Syntheses, Crystal Structures and Theoretical Calculation of Two Transition Metal Dinuclear Complexes

Two transition metal dinuclear complexes of [Mn2（OOCC6H4SSC6H4COO）- （Phen）2（H20）]n 1 and [CuE（OOCC6H4S）2（Phen）2] 2 were hydrothermally synthesized by the reaction of equivalent metal dichloride with 2,2＇-dithiobis（benzoic acid） （HE-DTBB）. Structure analysis indicates that each Mn2＋ ion in I is coordinated by one chelate phen ligand, one bridging water molecule and three DTBB ligands forming Mn2＋ dinuclear units which are further linked into one-dimensional chain by DTBB ligand. Under similar reaction conditions, the 2,2＇-dithio- his（benzoic acid） ligand undergoes thiol reduction to form 2-mercaptobenzoic （H-2-MBA） in 2 where two Cu2＋ ions are coordinated by phen and MBA ligands only constructing a dinuclear unit.     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

Hybrid Tungstocuprate [ Cu（2,2＇-bpy）3]2 H4 [ CuW12O40 ]· 6H2O Based on Keggin Polyoxoanion [CuW12O40]^6- with Cu^Ⅱ as Heteroatom

A novel hybrid tungstocuprate （ Ⅱ ） [ Cu （2,2＇-bpy） 3 ] 2 H4 [ CuW12O40 ] · 6H2O （ 2,2＇-bpy = 2,2＇-bipyfidine） was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [ CuW12O40 ]^6- and a pair of chiral complex cations [ Cu（2,2＇-bpy） 3 ]^＋ together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [ Cu （2,2＇-bpy）3 ]^＋v/a multiple C-H…O hydrogen bonds resulting in a dimer.     

Crystal Structures and Theoretical Calculation of Zn（Ⅱ） and Cu（Ⅱ） Supramolecular Complexes Based on Macrocyclic Triamine Ligand 1,4,7-Triazacyclodecane （tacd）

Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.     

A Diphenoxo-bridged Ferromagnetic Copper（Ⅱ） Dimer Based on N-（2-Hydroxybenzyl）salicylaldimine

A new dinuclear copper（Ⅱ） complex, [Cu（L）（py）]2 1 （H2L = N-（2-hydroxybenzyl）- salicylaldimine, py = pyridine）, has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes in space group P2 1/n with a = 8.2106, b = 10.715, c = 17.864A, β = 99.365°, V = 1550.7A3, Z = 4, C19H16CuN2O2, Mr = 367.88, Dc = 1.576 g/cm3,μ（MoKα） = 1.422 mm-1, F（000） = 756, the final R = 0.0280 and wR = 0.0746. Complex 1 is a centrosymmetric dimer with two copper（H） centers, two py ligands and two L2- ligands. Each L2- ligand donates its azomethine nitrogen and one of the phenolate groups to one copper（Ⅱ） ion and shares the other phenolate group between the two copper（H） ions, affording a Cu2O2 plane. Each copper（Ⅱ） center has a slightly distorted square pyramidal geometry with a bridging phenolate group at the apex. Magnetic studies suggest the presence of a weak ferromagnetic interaction Via two phenoxo bridges. The magnetic susceptibility data （2-300 K） of complex 1 were analyzed by means of H = -2JS1S2 -DSz. The least-squares fitting of the data to the theoretical equation leads to J = 10.3 cm-1, g = 2.03, D = 0.67 cm-1 and R = ∑（Xobsd -Xcalcd）2/∑Xobsd2= 2.76 × 10^-3.     

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex Based on a Carboxyl-substituted 1H-1,2,3-Triazole and Its DNA Cleavage Activity

