTCNQ/TCNQ and Et₃NH(TCNQ)₂ yielded [Ni(L)₃](TCNQ)₂ · H₂O, [Ni(L)₂(TCNQ)₂], [Ni(L)₃](TCNQ)₃, [Ni(L)₂(TCNQ)₃], and [Cu(L)₂(TCNQ)₃] · 3H₂O. These complexes were characterized by infrared, electronic absorption, variable temperature magnetic moments and electron paramagnetic studies. Magnetic moments increase with increase in temperature attributed to contribution from TCNQ, which has also been examined by electron paramagnetic resonance.     

Ni(II), Pd(II), Cu(II) And Zn(II) complexes with N-(2-Pyridyl)Carbonylaniline (L), Syntheses and X-Ray Crystal structures of [Cu(L)2(H2O)2](No3)2, [Cu(L)2(H2O)2](Clo4)2 and [Zn(L)2(H2O)2](Clo4)2

Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO₃)₂, Cu(ClO₄)₂, Zn(ClO₄)₂, Ni(NO₃)₂ and PdCl₂ gives complexes with stoichiometry [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, [Zn(L)₂(H₂O)₂] (ClO₄)_2, [Ni(L)₂(H₂O)Cl](NO₃) and PdLCl₂. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, and [Zn(L)₂(H₂O)₂](ClO₄)₂ were determined by X-ray crystallography. The cation complexes [M(L)₂(H₂O)₂] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.     

Copper(II), Cobalt(II), and Nickel(II) Complexes of two Novel Pyridine‐derived Macrocyclic Ligands bearing o‐ and pNitrobenzyl Pendant Groups

The pendant‐armed ligands L¹ and L² were synthesized by N‐alkylation of the four secondary amine groups of the macrocyclic precursor L using o‐nitrobenzylbromide (L¹) and p‐nitrobenzylbromide (L²). Nitrates and perchlorates of Cu^II, Ni^II and Co^II were used to synthesize the metal complexes of both ligands and the complexes were characterized by microanalysis, MS‐FAB, conductivity measurements, IR and UV‐Vis spectroscopy and magnetic studies. The crystal structures of L¹, [CuL¹](ClO₄)₂·CH₃CN·H₂O, [CuL²](ClO₄)₂·6CH₃CN, [CuL²][Cu(NO₃)₄]·5CH₃CN·0.5CH₃OH and [NiL²](ClO₄)₂·3CH₃CN·H₂O were determined by single crystal X‐ray crystallography. These structural analysis reveal the free ligand L¹, three mononuclear endomacrocyclic complexes {[CuL¹](ClO₄)₂·CH₃CN·H₂O, [CuL²](ClO₄)₂·6CH₃CN and [NiL²](ClO₄)₂·3CH₃CN·H₂O} and one binuclear complex {[CuL²][Cu(NO₃)₄]·5CH₃CN·0.5CH₃OH} in which one of the metals is in the macrocyclic framework and the other metal is outside the ligand cavity and coordinated to four nitrate ions.     

Influence of axial ligands and anions on the Ni–Ni distances in trinickel string complexes: synthesis,structure, and properties of [Ni3(dpa)4(CH3CN)2] · (ClO4)2 · (CH3CN) · H2O

A cation–anion metal string complex with neutral axial ligands, [Ni₃(dpa)₄(CH₃CN)₂] · (ClO₄)₂ · (CH₃CN) · H₂O (1) where dpa^? is 2,2′-dipyridylamine anion, was synthesized and characterized by elemental analysis, IR, fluorescence, UV, and CV spectroscopic methods, and single crystal X-ray analysis. The Ni–Ni distances in 1 are longer than those in [Ni₃(dpa)₄(CH₃CN)₂] · (PF₆)₂ · 3.14CH₃CN (2) and [Ni₃(dpa)₄F₂] · [Ni₃(dpa)₄(H₂O)₂] · (BF₄)₂ · 2CH₃OH, indicating that the counter anions affect the Ni–Ni distances of trinickel string complexes. Compared with Ni₃(dpa)₄Cl₂ and Ni₃(dpa)₄(ClO₄)₂, 1 also has different fluorescence, UV, and CV properties. Therefore, this study clearly indicates that ligands and counter anions largely influence the structures and properties of trinickel string complexes.     

