Flexible and Asymmetric Ligand in Constructing Coordinated Complexes: Synthesis,Crystal Structures and Fluorescent Characterization

Flexible and asymmetric ligand L [L = 1-((pyridin-3-yl)methyl)-1H-benzotriazole], is used as a basic backbone to construct complicated metal-organic frameworks. Two new polymers, namely, [Ag₂(L)₂(NO₃)₂]_n (1) and [Ag(L)(ClO₄)]_n (2), were synthesized and characterized by X-ray structure analysis and fluorescent spectroscopy. The complex 1 gives an “S” type double helical conformation, whereas complex 2 exhibits a 1D zigzag configuration. Different anions affect the silver coordination geometry and crystal packing topology.     

Different coordination modes of a tripod phosphine in gold(i) and silver(i) complexes

The following gold(I) and silver(I) complexes of the tritertiary phosphine 1,1,1- tris(diphenylphosphinomethyl)ethane, tripod , have been synthesised: Au(3)(tripod)X(3) [X = Cl(1), Br(2), I(3)]; [Au(3)(tripod)(2)Cl(2)]Cl (4); Au(tripod)X [X = Br(5), I(6)]; Ag(3)(tripod) (NO(3))(4) (7), Ag(tripod)NO(3) (8). They were characterized by X-ray diffraction (complexes 2, 3 and 4), (31)P NMR spectroscopy, electrospray and FAB mass spectrometry and infrared spectroscopy. Complexes 2 and 3 show a linear coordination geometry for Au(I), with relatively short Au-P bond distances. Complex 3 has a Au***Au intramolecular distance of 3.326 A degrees , while complex 2 had a short Au***Au intermolecular interaction of 3.048 A degrees . Complexes 4-6 were found by (31)P NMR spectroscopy studies to contain a mixture of species in solution, one of which crystallised as [Au(3)(tripod|)(2)Cl(2)]Cl which was shown by X-ray diffraction to contain both tetrahedral and linear Au(I), the first example of a Au(I) complex containing such a mixture of geometries. The reaction of [Au(3) (tripod)Cl(3)] (1) with tripod led successfully to the formation of [Au(3)(tripod|)(2)Cl(2)](+) and [Au(3)(tripod)(2)Cl(3)](+) and [Au(3)(tripod|)(3)Cl](2+). The silver(I) complexes, 7 and 8 appear to contain linear and tetrahedral Ag(I), respectively.     

Exploration of Intermolecular Interaction of One Silver(I) Polymer with Bis(pyrazolyl)methane Derivative: Experimental Observations,Hirshfeld Surface Analyses and Fluorescent Properties

In the superbasic medium DMSO-KOH, bis(3,3-diethoxycarbonyl-1-pyrazolyl)methane (L) was synthesized. Besides, the single crystal of L has been obtained. Meanwhile, one novel coordination polymers, [Ag(L)(NO₃)] _n (1) was successfully prepared. The single X-ray diffraction data reveal that L crystallized in the P-1 space group. Novel bis(pyrazolyl)methane derivative ligand, L acts as multidentate ligands to coordinate with Ag ion to form a six-membered boat conformation. And furthermore the nitrate groups bridge each Ag(I) to construct a zigzag chain. The fluorescent properties of the complex were examined in solution and compared with the ligand. In order to investigate the intermolecular interactions, we also studied Hirshfeld surface analysis of ligand and the complex. The Hirshfeld surface analysis reveals that the main intermolecular interactions are H···H and O···H/H···O interactions which comprise 23.9 and 33.8 % of the total Hirshfeld surface area.     

