A new cyanide-bridged bimetallic assembly [Mn（3-meosalpn）（H2O）]2[Fe（CN）5NO]（1） was obtained by the reaction of [Fe（CN）5NO]2-with [Mn（3-meosalpn）]＋,and characterized by elemental analysis,IR and single-cry...A new cyanide-bridged bimetallic assembly [Mn（3-meosalpn）（H2O）]2[Fe（CN）5NO]（1） was obtained by the reaction of [Fe（CN）5NO]2-with [Mn（3-meosalpn）]＋,and characterized by elemental analysis,IR and single-crystal X-ray structure analysis.The complex crystallizes in the monoclinic system,space group P21/c with a = 12.992（5）,b = 13.274（6）,c = 14.644（6） ,β = 115.198（4）o,V = 2285.2（16）3,Z = 2,C43H44FeMn2N10O11,Mr = 1042.61,Dc = 1.515 g/cm3,F（000） = 1072,μ = 0.928 mm-1,S = 1.052,the final R = 0.0347 and wR = 0.0957 for 17377 observed reflections（Ⅰ 〉 2σ（Ⅰ））.X-ray single-crystal diffraction analysis reveals that 1 has a trinuclear molecular structure,in which the two [Mn（3-meosalpn）（H2O）]＋ cations are linked by the central [Fe（CN）5NO]2-anion via two trans CN-groups.Furthermore,the two [Mn（3-meo-salpn）（H2O）]＋ cations and [Fe（CN）5NO]2-anion are connected into a one-dimensional zigzag chain through hydrogen bonding interactions.展开更多
Lanthanum complex supported by the heterocyclic Schiff-base ligand of N-(2-pyridyl)-3,5-di-tert-butyl-salicylaldimine was prepared and employed for the ring-opening polymerization(ROP)ofε-caprolactone(ε-CL).The poly...Lanthanum complex supported by the heterocyclic Schiff-base ligand of N-(2-pyridyl)-3,5-di-tert-butyl-salicylaldimine was prepared and employed for the ring-opening polymerization(ROP)ofε-caprolactone(ε-CL).The polymers obtained with this initiator showed a unimodal molecular weight distribution implied that only one active species was present.Mechanism study revealed that the polymerization proceeds via acyl-oxygen bond cleavage.展开更多
Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene...Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide,H_(2)L_(2)=(E)-N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide,Hdbm=dibenzoylmethane,have been constructed by adopting the solvothermal method.Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd^(3+)ions,two dbm-ions,two CH_(3)OH molecules,and two polydentate Schiff-base ligands(HL_(1)^(2-)or L_(2)^(2-)).In addition,complex 1 contains four free methanol molecules,whereas complex 2 harbors two free methanol molecules.By investigating the interactions between complexes 1 and 2 and four types of bacteria(Bacillus subtilis,Escherichia coli,Staphylococcus aureus,Candida albicans),it was found that both complexes 1 and 2 exhibited potent antibacte-rial activities.The interaction mechanisms between the ligands H_(3)L_(1),H_(2)L_(2),complexes 1 and 2,and calf thymus DNA(CT-DNA)were studied using ultraviolet-visible spectroscopy,fluorescence titration,and cyclic voltammetry.The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules,thereby inhibiting bacterial proliferation to achieve the antibacterial effects.CCDC:2401116,1;2401117,2.展开更多
Quantum density functional theory （DFT） results are reported for the building block [LaL^1（NO3）] of La complex [LaL^1（NO3）]NO3·5H2O （L^1 = （CH3）2CHCH2CH（NCHC4H3O）COO^-）. The structure was optimized an...Quantum density functional theory （DFT） results are reported for the building block [LaL^1（NO3）] of La complex [LaL^1（NO3）]NO3·5H2O （L^1 = （CH3）2CHCH2CH（NCHC4H3O）COO^-）. The structure was optimized and the calculation results show that the lanthanum ion is coordinated by one nitrogen atom and three oxygen atoms of L^1 and two oxygen atoms of nitrate ion. The bond length of La-N is 0.2637 nm and the average length of La-O is 0.2526 nm, which are consistent with the literatures. In addition, the stabilities, electronic structural characteristics and IR spectra of the complex have been analyzed, which describe the coordination of lanthanum ion with other atoms in detail.展开更多
Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal co...Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.展开更多