The novel dinuclear copper complex [Cu2(H2O)2(DMF)2(L)2](1, H2 L = 5-phenyl-2H-1,2,3-triazole-4-carboxylic acid, DMF = N,N-dimethyl-formamide) has been synthesized and characterized by X-ray single-crystal diffraction. The compound crystallizes in triclinic system, space group P1 with a = 9.591, b = 10.508, c = 15.515 ?, β = 75.11°, V = 1446.2 ?3, Z = 2, Mr = 683.62, Dc = 1.570 g/cm3, μ = 1.531 mm-1, F(000) = 700, the final R = 0.0404 and w R = 0.1130 for 5327 observed reflections with I 2σ(I). In each unit of the complex, two Cu2+ ions coordinated with two triazole ligands to form a dimeric [5,6,5] tricyclic structure. The central Cu atom is five-coordinated, and each copper atom shows a square pyramidal geometry. The crystal structure is stabilized by the inversion-related O–H···O hydrogen bond and C–H···O hydrogen bonding interactions to form a layer structure. Fluorescent spectra show an obvious quenching of fluorescence compared with free 1,2,3-triazole ligand. The results of agarose gel electrophoresis indicate that this complex can cleave the plasmid supercoiled DNA within shorter time in the 50-folds excess of ascorbate under physiological conditions, providing a new example in the research for artificial metal nucleic acid enzyme.     

Macro-, Micro-, Nano- and Crystal Structures of a Homodinuclear Complex [NH3（ CH2）3NH3]2{Na2[（C6H4O2）2]（C6H4O2H）2}

A homodinuclear complex （NH3CH2CH2CH2NH3）2 {Na2[（C6H4O2）2] （C6H4O2H）2} （1） has been synthesized by a solution-based self-assembly route. It crystallized in monoclinic system with space group P21/c. Every sodium ion coordinates in a tetragonal prism fashion with two O atoms of a terminal chelating catecholate ligand and three O atoms from two bridging catecholate ligands. Two neighboring NaO5 tetragonal prisms are edge-shared and centrosymmetric with regard to the inversion center to form a binuclear cluster {Na2[（C6H4O2）2]（C6H4OOH）2}^4- anion. The complex anions were aligned parallelly by n-n interaction and linked with the protonated 1,3-propylenediamine through hydrogen bonds which were assembled into a multi-lamellar structure with channels. The crystal exhibits rectangular geometry with an interior triangle hollow structure under optical microscopy. And the scanning electron microscopy （SEM） indicates that the wall of the tubes shows multi-lamella morphologies. Further, the transmission electron microscopy （TEM） reveals that the crystal is composed of multi-lamellar nano-tubes with diameters less than 100 nm. The molecular structure of the complex was compared with that of its isomer complex 2.     

硫酰杯[4]芳烃与铜(II)双核配合物的合成与晶体结构

The X-ray crystallographic structure was reported for a dinuclear copper（Ⅱ） complex with a tetraanionic ligand of p-tert-butylsulfonylcalix[4]arene [Cu2L（CH3OH）6]·4CH3OH （H4L=p-tert-butylsuffonylcalix[4]arene）. The complex belongs to triclinic system, P1^-- space group, with a = 1.2303（3） nm, b = 1.2377（3） nm, c = 1.3110（3） nm, a =66.862（4）°, β= 67.206（4）°, γ=61.711（3）°, Z= 1, V= 1.5659（7） nm^3, Dc= 1.371 g/cm^3, F（000） = 682,μ（Mo Kα） = 0.883 mm^-1, R1 =0.0325, wR2=0.0870. In this complex, the calix[4]arene acts as a bis-tridentate chelating ligand with the 1,2-alternate conformation.     

One-Pot Hydrothermal Synthesis of Two New Copper（Ⅱ） Complexes with 4-Carboxyphenoxy Acetic Acid

The one-pot hydrothermal reaction of CuCl2 with H2CPOA and 4,4＇-bpy results in two new coordination polymers, [Cu（CPOA）（4,4＇-bpy）（H2O）2]·1.5H2O （1） and [Cu2（HCPOA）4（4,4＇-bpy）4] （2） （H2CPOA=4-carboxyphenoxy acetic acid, 4,4＇-bpy=4,4＇-bipyridine） since CPOA^2- anions reach equilibrium with HCPOA^- anions in the reaction system. The crystal structure of 1 shows a triple interpenetration CdSO4-like net with 1D channel, in which lattice water molecules are located. Complex 2 is a ladder-like 1D double chain structure assembled through coordination bonds and O—H…N hydrogen bonds.     