Ag(I)(Et(2)PCH(2)CH(2)PPh(2))(2)]NO(3): An Antimitochondrial Silver Complex

The silver(I) complex [Ag(eppe)(2)]NO(3) (eppe = Et(2)PCH(2)CH(2)PPh(2)) is shown by X-ray crystallography to be tetrahedral with Ag - PEt(2) and Ag - P Ph(2) bond lengths of 2.482 and 2.518 A, respectively. The complex is selectively antimitochondrial and inhibits the growth of a number of yeast strains in non-fermentable media at concentrations as low as 2.5 muMu and induces the mitochondrial mutation petite The effect is largely reversed by the presence of aspirin. The complex is shown to be stable in the cell culture media and in the presence of glutathione, but readily reacts with disulfides of oxidized glutathione and serum albumin. Surprisingly, neither [Au(eppe)(2)]Cl nor [Au(eppe)(2)]Cl (dppe = Ph(2)PCH(2)CH(2)PPh(2)) showed any mitochondrial selectivity in the same screening protocol.     

Synthesis, Characterisation and Antifungal Activities of Some New Copper(II) Complexes of Isomeric 3,5,7,7,10,12,14,14-Octamethyl-1,4,8,11-Tetraazacyclotetradecanes

Three isomeric Me(8)[14]anes, L(A), L(B) and L(C), undergo complexation with copper(II) salts to form a series of [CuLX(n)(H(2)O)(x)]X(y).(H(2)O)(z) complexes where L = L(A), L(B) and L(C); X = Cl, Br, NO(3); n, x, y and z may have values of 0, 1 or 2. The complexes have been characterised on the basis of analytical, spectroscopic, magnetic and conductance data. Further, the X-ray crystal structure of one complex, [CuL(B)(OH(2))(2)](NO(3))(2), has been determined. The antifungal activity of all three isomeric ligands and their complexes has been investigated against a range of phytopathogenic fungi.     

Synthesis, Characterisation and Anti-Fungal Activities of Some New Copper(II) Complexes of Octamethyl Tetraaza-Cyclotetradecadiene

The ligand Me(8)[14]diene, L, in its free state as well as in the dihydroperchlorate form, L.2HClO(4), coordinates copper(ll) in different salts to yield a series of [CuLX(x)] X(y)(H(2)O)(z) complexes where X = NO(3), ClO(4), NCS, Cl and Br; x and y may have values of 0 or 2 and z = 0, 1 or 2. The complex, [CuL(ClO(4))(2)].2H(2)O is found to undergo axial ligand substitution reactions with SCN(-), NO(3) and Cl(-) to give a variety of substitution derivatives: [CuL(ClO(4))(m) X(n)] where X = NCS, NO(3) and Cl; m = 0 or 1, and n = 1 or 2. The complexes .have been characterised on the basis of analytical, spectroscopic, magnetic and conductance data. The anti-fungal activities of the ligand and its complexes have been investigated against a range of phytopathogenic fungi.     

一维链状磺酸银配合物[Ag_2(2-Pyr)(H_2O)_4]L_2的合成与晶体结构

由Ag2CO3、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=1.999g/cm3,R1=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。     

Redox and catalytic properties of new polypyrrole modified electrodes functionalized by [Ru(bpea)(bpy)H2O] complexes; bpea=N,N′-bis(2-pyridylmethyl)ethylamine, bpy=2,2′-bipyridine

New ruthenium(II) complexes containing one or two pyrrole-functionalized polypyridylic ligands have been prepared in order to study their electrochemical behaviour in heterogeneous phase, after anodic polymerization from CH₂Cl₂ solution on an electrode surface. Complexes containing one pyrrole unit have general formula [Ru(bpea-pyr)(bpy)(L)]²⁺ (bpea-pyr=N-[3-bis(2-pyridylmethyl)aminopropyl]pyrrole, bpy=2,2′-bipyridine, L=Cl, complex 3, or L=H₂O, complex 1), whereas compounds having two pyrrole units correspond to [Ru(bpea-pyr)(bpy-pyr)(L)]²⁺ (bpy-pyr=4-methyl-4′-pyrrolylbutyl-2,2′-bipyridine, L=Cl, complex 4, or L=H₂O, complex 2). Upon oxidative polymerization, all complexes form highly stable polypyrrolic films on a graphite disk electrode surface. An electrode modified with complex 2 polypyrrole coating film, C/poly-2, has been tested as heterogeneous catalyst for the oxidation of benzyl alcohol, showing a remarkably high efficiency and notably improving the results obtained with analogous complexes in homogeneous phase.     

