A New One-dimensional Chain-like Ag(I) Complex with Schiff Base Ligand Containing 4-Amino-1,2,4-triazole

The title compound,poly[N-[1-（3-pydidyl）ethylidene]-4H-1,2,4-triazol-4-amine sil-ver（I） tetrafluoroborate],[Ag（C9H9N5）（BF4）]n,is the result of complexing Ag cation with N-[1-（3-pydidyl）ethylidene]-4H-1,2,4-triazol-4-amine （L）,and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group C2/c with a= 18.899（6）,b=9.882（2）,c=15.472（4）,β=120.158（3）°,V=2498.5（11）3,C9H9AgBF4N5,Mr= 381.89,Dc=2.031 g/cm3,μ（MoKα）=1.659 mm-1,F（000）=1488,Z=8,the final R=0.0441 and wR=0.0619 for 1094 observed reflections （I 〉 2σ（I））.In the structure,ligand L bridges the two metal Ag（I） centers in a bidentate fashion and each metal ion coordinates with two nitrogen atoms,forming a one-dimensional rectangular chain.The neighboring chains are connected by two additional Ag-N weak interactions into a 3D framework structure.The title compound shows blue fluorescence property at room temperature.

Synthesis, Characterization and Antibacterial Activity of New Ln(Ⅲ) Complex with Unsymmetrical Schiff Base Ligand

A new unsymmetrical Schiff base ligand (H_2LLi) was synthesized using L-lysine, o-vanillin and salicylaladyde. Three solid metal complexes of this ligand [Ln(H_2L)(NO_3)] NO_3·2H_2O (Ln=Sm, Ho, Tm) were prepared and characterized by elemental analyses, IR spectra, UV spectra, TG-DTG and molar conductance. The ligand synthesized are chelating agent. The nitrogen atoms of Schiff base, oxygen atoms of hydroxybenzene, methoxide and carboxyl are all coordinated to the metal ions. Carboxyl and the nitrate ion within the coordination sphere are coordinated to the metal ion in a mondentate or bidentate fashion. Water molecules are lied in crystal substances. The antibacterial activity of the ligand and its complexes was also studied. The antibacterial experiments indicate that they have antibacterial activity to E. coli, S. aureus, B. subtilis and the complexes have higher activity than the ligand.

Two Cobalt(II) Complexes Derived from the Hydrolysis Product of Di-Schiff Base Ligand N,N'-Bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine:Preparation,Characterization and Crystal Structure of the 6-Coordinate Species [CoL_2]X·H_2O (X = ClO_4^-, N

The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.

Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand

Excited-state double proton transfer(ESDPT)in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol(HYDRAVH_(2))ligand was studied by the density functional theory and time-dependent density functional theory method.The analysis of frontier molecular orbitals,infrared spectra,and non-covalent interactions have crossvalidated that the asymmetric structure has an influence on the proton transfer,which makes the proton transfer ability of the two hydrogen protons different.The potential energy surfaces in both S_(0)and S_1 states were scanned with varying O-H bond lengths.The results of potential energy surface analysis adequately proved that the HYDRAVH_(2)can undergo the ESDPT process in the S_1 state and the double proton transfer process is a stepwise proton transfer mechanism.Our work can pave the way towards the design and synthesis of new molecules.

Synthesis, Spectroscopic, Structural Characterization, Conductivity and Electrochemical Studies of a Schiff Base Ligand and Its Copper Complexes

Schiff base ligand (L) derived from glyoxal and 4-aminoantipyrine was synthesized. The ligand (L) has been characterized by IR, NMR, electronic spectral studies and electrochemical studies. Cu(II) complexes of a Schiff base ligand (L) from 4-aminoantpyrine and glyoxal having the composition [CuL1]X2 where X = Cl¯?or NO3¯? have been prepared and characterized by elemental analysis, electrical conductivity in non-aqueous solvent, infrared and electronic, as well as cyclic voltammetric studies. L acts as a neutral tetradentate ligand coordinating through both the carbonyl oxygen and azomethine nitrogen. On both the complexes both the anions are not coordinated. A square planar geometry is assigned for complexes. The electrochemical studies of ligand show a typical cyclic voltammogram for an irreversible process. While copper(II) complexes show the typical cyclic voltammograms for quasi reversible process.