Phosphodiester hydrolysis promoted by dinuclear iron(III) complexes

We report the reactivity of three binuclear non-heme Fe(III) compounds, namely [Fe₂(bbppnol)(μ-AcO)(H₂O)₂](ClO₄)₂ (1), [Fe₂(bbppnol)(μ-AcO)₂](PF₆) (2), and [Fe₂(bbppnol)(μ-OH)(Cl)₂]·6H₂O (3), where H₃bbppnol = N,N′-bis(2-hydroxybenzyl)-N,N′-bis(2-methylpyridyl)–1,3-propanediamine-2-ol, toward the hydrolysis of bis-(2,4-dinitrophenyl)phosphate as models for phosphoesterase activity. The synthesis and characterization of the new complexes 1 and 3 was also described. The reactivity differences observed for these complexes show that the accessibility of the substrate to the reaction site is one of the key steps that determinate the hydrolysis efficiency.     

基于季戊四胺席夫碱的Ni(Ⅱ)和Cu(Ⅱ)配合物的合成、结构及其抑菌活性

以4-甲氧基水杨醛和季戊四胺进行缩合反应得到席夫碱化合物 H₄L, 然后将配体H₄L分别与Ni(ClO₄)₂·6H₂O、Cu(ClO₄)₂在乙醇溶液中进行配位反应, 得到2个席夫碱配合物[Ni₂(L)]·DMF (1)和[Cu₄(L)₂(DMSO)₃]·2DMSO (2)。并用元素分析、FT-IR和X射线单晶衍射进行了表征。配合物1和2都属于三斜晶系, P1 空间群, 配合物1和2都为双核配合物。初步研究了配体和配合物的体外抑菌活性, 结果表明, 配体及其配合物1和2对金黄色葡萄球菌具有一定的抑菌活性。     

Two linear trinuclear clusters with bridging triazole: crystal structure and magnetism

Two linear trinuclear clusters, [Co₃(L)₆(H₂O)₆](ClO₄)₆ (1) and [Ni₃(L)₆(H₂O)₆](ClO₄)₆?·?3H₂O (2) (L?=?4-(4-hydroxyphenyl)-1,2,4-triazole), obtained by the reactions of M(ClO₄)₂?·?6H₂O and 4-(4-hydroxyphenyl)-1,2,4-triazole have been isolated and structurally characterized. The two isostructural clusters, linear hexapositive trimers, are linked by three N1,N2-1,2,4-triazoles to the divalent central and terminal metal ions. The magnetic behaviors of the clusters were investigated from 1.8 to 300?K. Magnetic susceptibility measurements reveal antiferromagnetic exchange interactions between the metal centers in the clusters. The magnetic data were analyzed by using linear trinuclear modes with S?=?3/2 and S?=?1 for 1 and 2, respectively. Further studies were performed by accounting spin–orbital coupling for 1 and involving zero-field splitting within the ground state for 2.     

基于多齿希夫碱配体的四核和十核锰簇合物的合成、结构和磁性

合成了一种具有{NO₄}给电子组成的多齿水杨醛希夫碱配体,3,5-二-叔丁基水杨醛-三(羟甲基)氨基甲烷(H₄L),并利用元素分析、红外光谱以及核磁共振氢谱表征其结构。Mn(ClO₄)₂或MnCl₂·4H₂O分别与该配体在溶液中反应生成了一个四核锰簇合物[Mn^III₄(HL)₂(H₂L)₂(MeCN)₄](ClO₄)₂·2MeCN(1)和一个十核锰簇合物[Mn^III₆Mn^II₄(bz)10(L)₄(H₂O)₂]·10MeCN(2)。X-射线衍射分析表明化合物1的晶体结构空间群为三斜P1,而化合物2为正交Aba2。2~300 K温度区间的磁性测量数据表明化合物2中存在反铁磁相互作用。     