Synthesis, characterization and crystal structure of a novel thiocyanate–ruthenium(II) complex

The cis-[Ru(dppb)(Me-bipy)(NCS)₂], dppb = 1,4-bis (diphenylphosphino)butane, Me-bipy = 4,4′-dimethyl-2,2′-bipyridine, and NCS = thiocyanate, was synthesized and characterized by spectroscopic and electrochemical techniques and its structure was determined by crystal X-ray analysis. The crystal structure reveals that the coordination geometry around the Ru(II) center is distorted octahedron where two molecules of thiocyanate are bonded to the ruthenium through nitrogen atom in cis orientation. The half-wave formal potential value E_1/2 = 0.8 V (versus Ag/AgCl) observed is considerable higher than that for the cis-[RuCl₂(dppb)(Me-bipy)] complex, E_1/2 = 0.6 V (versus Ag/AgCl), well illustrating the strong π-acceptor effect the NCS ligand toward the backbonding interaction with the Ru(II) metal center. The MLCT absorption bands of the thiocyanate complex present a higher molar absorptivity (about 12%) compared with the cis-[RuCl₂(dppb)(Me-bipy)] complex, in the same experimental conditions. These properties make the complex potentially promising for the photosensitization process.     

Three Ag(I)–cyanide coordination polymers with metal bonds tuned by N-heterocyclic ligands

Hydrothermal reactions of AgNO₃, K₃[Fe(CN)₆] with N-heterocyclic ligands afforded three novel Ag(I)–cyanide coordination polymers, [Ag₂(CN)₂(tpt)]_n (1), {[Ag(CN)(bpe)_0.5][Ag(CN)]}_n (2) and [Ag(CN)(btmb)_0.5]_n (3) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine, bpe = 1,2-bis(4-pyridyl)ethane, btmb = 1,2-bis(1,2,4-triazol-1-ylmethyl)benzene). In complex 1, two Ag(CN) linear chains are bridged by bidentate tpt ligand to form a ladder-like structure, which are further connected by AgAg metal bond to generate a 2D polymeric network. Complex 2 is an interesting 3D supramolecular architecture assembled by 2D [Ag¹(CN)(bpe)_0.5]_n network and linear [Ag²(CN)]_n chain combined by strong AgAg metal bond. Complex 3 is a 1D ladder-like double-chain polymer constructed from Ag–cyanide linear chains and btmb spacer, which is further extended to a 2D supramolecular network by Ag–Ag weak interaction. The Ag–Ag metal interactions play important roles in the construction of three coordination polymers. Complexes 1 and 2 are respectively thermally stable at 300 and 180 °C. Complexes 1 and 3 emit strong blue luminescence.     

水杨醛缩对氯苯胺Co(Ⅱ)配合物的合成、表征及其荧光性质研究

以水杨醛和对氯苯胺为原料合成了水杨醛缩对氯苯胺(HL),将其作为主要配体与1,4-对苯二酚以及氯化钴(CoCl2·6H2O)反应生成了Co(Ⅱ)的配合物[Co(C6H4O2)(L)2]n,用元素分析、红外吸收光谱、紫外可见吸收光谱对其结构进行了表征,并通过荧光光谱对配体、配合物荧光发光性质进行了研究。结果表明,配体水杨...     

Synthesis and Structural Characterization of Two New Nano-Coordination Compounds Based on Mercury(II) NN Donor Schiff Base

Two new nano mercury(II) coordination compounds, [Hg₂(μ-L1)(μ-I)₂I₃]_n (1) and [Hg(L2)(I)₂] (2) {L1?=?(E)-N′-(pyridin-2-ylmethylene)isonicotinohydrazide and L2?=?(E)-N′-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide} have been synthesized by a sonochemical method. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, elemental analysis and IR spectroscopy. The compounds were also characterized by single crystal X-ray diffraction and the results indicate a 1D fishbone-like structure containing dinuclear units for 1 and a mononuclear structure for 2. In coordination polymer 1, the two Hg(II) centers are four coordinate into a chain-axis and also in the terminal linkages. In complex 2, the Hg(II) center is four coordinate. The chains of polymer 1 interact with each other through π–π stacking interactions which create a 3D framework.     