Synthesis, Characterization and Crystal Structure of a New Schiff Base Ligand from a Bis(Thiazoline) Template and Hydrolytic Cleavage of the Imine Bond Induced by a Co(II) Cation

The reaction of bis-[2-amino-4-pheny1-5-thiazolyl] disulfide with 5-nitro-salicylaldehyde in absolute ethanol resulted in the formation of a new Schiff base ligand H2L (1). Characterization of the ligand was performed by FT-IR, 1H NMR, 13C NMR, UV-Vis, elemental analysis and single crystal X-ray diffraction. The ligand, (1), possesses a disulfide –S–S– bridge of 2.1121 (3) ? length, and the molecule adopts a cis-conformation around this bond. In the crystal structure of (1), an intramolecular O–H···N hydrogen bond with D… A distance of 2.69 (3) ? was present. The reaction of (1) with Co(NO3)2·6H2O and CuCl2·2H2O in methanol afforded the corresponding metal complexes. The obtained solids were further investigated by elemental analysis and UV-Vis titration that confirmed the formation of [CoL] and [ClCuHL] complexes. However, recrystallizaion of the Co(II) complex in dimethylsulfoxide caused the complete hydrolysis of the imine bond and afforded a Co(II) complex in which two 5-nitro-salicylaldehyde and two DMSO molecules were coordinated to the central metal in an octahedral fashion. This structure (2) was also confirmed by single crystal X-ray analysis.

Synthesis and Thermal Decomposition Kinetics of La(Ⅲ) Complex with Unsymmetrical Schiff Base Zwitterion Ligand

A new unsymmetrical solid Schiff base (LLi) was synthesized using L-lysine, o-vanillin and 2-hydroxy-l-naphthaldehyde. Solid La(Ⅲ) complex of this ligand [LaL(NO3)](NO3)·2H2O was prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics of the complex for the second stage were studied under non-isothermal condition by TG and DTG methods. The kinetic equation may be expressed as: dα/dt=A·e-E/RT·(1-α)2. The kinetic parameters(E, A), activation entropy S≠ and activation free-energy G≠ were also gained.

A New Method of Synthesis of Azo Schiff Base Ligands with Azo and Azomethine Donors： Synthesis of N-4-Methoxybenzylidene-2-（3-hydroxyphenylazo）-5-hydroxyaniline and Its Nickel（Ⅱ） Complex

A new method for the synthesis of azo Schiff an base ligand in which the azo and azomethine groups are coordination sites was developed through a Schiff base precursor. The precursor, N-4-methoxybenzylidene-3-hydroxyphenylamine （SB） derived from 3-aminophenol was regioselectively coupled with a diazonium ion para to the hydroxyl group of the amine component of the Schiff base. The para selectivity was controlled by the directing effect of the hydroxyl group. The ligand and its nickel（Ⅱ） complex were characterized by elemental analyses, IR and UV-Vis spectroscopy. The analytical and spectral data supported the mononuclear formulation of the complex with metal to ligand ratio （M ： L = 1 ： 2） and suggested a square planar geometry for the complex.