A novel binuclear complex （[Cu^2（μ2-shed）（hshed）].（CIO4）,H2O, h2shed = N-salicylidene-N＇-（2-hydroxyethyl）ethylenediamine） has been synthesized and structurally characterized by X-ray diffraction analysis. ...A novel binuclear complex （[Cu^2（μ2-shed）（hshed）].（CIO4）,H2O, h2shed = N-salicylidene-N＇-（2-hydroxyethyl）ethylenediamine） has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 12.511（10）, b = 15.750（12）, c = 14.281 （12） A, β = 100.564（14）°, C22H31CIN4O9Cu2, Mr = 658.04, V = 2766（4） A^3, Z = 4, Dc = 1.580 g/cm^3,μ（MoKα = 1.689 mm^-1, F（000） = 1352, the final R = 0.0528 and wR = 0.1433 for 4880 independent reflections with Rint = 0.0577. The complex is a binuclear copper compound, and two Cu（Ⅱ） ions in the binuclear cation are in different coordination environments. The Cu（1） ion adopts a distorted square pyramidal geometry （x = 0.22） with four donor atoms （N2O2） of the ligand in the basal plane, and one hydroxyl oxygen atom with protonated form occupying the apical position. The Cu（2） ion assumes the geometry of a distorted square plane with four donor atoms （N2O2） of the ligand. The Cu...Cu separation is 3.103 A,. In addition, N-H…O and C-H…O intermolecular hydrogen bonding interactions link these binuclear cations into a quasi one-dimensional chain along the a axis.展开更多
The title complex, [Mn2L2(EtOH)2 (bipy )](ClO4)2 (L=N,N'-ethylenebis (1-phenyl-3-imino-1-butanonato), bipy = 4, 4'-bipyridine] crystallizes inmonoclinic system, space group P21/c with a= 12. 63O(5), b=13- 151 ...The title complex, [Mn2L2(EtOH)2 (bipy )](ClO4)2 (L=N,N'-ethylenebis (1-phenyl-3-imino-1-butanonato), bipy = 4, 4'-bipyridine] crystallizes inmonoclinic system, space group P21/c with a= 12. 63O(5), b=13- 151 (2), c=18. 3773001 reflections The two [MnL(EtOH)]+ units are joined by one 4, 4'-bipyridine molecule to form a centrosymmetric binuclear complex cation [Mn2L2(EtOH)2 (bipy]2+. The coordination geometry around Mn atoms is a distorted octahe-dron with equatorial plane N2O2 from the Schiff base ligand L.展开更多
A hydrophobic complex of Cu2＋[bis-salicylic aldehyde-o-phenylenediamine], Cu-SPA, was prepared and used as a heterogeneous photocatalyst to degrade organic pollutants in water under visible irradiation （λ≥420 nm）...A hydrophobic complex of Cu2＋[bis-salicylic aldehyde-o-phenylenediamine], Cu-SPA, was prepared and used as a heterogeneous photocatalyst to degrade organic pollutants in water under visible irradiation （λ≥420 nm） at neutral pH. The structure of complex was characterized by using nuclear magnetic resonance （NMR）, elemental analysis, IR and UV-vis spectrometries. Degradation of Rhodamine B （RhB）, Sulforhodamine B （SRB） and Benzoic acid （BA） in water were used as model reactions to evaluate the photocatalytic activities of Cu-SPA. The results indicated that RhB and SRB were easily adsorbed on the hydrophobic surface of Cu-SPA from aqueous solution （the maximum adsorption amount： Qmax = 11.09 and 8.05 μmol/g, respectively）. Under visible irradiation, RhB and SRB were decolorized completely after 210 and 240 min, respectively, and BA was removed completely after 5 h. The efficiency of H202 was 〉 95%, in contrast to that of the reaction without catalyst or light （〈 20%）. In water soluble medium, the hydrophobic Cu-SPA can be used more than 6 cycles. ESR results and the behavior of cy- clic voltammetry showed that, in the reaction process, Cu2＋-SPA was reduced to intermediate state Cu＋-SPA firstly, which was extremely unstable and reacted rapidly with H2O2, leading to high reactive oxygen species （.OH radical ） to degrade the substrate.展开更多
A novel copper complex Cu2（L）4（1, HL = 2-ethoxy-6-（[1,2,4]triazol-4-yliminomethyl）-phenol） has been synthesized and characterized by IR, single-crystal X-ray diffraction, and elemental analysis（CHN）. The singl...A novel copper complex Cu2（L）4（1, HL = 2-ethoxy-6-（[1,2,4]triazol-4-yliminomethyl）-phenol） has been synthesized and characterized by IR, single-crystal X-ray diffraction, and elemental analysis（CHN）. The single crystal belongs to the triclinic system, space group P1 with a = 10.0991（10）, b = 10.5280（12）, c = 10.5777（11） A, α = 97.230（9）, β = 90.640（8）, γ = 92.412（9）°, Mr = 1052.05, V = 1114.6（2） A3, Z = 1, Dc = 1.567 g/cm3, F（000） = 542, μ = 1.029 mm–1, R = 0.0562 and w R = 0.1562. The fluorescence and electrochemiluminescence（ECL） of 1and HL ligand were studied. The luminescence properties of 1 can be attributed to the ligand-metal charge transfer.展开更多