Silver(I)-mediated isomerisation of trans-[RuCl2(P-P)2] (P-P=4-membered ring chelate diphosphine ligand) and its application in the syntheses of [RuCl(L)(P-P)2]+ (L=neutral ligand)

Conversion of trans-[RuCl₂(P-P)₂] (P-P=4-membered chelate diphosphine) to cis is facilitated by treatment with AgOTf or AgBF₄ in 1,2-dichloroethane, which gives mixtures of Ru–Cl–Ag heterobimetallic complexes with cis stereochemistry at Ru(II), characterised by ³¹P{¹H} and ¹H NMR spectroscopy and by FAB mass spectrometry. Treatment of these mixtures with neutral ligands (CO, CH₃CN) gives cis-[RuCl(L)(P-P)₂]⁺, whereas simultaneous treatment of trans-[RuCl₂(P-P)₂] with L and Ag(I) salt gives trans-[RuCl(L)(P-P)₂]⁺.     

Supramolecular Architectures in Three Metal(II) Coordination Polymers with 2,5-Dichloroterephthalate and Flexible Bis(Benzimidazole) Ligands

Three supramolecular coordination polymers, namely [Ni(L1)(DCTP)(H₂O)] _n (1), [Cu(L2)(DCTP)] _n (2), [Co(L3)(DCTP)] _n (3) (L1?=?1,5-bis(5,6-dimethylbenzimidazole)pentane, L2?=?1,4-bis(5,6-dimethylbenzimidazole)butane, L3?=?1,4-bis(benzimidazole)-2-butylene) have been hydrothermally synthesized and characterized by single crystal X-ray structure determination, FT-IR, elemental analysis, X-ray powder diffraction (XPD), and thermogravimetric analysis (TGA). CP 1 exhibits 2D 6³ honeycombed network structure, which is further extended into a 3D Moganite (mog) supramolecular framework by classical O–H?O hydrogen-bonding interaction. CPs 2 –3 present 2D (4,4) layers, and 3D supramolecular frameworks that are formed by π–π stacking interactions. Furthermore, the catalytic activities of CPs 1–3 for the degradation of methyl orange in a Fenton-like process has been investigated, and CPs 1–3 show strong photoluminescence properties at room temperature in solid state.     

Surface decorated platinum carbonyl clusters

Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt(13)(CO)(12){Cd(5)(μ-Br)(5)Br(2)(dmf)(3)}(2)](2-) (1), [Pt(19)(CO)(17){Cd(5)(μ-Br)(5)Br(3)(Me(2)CO)(2)}{Cd(5)(μ-Br)(5)Br(Me(2)CO)(4)}](2-) (2), [H(2)Pt(26)(CO)(20)(CdBr)(12)](8-) (3) and [H(4)Pt(26)(CO)(20)(CdBr)(12)(PtBr)(x)](6-) (4) (x = 0-2), have been obtained from the reactions between [Pt(3n)(CO)(6n)](2-) (n = 2-6) and CdBr(2)·H(2)O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt(26)Cd(12) metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.     

Two New Ternary Cd(II) Coordination Polymers Containing Bis(thiabendazole) Ligands as Luminescent Sensors for Benzaldehyde and MnO4− Anions

Journal of Inorganic and Organometallic Polymers and Materials - Two new ternary Cd(II) coordination polymers (CPs), [Cd2(L)(mip)2·2H2O]n (1) and {[Cd2(L)(hip)2]·3.5H2O}n (2)...     