Two 3-D Neutral Zn(Ⅱ)-MOFs Generated from the Asymmetric Schiff-base Ligand

Two new Zn（Ⅱ）-MOFs were synthesized based on an asymmetric Schiff-base ligand LH, which is obtained by the condensation of 5-formyl-8-hydroxyquinoline and 3-pyridinecar- boxylic acid hydrazide. In different mixed solvents, we get two new isomorphism compounds, [Zn（L）2]＇CaHsO2-2MeOH （1） and [Zn（L）2]＇CH2CIz＇2MeOH （2）. Compounds 1 and 2 have been characterized by single-crystal X-ray diffraction, elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P2/c, with a - 13.856（4）, b = 14.156（4）, c = 9.620（3）А, β = 110.167（5）°, V = 1771.3（9） /k3, Dc = 1.500 g/cm3, C3sH3sNsOsZn, Mr = 800.13, F（000） = 832, p（MoKa） = 0.761 mm-1, Z = 2, the final R = 0.0596 and wR = 0.1221 for 2112 observed reflections （I 〉 2σ（0）. Compound 2 belongs to monoclinic, space group P21/c, with a = 13.575（3）, b = 14.130（3）, c = 9.485（2） A, β = 107.908（3）°, V= 1731.2（6） A3, Dc = 1.529 g/cm3, CasH32C12NsO6Zn, Mr = 796.96, F（000） = 820, g（MoKa） = 0.926 mm-1, Z = 2, the final R -- 0.0527 and wR = 0.1395 for 2501 observed reflections （I 〉 2σ-（/））. The Zn（II） centers in both 1 and 2 display a distorted octahedral coordination geometry. The octahedral Zn（lI） nodes and L linkages build up 2-D nets consisting of parallelogram-like grids in the ab plane. The neighboring nets stack through hydrogen bonds to generate 3-D rhombic channels. In 1, the 1,4-dioxane and MeOH guests alternatively arrange in the channels and effectively take up the free space; while in 2, the CH2CI/guests are arranged in the channels. In addition, the encapsulated MeOH molecules are bonded to the framework by hydrogen bonds.

Construction of NIR luminescent nanoscale lanthanide complexes with new flexible Schiff base ligands

Four mono-and bi-nuclear lanthanide complexes [LnL1(No3)(H2O)DMF](Ln=Nd(1) and Yb(2)) and[Ln2(L2)2(OAc)2](Ln=Nd(3) and Yb(4)) were synthesized by using two new Schiff base ligands with long(CH2)2 NH(CH2)2 backbone.The lengths of the Schiff base ligands are about 1.8 nm.The bi-nuclear lanthanide complexes 3 and 4 have nanoscale structures with sizes of approximately 0.7 nm×1.1 nm×1.6 nm.For 3,the molar ratio of Nd:Br:O obtained by the energy dispersive X-ray spectroscopy analysis is in agreement with the crystal structure.The chromogenic Schiff base ligands in1-4 can efficiently transfer energy to lanthanide ions,thus,these complexes exhibit the typical NIR luminescence of lanthanide ions.Interestingly,3 and 4 have higher NIR emission quantum yields(Φem)than 1 and 2,respectively.

Syntheses and structures of tetranuclear Zn(Ⅱ) complexes with in situ generated macrocyclic Schiff base ligands:Applications in Zn^(2+) sensing

Three novel Zn（II） complexes,[Zn4L1Cl4]-3H2O（1）,[Zn4L2Cl4]-2DMF（2） and[Zn4L^3Cl4]H2O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ＇2 ＋ 2＇ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn^2＋ sensors have been investigated.Take H4L^1 for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn^2＋ in MeOH.

Crystal Structure of C 19 H 22 N 2O 3 and Synthesis of Two Potential Schiff base Ligands ①

Two new Schiff base compounds, as potential ligands, 3, 3’ dimethyl 4, 4’ di(acetylacetonylideneimino)biphenyl C 19 H 22 N 2O 3(1) and 3, 3’ dimethyl 4 acetylacetonylideneimino 4’ aminobiphenyl C 24 H 28 N 2O 4(2), were synthesized and characterized by elemental analyses, IR, UV and 1H NMR spectra. The crystal structure of 1 has been determined by X ray diffraction technique. The crystal is monoclinic, space group P2 1/c , with a=14.871(3), b=7.290(1), c=16.787(3) , β =106.97(3)°, V=1741(1) 3, D x =1.246 g/cm 3, Z=4, M r=326.40, λ =0 71073 , μ (Mo Kα) =0.792 cm -1 , F(000) =696. The final refinement is converged with R =0.057 and R w =0.058 for 1615 observed reflections I≥3σ(I) . The result of structure analysis indicates that atoms N(1), O(2) and O(3) are included in a conjugate system.