A new complex [Cu2（sala）2（H20）2（4,4＇-bipy）]＇H20 （sala = N-（2-hydroxybenzyl）- D,L-alaninate, 4,4＇-bipy = 4,4＇-bipyridine） has been synthesized and characterized by elemental analysis, IR spectroscopy, the...A new complex [Cu2（sala）2（H20）2（4,4＇-bipy）]＇H20 （sala = N-（2-hydroxybenzyl）- D,L-alaninate, 4,4＇-bipy = 4,4＇-bipyridine） has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. The complex crystallizes in monoclinic system, space group C2/c with a = 42.44（3）, b = 10.416（8）, c = 15.487（13） ./k, fl = 97.455（14）°, C30H36Cu2N4O9, Mr = 723.71, V = 6789（9） A3, Dc = 1.416 g/cm3, Z = 8, F（000） = 2992, μ（MoKa） = 1.308 mm-1, R = 0.0493 and wR = 0.1004 for 4878 observed reflections （I 〉 2σ（I））. Structural analysis shows that each copper（II） atom displays a distorted square-based pyramidal coordination geometry with two oxygen atoms and one nitrogen atom from one N-（2-hydroxybenzyl）-D,L-alaninate, one nitrogen atom from 4,4＇-bipyridine ligand and one water molecule. 4,4＇-Bipyridine ligand bridges two Cu（II） ions to form a dinuclear compound. The molecular structure is extended into a one-dimensional wavy chain through hydrogen bonds. These 1D chains are further expanded into 2D networks through hydrogen bonds.展开更多
The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of...The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy_(2)(L_1)_(2)(L_(2))_(2)(CH_(3)OH)_(2)·CH_(2)Cl_(2)·CH_(3)OH(1) and Dy_(2)(L_1)_(2)(L_(3))_(2)(CH_(3)OH)_(2)·CH_(3)CN(2),where L_1,L_(2) and L_(3) represent the deprotonated form of 4-tert-butyl-2-(7-methoxybenzo[d]oxazol-2-yl)phenol,(E)-1-(((3,5-di-tert-butyI-2-hydroxyphenyI)imino)methyl)naphthalen-2-ol and(E)-2,4-di-tertbutyl-6-((2-hydroxybenzylidene)amino)phenol.The tiny difference of the core structure of 1 and 2 is derived from the steric hindrance of Schiff base ligands L_(2) and L_(3).Dynamic magnetic measurements reveal that 1 and 2 show frequency-dependent out-of-phase alternating-current susceptibility signal peaks at different temperatures under zero dc field,diagnostic of single-molecule magnet behavior.The experimental derived energy barrier to magnetization reversal for 1 and 2 is 108(1),47(2) and 33(3) K.Ab initio CASSCF calculations performed on 1 and 2 suggest that the origin of the difference in magnetic properties originates from the variation in the single-ion anisotropy that arises due to minor structural variation.Further,the equation to calculate the effective energy barrier for Dy_(2) proposed earlier is found to yield an excellent agreement with the experimental results.Solid state fluorescence measurements performed on 1 and 2 demonstrate that both exhibit two ligands centered components of fluorescent emissive,in addition,with different emitting colors and chromaticity coordinates.The discrepancy of fluorescence and single molecule magnet behavior showed by 1 and 2 can be attributed to the steric hindrance effect of Schiff base ligands.展开更多
Two novel zinc Schiff-base complexes, bis-(N-(2-hydroxybenzidene)-p-aminodimethylaniline)zinc(II) (2) and bis-(N-(2-hydroxy-1-naphthidene)-p-aminodimethylaniline)zinc(II) (4) were designed and synthesized. Both the co...Two novel zinc Schiff-base complexes, bis-(N-(2-hydroxybenzidene)-p-aminodimethylaniline)zinc(II) (2) and bis-(N-(2-hydroxy-1-naphthidene)-p-aminodimethylaniline)zinc(II) (4) were designed and synthesized. Both the complexes exhibit good solubility in organic solvents and excellent thermal stabilities. A single crystal of 2 was grown and its crystalline structure was determined from X-ray diffraction data. Analysis of the electronic structures of both the zinc complexes calculated by density functional theory reveals a localization of orbital. The UV-Vis absorption and photoluminescence profiles of 4 in thin film are similar to those of 2, but the emission for 4 is red-shifted compared to 2. Three-layered devices with a configuration of ITO/NPB/2/Alq 3 /LiF/Al and ITO/NPB/4/Alq 3 /LiF/Al show a yellow and red emission, respectively.展开更多