Synthesis and characterization of palladium (II) complex of Schiff base ligand: CS bond cleavage and catalytic activity

Reaction of ligand, L-CH₂Ph with Pd(CH₃CN)₂Cl₂ in acetonitrile in presence of PPh₃ and subsequent addition of NaClO₄ yielded Pd(II) complex, [Pd(L)(PPh₃)](ClO₄) 1 due to the SC (CH₂Ph) bond cleavage during complexation. Complex 1 was characterized by spectral analysis and the structure was authenticated by single crystal X-ray diffraction. The diffraction analysis revealed that the monoanionic ligand binds with palladium (II) in (N, N, S) fashion in a distorted square planar geometry where the fourth position is occupied by one tri phenyl phosphine group. One ClO₄⁻ ion satisfies the charge of the former aggregate, [Pd(L)(PPh₃)]⁺. The complex [Pd(L)(PPh₃)](ClO₄), 1 exhibits a very good catalytic activity towards CC bond formation.     

Oxotungsten(VI) complexes with amino(phenolate)alcoholate ligand

The reaction between tungsten(VI) complex [W(eg)₃] (eg = 1,2-ethanediolato dianion) and a phenolic ligand precursor 2,4-di-tert-butyl-6-(((2-hydroxyethyl)(methyl)amino)methyl)phenol (H₂L) affords a monomeric oxotungsten complex [WO(eg)(L)]. This complex reacts further with Me₃SiCl, which leads to the displacement of ethanediolato ligand from the complex unit and formation of cis- and trans-isomers of corresponding dichloro complex [WOCl₂(L)]. Identical dichloro complexes were also prepared by the reaction between H₂L and WOCl₄. Molecular structure of [WO(eg)(L)] was verified by X-ray crystallography.     

Cu(Ⅱ)配合物的制备、结构多样性及超氧化物歧化酶活性

To construct superoxide dismutase (SOD) mimetics, three Cu(Ⅱ) coordination polymers (CPs), [Cu3(L1)4(OH)2(H2O)2]n (CP 1), [Cu(L2)(OH)]n (CP 2) and [Cu(L2)(CH3O)]n (CP 3), in which n is a positive integer, are synthesized by solvothermal method using nicotinate N-oxide (HL1) or isonicotinate N-oxide (HL2) as organic ligands and Cu(OAc)2·H2O as metal salt. Their structures and properties are characterized by single crystal X-ray diffraction, X-ray powder diffraction, infrared spectroscopy, elemental analysis, thermogravimetric analysis and ultraviolet spectroscopy. CPs 1~3 are synthesized under similar solvothermal conditions, but show a multi-dimensional configurations from one-dimensional, two-dimensional to three-dimensional, respectively, exploring the possible mechanisms of the relative position of functional groups in ligand, the coordination mode of ligand and the solvent system on the structural diversity of CPs. Thermogravimetric analysis shows that CPs 1~3 can be stabilized up to 202, 228, and 250 ℃, respectively, which display good thermal stability, and the higher the dimension of CPs 1~3, the better the thermal stability. Nitrotetrazolium blue chloride (NBT) photoreduction test shows that the semi-inhibitory concentration values (IC50) of CPs 1~3 are 0.21, 0.26 and 0.62 μmol/L, respectively, which display certain SOD activity, and the lower the dimension of CPs 1~3, the better the SOD activity. The lower IC50 of CP 1 and CP 2 indicating that they can be used as potential SOD mimetics.     

Synthesis, Crystal Structures and Luminescent Properties of pH-Dependent Zn (II) Coordination Polymers

Two new coordination polymers [Zn(L)(bib)] _n (1) and [Zn(L)(bib)_0.5] _n (2) [L = 5-hydroxyisophthalic acid and bib = 1,4-bis(2-methyl-imidazol-1-yl)butane] have been synthesized and characterized. X-ray single crystal diffractions show that complex 1 is a 2D layered structure and complex 2 is a 3D 6-connected topological net. Complex 1 are further assembled into a 3D supramolecular structure by intermolecular hydrogen bonding. Complex 2 features a two-fold interpenetrated pcu topology. Moreover, the fluorescent properties of complexes 1 and 2 were studied in the solid state at room temperature.