Two Cd(Ⅱ) and Cu(Ⅱ) Complexes Based on 1-Butylbenzimidazole: Crystal Structures and Weak Interactions

1-Butylbenzimidazole L reacted with Cd(NO3)2·4H2O to afford complex [CdL(NO3)3H2O]·[HL] 1. The heptacoordinated Cd(Ⅱ) center adopts a distorted pentagongal bipyramidal geometry, and complex [CdL(NO3)3H2O]-entity and the protonated benzimidazium salt [HL]+ are connected via N-H···O hydrogen bond to form a dimeric unit [CdL(NO3)3H2O]·[HL]. A 3-D supramolecular network of 1 is formed through N-H···O and O-H···O hydrogen bonds together with π-π stacking interactions. Reaction of L with CuCl2 afforded a mononuclear complex, [CuL2Cl2] 2, in which the tetracoordinated Cu(II) center adopts a distorted tetrahedral geometry. In contrast, 2-D supramolecular layers of 2 are formed by C-H···Cl hydrogen bonds. The fluorescent emission spectra of L, 1 and 2 are described.     

Studies of the Intramolecular Aromatic-ring Stacking Interactions in the Ternary Platinum(Ⅱ) Complexes

The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA) , where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.     

Synthesis and Properties of u-Oxamido Heterobinuclear Cu(Ⅱ)-Co(Ⅱ) Complexes

Three heterobinuclear complexes were synthesized, namely [Cu (oxpn) Co (L)2] (ClO4)2·xH2O(L= 2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen) , and 5-nitro-1, 10-phenanthroline (NO2-phen)), where oxpn represents N, N'-bis(3-aminopropyl) oxam-ido. Based on 1R, elemental analysis, conductivity measurement and electronic spectra, these complexes were characterized by an extended oxamido-bridged structure with Cu(Ⅱ) in a planar environment and Co(Ⅱ) in a octahedral environment. The symmetry of the cation is very close to C2v.The complexes were also characterized with variable temperature (4~300K) magnetic susceptibility, and the data were fit for the susceptibility equation derived from spin Hamilton, H= -2JS1.S2-DSx12 by least square strategy. The exchange integral, J, was found to be -22.36 cm-1 (for bpy);-15.45 cm-1 (for phen); -19. 10cm-1(for NO2-phen), indicating that there is a weak antiferromagnetic spin-exchange interaction between the metal ions.     

Synthesis and Crystal Structure of Cobalt(Ⅱ) and Copper(Ⅱ) Complexes Involving L-Aamino Alcohols

Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co(Ⅱ) acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu(Ⅱ) chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I: [Co3(C51H66N3O16)]2(OAc), monoclinic, space group P21, a = 15.022(3), b = 14.242(3), c = 28.922(6) , β = 98.944(4)o, V = 6112(2) 3, Z = 4, Dc = 1.339 g/cm3, the final R = 0.0860 for 21906 observed reflections with I 2(I). For Ⅱ: Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861(13), b = 20.838(4), c = 28.274(6) , V = 3644.6(13) 3, Z = 4, Dc = 1.310 g/cm3, the final R = 0.0642 for 11106 observed reflections with I 2(I). The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.     

Synthesis and Magnetic Studies of Oxamido-Bridged Cu(Ⅱ)-Fe(Ⅱ) Heterobinuclear Complexes

~The~andmagneti~Of~~areatoPicthahasndchinndinndnd.bondinthewiin-wtofbinudearCU(n)-Fe(u)-,chewedwiththe~alleq-nettrioftwnew~-,[CU(oxa)Fe(L)21sa(Lbo1,1o-~(Phen)nd5-nithe1'1o-~(NQ-Phen)),whereOxaisN,N'-bis(2-amhathy).edfor.-Synboor(1)ToCh(oxae)2(94.2mp'o.4ed)theindri(5nd)wasbo-lyadtalaedboofso.Wio(111.2mp,o.4nuno)inmeto(1ond)ndaboofPhen(144-2mp,o.8mrnO)inrne~(1OrnL)underN2atrmpe.theedfor2hthegreddebm~thuSfo~wereforoff,washededtimeswithrne~anddiethyletheranddriedoverP2QUnderededpe.ha:C,…     