The nickel(Ⅱ) complex with the new ligand of S-benzyl-b-N-[10-ethyl- phenothiazine-3-methylene]dithiocarbazate(HL) crystallizes in the triclinic system, space group P?with a = 7.516(1), b = 11.322(1), c = 13.366(1) ,...The nickel(Ⅱ) complex with the new ligand of S-benzyl-b-N-[10-ethyl- phenothiazine-3-methylene]dithiocarbazate(HL) crystallizes in the triclinic system, space group P?with a = 7.516(1), b = 11.322(1), c = 13.366(1) , a = 84.818(1), b = 81.688(1), g = 76.037(1), V = 1090.26(3) 3, Z = 1, Dc = 1.413 g/cm3, F(000) = 482, m(MoKa) = 0.774 mm-1 (l = 0.7103 ?, R = 0.0573 and wR = 0.1375 for 3357 observed reflections with I ≥ 2s(I). The HL has lost a proton from its tautomeric thiol form and acts as a single negatively charged bidentate ligand coordinating to the nickel ion via the mercapto sulfur and b-nitrogen atoms. The geometry around Ni(Ⅱ) is almost square-planar with two equivalent NiN and NiS bonds. The nonlinear absorption of HL and NiL2 solutions (in DMF) was measured by open-aperture Z-scan technique at the wavelength of 532 nm.展开更多
Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other ...Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other is a novel dinuclear V(V,V)complex with an oxo bridge.The conversion between the two complexes had been discussed.展开更多
The catalyst system composed of lanthanide Schiff-base complexes with[3,5-tBu_(2)-2-(O)C_(6)H_(2)CH=NC_(6)Hs]_(3)Ln(THF)(Ln(Salen)_(3),Ln=Sc,Y,La,Nd,Sm,Gd,Yb)and triisobutyl aluminum shows high activity for n-octyloxy...The catalyst system composed of lanthanide Schiff-base complexes with[3,5-tBu_(2)-2-(O)C_(6)H_(2)CH=NC_(6)Hs]_(3)Ln(THF)(Ln(Salen)_(3),Ln=Sc,Y,La,Nd,Sm,Gd,Yb)and triisobutyl aluminum shows high activity for n-octyloxyallene(A)homopolymerization with narrow molecular weight distribution(MWD).The influences of reaction conditions on polymerization behavior are in-vestigated,and poly(n-octyloxyallene)has a weight average molecular weight(Mw)of 20.6~10^(3) with MWD of 1.39 and 100%yield is obtained under the optimum conditions:[A1]/[Y]=50 mol/mol,[A]/[Y]=100 mol/mol,with polymerization at 80℃ for 16 h in bulk.The kinetic studies of n-octyloxyallene homopolymerization indicate that the polymerization rate is first-order with respect to the monomer concentration and shows some controlled polymerization characteristics.Random co-polymer of n-octyloxyallene with styrene is obtained by using the same binary catalyst system;the reactivity ratios of the comonomer determined by Kelen-Ttld/Ss method are rA=1.20 and r_(st)=0.35,respectively,the ratio of each segment and Mw of the resulting copolymer could be controlled by varying the feed ratio of each monomer.Determined by differential scanning calorimetry,the copolymers obtained show only one glass transition temperature,which increases gradually with the increase of styrene content in the copolymer.展开更多
Four stereoisomers of a copper-(Schiff-base) complex with double chiral centers were applied to catalyze the asymmetric cyclopropanation. Two of the stereoisomers were also efficient catalysts affording high enantiom...Four stereoisomers of a copper-(Schiff-base) complex with double chiral centers were applied to catalyze the asymmetric cyclopropanation. Two of the stereoisomers were also efficient catalysts affording high enantiomeric excess of up to 91.8%. A mechanism that predicts the observed results accurately was proposed.展开更多
A complete study of the asymmetric addition of phenylacetylene to ketones catalyzed by Schiff-base amino alcohol-Zn complex is reported in this article. The Schiff-base amino alcohols were easily prepared from amino a...A complete study of the asymmetric addition of phenylacetylene to ketones catalyzed by Schiff-base amino alcohol-Zn complex is reported in this article. The Schiff-base amino alcohols were easily prepared from amino acids in three steps. When the amount of ligand was 1%（molar fraction）, an e.e. value up to 94% was obtained. A series of practical chiral ligands were applied in the enantioselective addition of phenylacetylene to ketones without adding another stronger Lewis acid except zinc.展开更多
Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(...Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.展开更多
Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'...Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.展开更多
基金supported by Industry High Technology Foundation of Jiangsu (BG2007025)Doctoral Fund from National Ministry of Education (20093227110009),China
文摘A new cyanide-bridged bimetallic assembly [Mn（3-meosalpn）（H2O）]2[Fe（CN）5NO]（1） was obtained by the reaction of [Fe（CN）5NO]2-with [Mn（3-meosalpn）]＋,and characterized by elemental analysis,IR and single-crystal X-ray structure analysis.The complex crystallizes in the monoclinic system,space group P21/c with a = 12.992（5）,b = 13.274（6）,c = 14.644（6） ,β = 115.198（4）o,V = 2285.2（16）3,Z = 2,C43H44FeMn2N10O11,Mr = 1042.61,Dc = 1.515 g/cm3,F（000） = 1072,μ = 0.928 mm-1,S = 1.052,the final R = 0.0347 and wR = 0.0957 for 17377 observed reflections（Ⅰ 〉 2σ（Ⅰ））.X-ray single-crystal diffraction analysis reveals that 1 has a trinuclear molecular structure,in which the two [Mn（3-meosalpn）（H2O）]＋ cations are linked by the central [Fe（CN）5NO]2-anion via two trans CN-groups.Furthermore,the two [Mn（3-meo-salpn）（H2O）]＋ cations and [Fe（CN）5NO]2-anion are connected into a one-dimensional zigzag chain through hydrogen bonding interactions.
文摘Lanthanum complex supported by the heterocyclic Schiff-base ligand of N-(2-pyridyl)-3,5-di-tert-butyl-salicylaldimine was prepared and employed for the ring-opening polymerization(ROP)ofε-caprolactone(ε-CL).The polymers obtained with this initiator showed a unimodal molecular weight distribution implied that only one active species was present.Mechanism study revealed that the polymerization proceeds via acyl-oxygen bond cleavage.
文摘Two Gd_(2)complexes,namely[Gd_(2)(dbm)_(2)(HL_(1))_(2)(CH_(3)OH)_(2)]·4CH_(3)OH(1)and[Gd_(2)(dbm)_(2)(L_(2))_(2)(CH_(3)OH)_(2)]·2CH_(3)OH(2),where H_(3)L_(1)=(Z)-N'-[4-(diethylamino)-2-hydroxybenzylidene]-2-hydroxyacetohydrazide,H_(2)L_(2)=(E)-N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)nicotinohydrazide,Hdbm=dibenzoylmethane,have been constructed by adopting the solvothermal method.Structural characterization unveils that both complexes 1 and 2 are constituted by two Gd^(3+)ions,two dbm-ions,two CH_(3)OH molecules,and two polydentate Schiff-base ligands(HL_(1)^(2-)or L_(2)^(2-)).In addition,complex 1 contains four free methanol molecules,whereas complex 2 harbors two free methanol molecules.By investigating the interactions between complexes 1 and 2 and four types of bacteria(Bacillus subtilis,Escherichia coli,Staphylococcus aureus,Candida albicans),it was found that both complexes 1 and 2 exhibited potent antibacte-rial activities.The interaction mechanisms between the ligands H_(3)L_(1),H_(2)L_(2),complexes 1 and 2,and calf thymus DNA(CT-DNA)were studied using ultraviolet-visible spectroscopy,fluorescence titration,and cyclic voltammetry.The results demonstrated that both complexes 1 and 2 can intercalate into CT-DNA molecules,thereby inhibiting bacterial proliferation to achieve the antibacterial effects.CCDC:2401116,1;2401117,2.
基金This work was supported by the National Natural Science Foundation of China (20203011)
文摘Quantum density functional theory （DFT） results are reported for the building block [LaL^1（NO3）] of La complex [LaL^1（NO3）]NO3·5H2O （L^1 = （CH3）2CHCH2CH（NCHC4H3O）COO^-）. The structure was optimized and the calculation results show that the lanthanum ion is coordinated by one nitrogen atom and three oxygen atoms of L^1 and two oxygen atoms of nitrate ion. The bond length of La-N is 0.2637 nm and the average length of La-O is 0.2526 nm, which are consistent with the literatures. In addition, the stabilities, electronic structural characteristics and IR spectra of the complex have been analyzed, which describe the coordination of lanthanum ion with other atoms in detail.