以Schiff base为配体的Cu(Ⅱ)-金属凝胶的制备和表征

以间苯二甲醛分别与异烟肼、烟酸酰肼和2-吡啶甲酰肼反应,合成了3种含吡啶环的Schiff base配体间苯二甲醛双缩4-吡啶甲酰腙(S1)、间苯二甲醛双缩3-吡啶甲酰腙(S2)和间苯二甲醛双缩2-吡啶甲酰腙(S3);测试了这3个化合物与醋酸铜通过配位作用在不同溶剂中形成金属凝胶的能力,结果发现,配体S1与醋酸铜在DMF/H_2O和DMSO/H_2O的混合溶剂中、配体S3与醋酸铜在DMF/H_2O的混合溶剂中均可以形成金属凝胶。胶凝测试结果表明,吡啶环上N原子位置的不同,对化合物形成金属凝胶的能力有极大影响。利用扫描电子显微镜(SEM)观察了金属凝胶的微观形貌,结果表明,配体分子的结构对金属凝胶的微观形貌也有较大影响;红外光谱和紫外可见光谱的研究证明了配位作用在金属凝胶形成过程中的推动作用;X射线衍射分析(XRD)研究表明,配体S1与醋酸铜在两种混合溶剂中形成的金属凝胶均表现出了四方堆积结构。

Schiff bases及配合物的研究进展

希夫碱配体及与后过渡金属元素所形成的配合物,以其多样的结构和广泛的用途愈来愈受到人们的重视。文章综述了Schiff base配体及配合物的发展状况以及在生物化学、催化化学、分析化学、材料化学等方面的研究与应用,并指出了它的美好前景。

A Novel Copper(Ⅱ)Complex Based on 4-Amino-1,2,4-triazole Schiff-base:Synthesis,Crystal Structure,Spectral Characterization,and Hirshfeld Surface Analysis

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.

Synthesis, Characterization and Antimicrobial Studies of Co(II), Ni(II), Cu(II) and Zn(II) Complexes of (E)-2-(4-Dimethylbenzydimino)-Glycylglycine, (Glygly-DAB) a Schiff Base Derived from 4-Dimethylaminobenzaldehyde and Glycylglycine

A tridentate Schiff base ligand, (E)-2-(4-dimethylbenzydimino) glycylglycine (glygly-DAB), derived from the condensation of 4-Dimethylaminobenzaldehyde (DAB) and glycylglycine (glygly) together with its Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized and characterized using various physico-chemical methods including C,H,N elemental analysis, melting point determination, molar conductivity measurement, IR, 1H NMR and UV-Vis. The ligand and metal complexes were screened in vitro for antimicrobial and antifungal activities on four bacterial strains (Staphylococcus aureus, Escherichia coli, Salmonella thyphi and Pseudomonas aeruginosa) and two fungal strains (Candida albicans and Cryptococcus neoformans). glygly-DAB showed remarkable antifungal activities on all the fungal strains and antibacterial activities on one bacterial strain.

Synthesis and Characterisation of Cr(III) and Co(II) Schiff Base Complexes

Co(II) and Cr(III) metal complexes of Schiff bases were synthesized from the condensation reaction between 4-(dimethylamino)benzaldehyde and 4-amino-3-hydroxy-naphthalene-1-sulfonic acid. Their structures were investigated by elemental analysis, molar conductance measurements, infrared spectroscopy, electronic spectroscopy, and 1HNMR spectroscopy. The elemental analysis data suggested a 1:1 [M:L] ratio for the complexes. The molar conductance measurements of the complexes indicate their electrolytic nature in DMSO as a solvent. The absorption bands in the electronic spectra verified an octahedral environment around the metal ions in the complexes.

Schiff-base Amino Alcohol-zinc Complex for Enantioselective Addition of Phenylacetylene to Aromatic Ketones

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.