Crystal Structures of Cu(Ⅰ) and Cu(Ⅱ) Complexes of Tris(N-n-propylbenzimidazol-2-ylmethyl)amine

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Halogen Mediated Self-assembly of Three Mixed Valent Cu(Ⅰ)/Cu(Ⅱ) Complexes

Reaction of the ligand dmpt(dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline)with CuCl_2 afforded mixed valent Cu(Ⅰ)/Cu(Ⅱ) discrete tetranuclear complexes[Cu(Ⅱ)Cl_2(dmpt)Cu(Ⅰ)Cl](1),while the reaction of ligand dppz(dppz = dipyrido[3,2-a:20,30-c]phenazine) with divalent halogen copper salt CuX_2(X=Cl,Br) gave one-dimensional chain mixed valent Cu(Ⅰ)/Cu(Ⅱ) complexes [Cu(Ⅱ)Cl_2(dppz)Cu(Ⅰ)Cl]_n(2) and discrete mixed valent Cu(Ⅰ)/Cu(Ⅱ)complexes [Cu(Ⅱ)Br_2(dppz)(DMF)Cu(Ⅰ)Br](3). Complex 2 consists of a one-dimensional chain-dppzC u(Ⅱ)-Clμ_2-Cu(Ⅰ)-Cl-dppzC u(Ⅱ)-Clμ_2-Cu(Ⅰ)-with Cu(Ⅱ) and Cu(Ⅰ) atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu(Ⅰ) and Cu(Ⅱ). The Cu(Ⅰ) ion presents a pseudo-trihedral geometry,while the Cu(Ⅱ) ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.     

Synthesis and Properties of Dinuclear Cu( Ⅱ ) Complexes Derived from Oxamidobis(propionato)cuprate( Ⅱ )

Three dinuclear complexes were synthesized and designated as Cu(obp)CuL where obp =oxamidobis(propionato), L=2,2' -bipyridyl(bpy) (1), 1 , 10-phenathroline(phen)(2) and 5-nitro-1, 10-phenathroline(NO2-phen)(3). The complexes were characterized by elemental analyses, in fared and electronic spectra, magnetic susceptibilities and ESR spectra, indicating antiferromagnetic spin exchange interactions between metal ions.     

Syntheses and Crystal Structures of Mono-and Binuclear Copper(Ⅱ) Mixed-ligand Complexes Involving Schiff Base

1 INTRODUCTION The chemistry of copper compounds has been extensively investigated and the relationship be- tween structure and reactivity, ranging from indus- trial catalysis to biochemistry activity, is of major importance. For binuclear copper(II) complexes equa- torially bridged by pair of hydroxide[1] or alkoxide[2, 3] groups, satisfactory linear correlation is found be- tween the Cu–O–Cu bridging angle and spin coupling between the metal centers. However, for binuclear copper(I…     

Variance of Solid-state Pt···Pt Interactions in Luminescent Cyclometalated Cationic Pt(Ⅱ)-isocyanide Complexes

Polymorphic structures of cyclometalated cationic Pt(Ⅱ)-isocyanide complexes(–)-1 [Pt((-)-NNC)(Dmpi)]Cl with different packing modes can be isolated before. In this paper, a series of solid-state powders with variable colors(yellow, orange and red) have been obtained from the evaporation of complex(–)-1 in different solvents. The crystallinity, thermogravimetric properties, absorption, luminescence and excited state lifetimes have been studied. In addition, intermolecular Pt···Pt interactions in the optimized configurations of different aggregates have been explored, and calculations of frontier molecular orbitals of monomer, dimer, trimer and tetramer have been carried out.     