文摘Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.
文摘A novel binuclear complex （[Cu^2（μ2-shed）（hshed）].（CIO4）,H2O, h2shed = N-salicylidene-N＇-（2-hydroxyethyl）ethylenediamine） has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 12.511（10）, b = 15.750（12）, c = 14.281 （12） A, β = 100.564（14）°, C22H31CIN4O9Cu2, Mr = 658.04, V = 2766（4） A^3, Z = 4, Dc = 1.580 g/cm^3,μ（MoKα = 1.689 mm^-1, F（000） = 1352, the final R = 0.0528 and wR = 0.1433 for 4880 independent reflections with Rint = 0.0577. The complex is a binuclear copper compound, and two Cu（Ⅱ） ions in the binuclear cation are in different coordination environments. The Cu（1） ion adopts a distorted square pyramidal geometry （x = 0.22） with four donor atoms （N2O2） of the ligand in the basal plane, and one hydroxyl oxygen atom with protonated form occupying the apical position. The Cu（2） ion assumes the geometry of a distorted square plane with four donor atoms （N2O2） of the ligand. The Cu...Cu separation is 3.103 A,. In addition, N-H…O and C-H…O intermolecular hydrogen bonding interactions link these binuclear cations into a quasi one-dimensional chain along the a axis.
文摘The title complex, [Mn2L2(EtOH)2 (bipy )](ClO4)2 (L=N,N'-ethylenebis (1-phenyl-3-imino-1-butanonato), bipy = 4, 4'-bipyridine] crystallizes inmonoclinic system, space group P21/c with a= 12. 63O(5), b=13- 151 (2), c=18. 3773001 reflections The two [MnL(EtOH)]+ units are joined by one 4, 4'-bipyridine molecule to form a centrosymmetric binuclear complex cation [Mn2L2(EtOH)2 (bipy]2+. The coordination geometry around Mn atoms is a distorted octahe-dron with equatorial plane N2O2 from the Schiff base ligand L.
基金supported by the National Natural Science Foundation of China(21207079,21307073,21177072,21377067)
文摘A hydrophobic complex of Cu2＋[bis-salicylic aldehyde-o-phenylenediamine], Cu-SPA, was prepared and used as a heterogeneous photocatalyst to degrade organic pollutants in water under visible irradiation （λ≥420 nm） at neutral pH. The structure of complex was characterized by using nuclear magnetic resonance （NMR）, elemental analysis, IR and UV-vis spectrometries. Degradation of Rhodamine B （RhB）, Sulforhodamine B （SRB） and Benzoic acid （BA） in water were used as model reactions to evaluate the photocatalytic activities of Cu-SPA. The results indicated that RhB and SRB were easily adsorbed on the hydrophobic surface of Cu-SPA from aqueous solution （the maximum adsorption amount： Qmax = 11.09 and 8.05 μmol/g, respectively）. Under visible irradiation, RhB and SRB were decolorized completely after 210 and 240 min, respectively, and BA was removed completely after 5 h. The efficiency of H202 was 〉 95%, in contrast to that of the reaction without catalyst or light （〈 20%）. In water soluble medium, the hydrophobic Cu-SPA can be used more than 6 cycles. ESR results and the behavior of cy- clic voltammetry showed that, in the reaction process, Cu2＋-SPA was reduced to intermediate state Cu＋-SPA firstly, which was extremely unstable and reacted rapidly with H2O2, leading to high reactive oxygen species （.OH radical ） to degrade the substrate.
基金financially supported by the National Natural Science Foundation of China(No.51569008)the Natural Science Foundation of Guangxi Province(No.2015GXNSFAA139240)Program for the Scientific Research and Guangxi Scientific Experiment Center of Mining,Metallurgy and Environment(No.KH2012ZD004)
文摘A novel copper complex Cu2（L）4（1, HL = 2-ethoxy-6-（[1,2,4]triazol-4-yliminomethyl）-phenol） has been synthesized and characterized by IR, single-crystal X-ray diffraction, and elemental analysis（CHN）. The single crystal belongs to the triclinic system, space group P1 with a = 10.0991（10）, b = 10.5280（12）, c = 10.5777（11） A, α = 97.230（9）, β = 90.640（8）, γ = 92.412（9）°, Mr = 1052.05, V = 1114.6（2） A3, Z = 1, Dc = 1.567 g/cm3, F（000） = 542, μ = 1.029 mm–1, R = 0.0562 and w R = 0.1562. The fluorescence and electrochemiluminescence（ECL） of 1and HL ligand were studied. The luminescence properties of 1 can be attributed to the ligand-metal charge transfer.