1-D Open-channeled 3-D Supramolecular Frameworks Built with 2,3-Dihydroxybutanedioic Acid （H4dhbd） and 2,2＇：6＇,2＇＇-Terpyridine （tpy）

The complex [Cu2（H2dhbd）2（tpy）2]·CH3OH·4H2O 1 （H4dhbd =2,3-dihydroxybutanedioic acid, tpy = 2,2＇：6＇,2＇＇-terpyridine） has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space groups Pi with a= 8.6859（17）, b = 11.223（2）, c = 12.275（2）A, α = 112.454（3）, β= 98.435（3）, γ = 105.593（3）°, V= 1022.5（3） A^3, Z = 1, C38H42Cu2N6O18, Mr = 997.86, Dc = 1.621 g/cm^3, μ= 1.127 mm^-1, F（000） = 514, T = 293（2） K, the final R = 0.0539 and wR = 0.1394 for 3550 observed reflections with I 〉 2σ（I）. In the dinuclear unit, two Cun atoms are bridged by two H2dhbd chelate anions, forming a 14-membered ring, in which the distance of Cu…Cu atoms is 7.0526（12）A. Adjacent dinuclear units are constituted through π-π interactions and C-H…O hydrogen-bonding interactions, fashioning the final 3-D supramolecular framework with 1-D open channels. Variable-temperature magnetic susceptibility measurement indicates the presence of weak antiferromagnetic exchange interactions between Cu^II ions.     

Synthesis,Structure, and Magnetic Properties of a Copper(II) Metal‐Organic Framework with Biphenyl‐2,2′,4,4′‐tetracarboxylic Acid

The 2D Cu^II metal‐organic framework [Cu₂(bptc)(H₂O)₄]_n · 4nH₂O ( 1 ) (H₄bptc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid) was hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and magnetic measurements. In the structure, bptc^4– serves as a twisted Π‐shaped organic building block to connect paddlewheel [Cu₂(COO)₄] dinuclear units and mononuclear units through 2‐/2′‐carboxylate and 4‐/4′‐carboxylate, respectively. According to the magnetic analysis using a dimer‐plus‐monomer model, strong antiferromagnetic coupling is operative within the dinuclear unit (J = –311 cm^–1 based on H = –J S ₁ S ₂), and the compound behaves like a mononuclear molecule at low temperature.     

Assembly of a Novel Dumbbell‐type Dinuclear Copper(II) Complex: Synthesis,Structure and Properties

A new dumbbell‐type 4,4′‐bipy‐bridged dinuclear copper(II) complex, [Cu₂(4,4′‐bipy)L₂(H₂O)₂](ClO₄)₄ · 8CH₃OH · 10H₂O, where L = 1‐[bis(3‐aminopropyl)amino]‐2‐ propanol and bipy = bipyridine, has been synthesized and characterized, X‐ray crystallographic analysis shows that the [Cu₂(4,4′‐bipy)L₂(H₂O)₂]⁴⁺ cations and water molecules generate layer structures extending parallel to bc planes through hydrogen bonding interactions of O–H ··· O and C–H ··· O. The layers are also connected by hydrogen bonding interactions involving methanol, water, and perchlorate anions. These interactions lead to the formation of rectangular channels of 12.3 Å × 6.0 Å along the crystallographic c axis. Perchlorate anions fill in each channel in a sandwich‐like packing mode, they are joined with the adjacent layers by water heptamers. Magnetic susceptibility measurements show that the magnetic exchange interaction is weak although it has a regular π‐type electron transfer pathway. Furthermore, the electrochemical and thermogravimetric properties of the complex were also investigated.     

A Homochiral Metal‐Dipeptide Supramolecular Framework Including a Hydrogen‐bonded Guest Network of Water and Uncoordinated 4, 4′‐Bipyridine

Abstract. The self‐assembly of glycyl‐L ‐leucine, Cu(NO₃)₂ · 3H₂O and 4, 4′‐bipyridine resulted in the tetranuclear‐based metal‐dipeptide supramolecular framework [Cu₄(C₈H₁₄N₂O₃)₄(H₂O)₂(C₁₀H₈N₂)₂] · (C₁₀H₈N₂) · 13H₂O ( 1 ). In the structure, the 4, 4′‐bipyridine‐bridged tetranuclear complex of Cu^II‐glycyl‐L ‐leucine interacts with each other to form a 1D hydrogen‐bonded chain including uncoordinated 4, 4′‐bipyridine and an interesting water chain in different channels. Under similar reaction conditions, racemic glycyl‐D ,L ‐leucine gave rise to the centrosymmetric dinuclear complex [Cu₂(C₈H₁₄N₂O₃)₂(C₁₀H₈N₂)] · 2H₂O ( 2 ), which is linked into a 2D hydrogen‐bonded structure without 4, 4′‐bipyridine included.     