Three polynuclear complexes with bridging triazole ligand: crystal structures

Three polynuclear clusters, [Cu₄L₈](ClO₄)₄·4H₂O (1), [Zn₃L₆(H₂O)₆](ClO₄)₆·6H₂O (2), and [Mn₃L₆(CH₃OH)₆](ClO₄)₆·4.5H₂O (3) (L?=?4-(4-hydroxyphenyl)-1,2,4-triazole), obtained by the reactions of M(ClO₄)₂·6H₂O with L have been isolated and structurally characterized. Complex 1 featured a tetranuclear Cu(I) structure. Both 2 and 3 are linear hexapositive trimers linked by three N1,N2–1,2,4-triazole ligands to the divalent central and terminal metal ions. Furthermore, the luminescence properties of 2 were investigated at room temperature in the solid state.     

基于季戊四胺席夫碱的Ni(Ⅱ)和Cu(Ⅱ)配合物的合成、结构及其抑菌活性

以4-甲氧基水杨醛和季戊四胺进行缩合反应得到席夫碱化合物H_4L,然后将配体H_4L分别与Ni(Cl O_4)_2·6H_2O、Cu(Cl O_4)_2在乙醇溶液中进行配位反应,得到2个席夫碱配合物[Ni_2(L)]·DMF(1)和[Cu_4(L)_2(DMSO)_3]·2DMSO(2)。并用元素分析、FT-IR和X射线单晶衍射进行了表征。配合物1和2都属于三斜晶系,P1空间群,配合物1和2都为双核配合物。初步研究了配体和配合物的体外抑菌活性,结果表明,配体及其配合物1和2对金黄色葡萄球菌具有一定的抑菌活性。     

Three Mn(II) complexes with 1,3-bis(4-pyridyl)propane and their supramolecular nets

Three complexes, [Mn(bpp)₄(H₂O)₂](ClO₄)₂?·?1.5H₂O (1), [Mn(bpp)₃Br₂]?·?2H₂O (2), and [Mn(bpp)₂(H₂O)₂](ClO₄)?·?I?·?H₂O?·?bpp (3) (bpp?=?1,3-bis(4-pyridyl)propane), were synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is mononuclear where M(II) is coordinated to a monodentate TT-bpp, three monodentate TG-bpp, and two water molecules. Complex 2 possesses a single-stranded helical chain formed from MnN₄Br₂ octahedra by a single TT-bpp, with pendant monodentate TG-bpp ligands. Complex 3 consists of a ribbon-type double-stranded chain formed from MnN₄O₂ octahedra by double TG-bpp ligands. 2-D supramolecular architectures of 1–3 are formed by hydrogen bonds. The fluorescence of the three complexes comes from the π*–π transition of the ligand.     

Preparation,characterization, reactivities and electrochemistry of some homo- and heterodinuclear complexes of 2-hydroxy-5- methylbenzene-1,3-dicarbaldehyde and 1,3-diacetyl- 2-hydroxy-5-methylbenzene

Homo- and heterodinuclear complexes of composition [M₂L₂](ClO₄)₂·4H₂O, [CuML₂](ClO₄)₂·nH₂O (M = Ni, Co or Mn; L = L¹ or L²) and [CuML²Cl₂]·2H₂O (M = Ni or Co) have been synthesized with the dinucleating ligands 2-hydroxy-5-methyl- benzene-1,3-dicarbaldehyde (HL¹) and 1,3-diacetyl-2-hydroxy-5-methylbenzene (HL₂). These compounds have been characterized and their chemical reactivities investigated. The electrochemical behaviour of [M₂L₂²](ClO₄)₂·4H₂O and [CuML₂²](ClO₄)₂·nH₂O complexes have been examined in acetonitrile and dimethyl sulfoxide using Hg and Pt electrodes. The cyclic voltammograms obtained with a Hg electrode show quasi-reversible electron transfers for both metal centres that often get complicated due to decomplexation of metal ions and adsorption phenomena. On a Pt electrode irreversible electron transfers occur at more negative potentials.