基金supported by the Science and Technology Research Project of Key Laboratory of Higher Institutions of Jiangxi Province(No.GJJ10732)the Science and Technology Research Projects of the Education Department of Jiangxi Province(No.GJJ10608)+1 种基金the Research Fund of Shangrao Normal University(No.0807)Fourth point of Specialty Construction College of Education Ministry(No.TS11524)
文摘A new complex [Cu2（sala）2（H20）2（4,4＇-bipy）]＇H20 （sala = N-（2-hydroxybenzyl）- D,L-alaninate, 4,4＇-bipy = 4,4＇-bipyridine） has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. The complex crystallizes in monoclinic system, space group C2/c with a = 42.44（3）, b = 10.416（8）, c = 15.487（13） ./k, fl = 97.455（14）°, C30H36Cu2N4O9, Mr = 723.71, V = 6789（9） A3, Dc = 1.416 g/cm3, Z = 8, F（000） = 2992, μ（MoKa） = 1.308 mm-1, R = 0.0493 and wR = 0.1004 for 4878 observed reflections （I 〉 2σ（I））. Structural analysis shows that each copper（II） atom displays a distorted square-based pyramidal coordination geometry with two oxygen atoms and one nitrogen atom from one N-（2-hydroxybenzyl）-D,L-alaninate, one nitrogen atom from 4,4＇-bipyridine ligand and one water molecule. 4,4＇-Bipyridine ligand bridges two Cu（II） ions to form a dinuclear compound. The molecular structure is extended into a one-dimensional wavy chain through hydrogen bonds. These 1D chains are further expanded into 2D networks through hydrogen bonds.
基金Project supported by National Natural Science Foundation of China (21601143)Natural Science Foundation of Shaanxi Province (2021JM309)+2 种基金Open Funds of the State Key Laboratory of Rare Earth Resource of Changchun Institute of Applied Chemistry (RERU2021012)Science and Technology Innovation Team Program of Shaanxi Province (2022TD-32) and DST/SERB (CRG/2018/000430,DST/SJF/CSA03/2018-10SB/SJF/2019-20/12)。
文摘The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy_(2)(L_1)_(2)(L_(2))_(2)(CH_(3)OH)_(2)·CH_(2)Cl_(2)·CH_(3)OH(1) and Dy_(2)(L_1)_(2)(L_(3))_(2)(CH_(3)OH)_(2)·CH_(3)CN(2),where L_1,L_(2) and L_(3) represent the deprotonated form of 4-tert-butyl-2-(7-methoxybenzo[d]oxazol-2-yl)phenol,(E)-1-(((3,5-di-tert-butyI-2-hydroxyphenyI)imino)methyl)naphthalen-2-ol and(E)-2,4-di-tertbutyl-6-((2-hydroxybenzylidene)amino)phenol.The tiny difference of the core structure of 1 and 2 is derived from the steric hindrance of Schiff base ligands L_(2) and L_(3).Dynamic magnetic measurements reveal that 1 and 2 show frequency-dependent out-of-phase alternating-current susceptibility signal peaks at different temperatures under zero dc field,diagnostic of single-molecule magnet behavior.The experimental derived energy barrier to magnetization reversal for 1 and 2 is 108(1),47(2) and 33(3) K.Ab initio CASSCF calculations performed on 1 and 2 suggest that the origin of the difference in magnetic properties originates from the variation in the single-ion anisotropy that arises due to minor structural variation.Further,the equation to calculate the effective energy barrier for Dy_(2) proposed earlier is found to yield an excellent agreement with the experimental results.Solid state fluorescence measurements performed on 1 and 2 demonstrate that both exhibit two ligands centered components of fluorescent emissive,in addition,with different emitting colors and chromaticity coordinates.The discrepancy of fluorescence and single molecule magnet behavior showed by 1 and 2 can be attributed to the steric hindrance effect of Schiff base ligands.