Synthesis and Characterization of Three Diverse Coordination Frameworks under Co-ligand Intervention

The chelating organic ligands of 2,2’-bipyridine (2,2’-bipy), di(pyrid-2-yl)amine (dpa) and 2,6-di(pyrid-2-ylamino)pyridine (dpap) were respectively applied to react with H2fum (fumaric acid) and copper salts, affording three different complexes [Cu2(fum)(2,2’-bipy)4]•2ClO4 (1), [Cu2(µ-OH)2(fum)(dpa)2]•2H2O (2) and [Cu(SO4)(H2O)(dpap)]•H2O (3). These complexes were determined by single-crystal X-ray diffraction. Each penta-coordinated Cu(II) ion exhibits a distorted trigonal bipyramidal geometry in 1. The fum ligand links copper ions to form a dinuclear copper unit. While in 2, the fum ligands connect [Cu2(µ-OH)2(dpa)2] unit to construct a 1D zigzag chain. Unexpectedly, when dpap instead of dpa was used under the same conditions, only one mononuclear complex 3 was formed. Crystal packings show that 1—3 form 3D supramolecular architectures through non-covalent interactions (multiple hydrogen bonds and C—H…π/π-π interactions). In addition, the study of the magnetic property reveals dominating ferromagnetic interactions between Cu(II) atoms in 1.     

New CuII and CdII Metal‐organic Coordination Polymers with 1,2,4‐triazolo[3,4‐b]‐1,3,4‐thiadiazole Ligands: Syntheses,Structures and Luminescent Properties

Three new complexes {[Cu( L¹ )₂(NO₃)₂]?H₂O}_oo ( 1 ), {[Cu₄( L² )₂(OAc)₈]‐CH₃CH₂OH}_oo ( 2 ) and [Cd₂( L³ )₃(NO₃)₄(H₂O)₂]_oo ( 3 ) ( L¹= 4‐phenyl‐7‐(pyridine‐3‐yl)‐1,2,4‐triazolo[3,4‐b]‐1,3,4‐thiadiazole, L²= 4‐(pyridine‐3‐yl)‐7‐phenyl‐1,2,4‐triazolo[3,4‐b]‐1,3,4‐thiadiazole, and L³= 4‐(pyridine‐4‐yl)‐7‐phenyl‐1,2,4‐triazolo[3,4‐b]‐1,3,4‐thiadiazole) have been synthesized and characterized by elemental analyses, IR spectra and single crystal X‐ray diffraction. The structural analyses reveal that complex 1 is a neutral 2‐D network structure with a 4⁴ topology, 2 has a 1‐D neutral coordination chain with a [Cu₂(CH₃COO)₄] dinuclear structural unit bridged by four acetate ions, and 3 is a neutral rhombohedral grid structure. All the complexes are air stable at room temperature. Furthermore, the fluorescent properties of complex 3 and corresponding ligand L³ have been investigated and discussed.     

Formation of a Dimer of Trinuclear Helicates which Encapsulates an Array of Six Hydrogen‐Bonded Anions

The amine‐containing ligand L, composed of two bidentate pyridyl‐thiazole moieties linked by a 1,3‐diaminophenylene unit, reacts with copper(II) ions to form a dinuclear double helicate [Cu₂L₂]⁴⁺. Reaction of [Cu₂L₂]⁴⁺ with dihydrogen phosphate (0.5 equivalents) gives the unsaturated dinuclear double helicate [Cu₂L₂(OPO₃H₂)]³⁺. [Cu₂L₂(OPO₃H₂)]³⁺ further reacts with another 0.5 equivalents of dihydrogen phosphate to give a trinuclear circular helicate which then self‐assembles into a hexameric cluster [{Cu₃L₃(OPO₃H₂)₃}]²⁶⁺.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Synthetic and Structural Studies on Copper 1 H‐[1,10]‐Phenanthrolin‐2‐one Coordination Complexes: Isolation of a Novel Intermediate During 1,10‐Phenanthroline Hydroxylation