Anion Directed Assembly of Cu(Ⅱ) Complexes Formed by a Flexible Ligand

Coordination polymers,consisting of metal,anion and organic ligands,have attracted much attention.The structure of coordination polymers is affected by various factors.To investigate the effects of anion,syntheses and structures of four Cu(II)complexes,namely[(Cu LCl_2)(PF_6)]_n(1),[(Cu LCl_2)(ClO_4)]_n(2),[(Cu LCl_3)?CH_3OH]_n(3)and Cu LCl_3(4),are reported based on a flexible ligand,1,3-bis(2-pyridylmethyl)imidazolium(L).The ligand is accommodative to kinds of anions,and forms 1-D chains generally upon reaction with Cu(II)salts.The effect is measured by the conformational variation through the dihedral angles between different aromatic rings of the ligand.In order to further investigate the effect of anion,a protonated sample of L,namely,LH(ClO_4)_2?H_2O(5)is also synthesized and structurally characterized,showing an intriguing hydrogen bonded helix.     

Carbon–Fluorine Reductive Elimination from Nickel(III) Complexes

We report a C−F reductive elimination from a characterized first-row aryl metal fluoride complex. Reductive elimination from the presented nickel(III) complexes is faster than C−F bond formation from any other characterized aryl metal fluoride complex.     

Crystal Structures and DNA Binding Properties of 2-Naphthoxyacetic Acid Cu(Ⅱ) Complexes

Two new copper complexes based on 2-naphthoxyacetic acid ligand, namely [Cu(L)_2(CH_3CN)]_2(1) and [Cu(L)(1,10-phen)_2](2), where L = 2-naphthoxyacetic acid and 1,10-phen = 1,10-phenanthroline, were obtained by hydrothermal reaction and characterized by single-crystal X-ray diffraction. The binuclear complex 1 and mononuclear complex 2 belong to space group C2/c and P■, respectively. The binding properties of the two compounds with ct-DNA were investigated by UV-Vis and fluorescence spectra. The two compounds could bind with ct-DNA through interactions. Compound 2 displays stronger binding ability in the reaction with ct-DNA.     

Crystal Structures and Characterizations of Bis(pyrrolidinedithiocarbamato)Cu（Ⅱ） and Zn(Ⅱ） Complexes

The structures of [Cu (S₂CN (CH₂)₄)₂] (1) and [Zn₂(S₂CN‐(CH₂)₄)₄] (2) have been determined by X‐ray crystallography analysis. They are all isomorphous and triclinic, space group of P1^?, with Z = 1. The lattice parameters of compound 1 is: a = 0.63483(2) nm, b = 0.74972(3) nm, c=0.78390(1) mn, α = 75.912(2)°, β = 78.634(2)° and γ = 86.845(2)°; compound 2: a = 0.78707(6) nm, b=0.79823(6) nm, c = 1.23246(9) nm, α = 74.813(2)°, β = 73.048(2)° and γ = 88.036(2)°. The copper atom is located on a crystallographic inversion center and zinc atom lies across centers of symmetry. The Cu(II) ion has a square‐planar geometry while Zn(II) has a distorted tetrahedral geometry. The thermal gravity (TG) data indicate that no structural transitions in the two compounds were abserved and the decomposition products can adsorb gas. Also they all have a high thermal stability.     

Studies of the Intramolecular Aromatic-ring Stacking Interactions in the Ternary Platinum（Ⅱ） Complexes

The stability constants of some ternary mixed-ligand complexes, Pt (Phen)(CA) , where Phen-1,10-phenanthroline and CA^-=carboxylate, were determined by means of potentiometric pH titration in aqueous solutions (I=0. 1mol/L, KNO3; 25℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands (PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen) (PCA)^- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.     

Spectroelectrochemical Studies on the Interactions of Complexes of Cu(phen)_2~(2 ) and Cu(bpy)_2~(2 ) with DNA

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