基金supported by the National Natural Science Foundation of China(20825208,61101051,51233006,and 21021091)the National Basic Research Program of China(2011CB808403and2011CB932303)
文摘Two novel zinc Schiff-base complexes, bis-(N-(2-hydroxybenzidene)-p-aminodimethylaniline)zinc(II) (2) and bis-(N-(2-hydroxy-1-naphthidene)-p-aminodimethylaniline)zinc(II) (4) were designed and synthesized. Both the complexes exhibit good solubility in organic solvents and excellent thermal stabilities. A single crystal of 2 was grown and its crystalline structure was determined from X-ray diffraction data. Analysis of the electronic structures of both the zinc complexes calculated by density functional theory reveals a localization of orbital. The UV-Vis absorption and photoluminescence profiles of 4 in thin film are similar to those of 2, but the emission for 4 is red-shifted compared to 2. Three-layered devices with a configuration of ITO/NPB/2/Alq 3 /LiF/Al and ITO/NPB/4/Alq 3 /LiF/Al show a yellow and red emission, respectively.
基金Supported by a grant for the State Key Program of China (G1998061402) the National Natural Science Foundation of China (29871001, 20071001, and 50272001)
文摘The nickel(Ⅱ) complex with the new ligand of S-benzyl-b-N-[10-ethyl- phenothiazine-3-methylene]dithiocarbazate(HL) crystallizes in the triclinic system, space group P?with a = 7.516(1), b = 11.322(1), c = 13.366(1) , a = 84.818(1), b = 81.688(1), g = 76.037(1), V = 1090.26(3) 3, Z = 1, Dc = 1.413 g/cm3, F(000) = 482, m(MoKa) = 0.774 mm-1 (l = 0.7103 ?, R = 0.0573 and wR = 0.1375 for 3357 observed reflections with I ≥ 2s(I). The HL has lost a proton from its tautomeric thiol form and acts as a single negatively charged bidentate ligand coordinating to the nickel ion via the mercapto sulfur and b-nitrogen atoms. The geometry around Ni(Ⅱ) is almost square-planar with two equivalent NiN and NiS bonds. The nonlinear absorption of HL and NiL2 solutions (in DMF) was measured by open-aperture Z-scan technique at the wavelength of 532 nm.
文摘Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other is a novel dinuclear V(V,V)complex with an oxo bridge.The conversion between the two complexes had been discussed.
基金the financial support of the National Natural Science Foundation of China (21174121)the Special Funds for Major Basic Research Projects (G2011CB606001)Zhejiang Provincial Top Key Discipline of New Materials and Process Engineering(20110926)
文摘The catalyst system composed of lanthanide Schiff-base complexes with[3,5-tBu_(2)-2-(O)C_(6)H_(2)CH=NC_(6)Hs]_(3)Ln(THF)(Ln(Salen)_(3),Ln=Sc,Y,La,Nd,Sm,Gd,Yb)and triisobutyl aluminum shows high activity for n-octyloxyallene(A)homopolymerization with narrow molecular weight distribution(MWD).The influences of reaction conditions on polymerization behavior are in-vestigated,and poly(n-octyloxyallene)has a weight average molecular weight(Mw)of 20.6~10^(3) with MWD of 1.39 and 100%yield is obtained under the optimum conditions:[A1]/[Y]=50 mol/mol,[A]/[Y]=100 mol/mol,with polymerization at 80℃ for 16 h in bulk.The kinetic studies of n-octyloxyallene homopolymerization indicate that the polymerization rate is first-order with respect to the monomer concentration and shows some controlled polymerization characteristics.Random co-polymer of n-octyloxyallene with styrene is obtained by using the same binary catalyst system;the reactivity ratios of the comonomer determined by Kelen-Ttld/Ss method are rA=1.20 and r_(st)=0.35,respectively,the ratio of each segment and Mw of the resulting copolymer could be controlled by varying the feed ratio of each monomer.Determined by differential scanning calorimetry,the copolymers obtained show only one glass transition temperature,which increases gradually with the increase of styrene content in the copolymer.
文摘Four stereoisomers of a copper-(Schiff-base) complex with double chiral centers were applied to catalyze the asymmetric cyclopropanation. Two of the stereoisomers were also efficient catalysts affording high enantiomeric excess of up to 91.8%. A mechanism that predicts the observed results accurately was proposed.
基金the National Natural Science Foundation of China(Nos.20472026 and 20525206)Chang Jiang Scholar Program of the Ministry of Education, China.
文摘A complete study of the asymmetric addition of phenylacetylene to ketones catalyzed by Schiff-base amino alcohol-Zn complex is reported in this article. The Schiff-base amino alcohols were easily prepared from amino acids in three steps. When the amount of ligand was 1%（molar fraction）, an e.e. value up to 94% was obtained. A series of practical chiral ligands were applied in the enantioselective addition of phenylacetylene to ketones without adding another stronger Lewis acid except zinc.
文摘Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.
文摘Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.