The synthesis and crystal structure elucidation of a novel dinuclear heteroleptic copper(II) complex has led to an alternative mechanism in the formation of covalent hydrates. During further studies on the synthesis and properties of [Cu₂(ophen)₂] ( 1 ), a dinuclear complex of copper(I) with 1 H‐[1,10]‐phenanthrolin‐2‐one (Hophen), two intermediates/alternative products 2 and 3 were isolated. The dinuclear, antiferromagnetic complex [Cu₂(ophen)₂(phen)₂] ? (NO₃)₂ ? 9H₂O ( 3 , phen=1,10‐phenanthroline) contains two five‐coordinate copper(II) ions, both with trigonal‐bipyramidal coordination, which are bridged together through deprotonated hydroxyl groups with a Cu? Cu non‐bonding distance of 3.100 Å. Complex [Cu(phen)₂(H₂O)] ? (NO₃)₂ ( 2 ) is a polymorph of a previously reported material. The occurrence of 2 and 3 has led us to propose a variation to the Gillard mechanism for the formation of covalent hydrates in bidentate N‐heterocycles in which the attacking nucleophile may be the deprotonated form of 2 , [Cu(phen)₂(OH)]^?, rather than free OH^?.     

Syntheses, Supramolecular Structures and Antibacterial Activities of Five Helical Transition Complexes with 5-Chloro-1-phenyl-1H-pyrazole-3,4-dicarboxylic Acid

Five new transition metal complexes [Cu(HL)₂(H₂O)₂] ( 1 ), [Cu(HL)₂(phen)] ( 2 ), [Cu(HL)₂(H₂O)]₂(4,4′‐bipy) ( 3 ), [Zn(HL)₂(H₂O)₂]·(4,4′‐bipy) ( 4 ), [Ag(HL)(4,4′‐bipy)]_n ( 5 ), (H₂L=5‐chloro‐1‐phenyl‐1H‐pyrazole‐3,4‐dicarboxylic acid, phen=1,10‐phenanthroline; 4,4′‐bipy=4,4′‐bipyridine) have been synthesized and characterized. Complexes 1 , 2 and 4 exhibit monomeric structures, 3 shows a dinuclear structure, 5 displays 1D chain structure, and all extend to 3D supramolecular network via rich hydrogen bonds. Complexes 1 , 2 , 3 , 5 comprise single helical chains, while complex 4 generates quadruple‐stranded helical chains. Furthermore, the antibacterial activities of the titled complexes against bacterial species, three Gram positive bacteria (Staphylococcus aureus, Bacillus subtilis and Candida albicans) and two Gram negative bacteria (Escherichia coli and Pseudomonas aeruginosa) were studied and compared to the activities of free ligands by using the microdilution method.     

Synthesis,Crystal Structure,Thermal Stability,Magnetic Property,and Biological Activity of a New Copper(II) Complex Based on 1,2,4‐Benzenetricarboxylic Acid and 2,2′‐Bipyridine

Based on an asymmetric 1,2,4‐benzenetricarboxylic acid (H₃btc) and 2,2′‐bipyridine (bpy), a new Cu^II complex, Cu₂(H₂btc)₄(bpy)₂ · 8H₂O ( 1 ), was synthesized and structurally characterized by single‐crystal X‐ray diffraction, hirshfeld surface (HS) analysis, IR spectroscopy, powder X‐ray analysis, thermal gravimetry analysis (TGA), magnetic susceptibility, EPR measurement, and UV/Vis spectrometry. Complex 1 shows a dinuclear copper structure. The Cu^II of each dinuclear moiety are in a slightly distorted square‐pyramidal environments. Magnetic susceptibility of 1 shows a ferromagnetic coupling between both metal atoms. The interaction of 1 with bovine serum albumin (BSA) is investigated using UV/Vis, fluorescence spectroscopic methods. The Cu^II complex shows strong binding propensity in albumin binding study.