Three novel carboxylic arylhydrazone compounds named 2- oxo propionic acid terephthalal acyl dihydrazone (1), 2-ketoglutaric acid terephthalal acyl dihydrazone (2) and 2-ketoglutaric acid salicyl- hydrazone (3) were prepared and characterized by elemental analysis, IR and 1H NMR. The antibacterial activities of 1 and 2 against wheat rust and coliform were investigated. The results showed that 1 had more excellent antibacterial properties than 2 against both wheat rust and coliform. In addition, the title compounds interaction with calf-thymus DNA (CT-DNA) were measured by fluorescence spectra method which indicating that they combined with CT-DNA by groove binding through hydrogen bonds.

以二丙酮酸缩对苯二甲双酰腙(C14H14N4O6,H4L)和稀土硝酸盐(RE(NO3)3·nH2O)为原料,在水-乙醇混合溶剂中,制备了13种二丙酮酸缩对苯二甲双酰腙稀土配合物.采用元素分析、摩尔电导率、红外光谱、紫外光谱、X-射线粉末衍射和热重分析等手段对目标产物的结构进行了表征和测试,确定出配合物的组成为RE2(H2L)3·nH2O(RE=Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Yb、Lu,n=1、2、3、4、5),推测配合物中稀土离子与配体按照2∶3的物质的量比进行配位,稀土离子的配位数为九,配合物分子中配体的化学环境相同,稀土离子的化学环境相同,配合物的外界无其它离子存在,晶格中含有一定数目的结晶水.采用孢子萌发法测试了部分配合物对小麦条锈病菌的生物活性,结果显示:配合物对小麦条锈病菌的生物活性随浓度的减小而降低,在浓度为2500 mg/L时,Nd2(H2L)3·2H2O、Dy2(H2L)3·2H2O和Y2(H2L)3·4H2O对小麦条锈病菌孢子萌发的抑制率为100％,La2(H2L)3·4H2O和Eu2(H2L)3·3H2O的抑制率分别为83.8％和84.1％,说明选取配合物Nd2(H2L)3·2H2O、Dy2(H2L)3·2H2O和Y2(H2L)3·4H2O对小麦条锈病孢子的萌发有较强的抑制作用,La2(H2L)3·4H2O和Eu2(H2L)3·3H2O的性能稍差.

A new Cu(II) complex with bi-[N-(propionic acid)] terephthalal diacythydrazon (H4L) was obtained by the reaction of CuCl2•2H2O and H4L in 1:1 pyridine and methanol. According to X-ray diffraction, the product was a binuclear complex, [Cu2L(pyridine)6]•2H2O. Each Cu(II) in the complex is six-coordinated by one N and two O atoms of H4L and three N atoms from pyridine. The coordination polyhedron around Cu(II) can be described as an octahedron with slightly distorted. Inaddition, antibacterial activities of the complex against coliform were investigated. The results showed that the inhibit rates of binuclear complex were 83% against coliform.

N-(2-(propionic acid)-salicyloyl hydrazone C10H10N2O4 center dot 2H(2)O (H3L) was synthesized by refluxing the aroylhydrazine and pyruvic acid in nonaqueous ethanol. Single crystals of H3L suitable for X-ray measurement were obtained by methanol-water (V/V = 1:1). The theoretical studies on the title compound were carried out at HF/6-31+G(d) and B3LYP/6-31+G(d) levels. The res-ults indicated that HF/6-31+G(d) gave better structural optimization data than B3LYP/6-31+G(d) method. In addition, the thermal stability had been tested by TG-DTG under a nitrogen atmosphere.

In order to study the antibacterial activity of hydrazone complexes,the ligand furan formaldehyde salicyloyl hydrazone(HL) was synthesized from methyl salicylate,hydrazine hydrate and furfural in anhydrous alcohol.Then the four rare earth complexes RE(HL)2(NO3)3(RE=Pr,Eu,Tb,Y) were synthesized by the reaction of HL and rare earth nitrate.The compositions and properties of the ligand and complexes were characterized by IR,UV,volumetric analysis,elemental analysis and molar conductance.The antibacterial activities of HL ligand and rare earth Pr(Ⅲ) complexes on Phytophthora capsici Leonian,Fusarium oxysporum,and Alternaria altemata were also studied.The results show that HL and Pr(HL)2(NO3)3 have no significant inhibition to Fusarium oxysporum(the inhibition rates70%).The inhibition rates of HL ligand on Phytophthora capsici Leonian and Alternaria altemata are 71.0% and 82.5% respectively,and Pr(HL)2(NO3)3 on Phytophthora capsici Leonian and alternaria altemata are 73.0% and 85.9% respectively.The complexes have better antibacterial activities than the corresponding ligand.

[N-(Propionic acid)] terephthalal acyl dihydrazone(H4L) was synthesized and characterized by element analysis, IR, H-1 NMR and MS. The theoretical studies on H4L were carried out at HF/6-31+G(d) and B3LYP/6-31+G(d) levels. The main decomposition stage of it was studied with IR track. The kinetic parameters[the apparent activation energy(E-a) and pre-exponential constant(A) of the first and second stages of decomposition reaction] were obtained by Kissinger and Ozawa's methods. Furthermore, the antimicrobial activity of H4L against wheat rust was investigated by spore sprout method.

The reaction of Zn(Ac)2·2H2O with N-(2-propionic acid)-salicyloyl hydrazone, a tridentate ligand (C10H10N2O4, H3L), and imidazole (C3H4N2), a monodentate ligand, in MeOH:H2O = 3:1 (V/V) yields [Zn(HL)(C3H4N2)(H2O)]. The crystal structure has been determined by X-ray diffraction. In the compound, it crystallizes with two independent molecules in the unit and the two molecules are linked by an intermolecular hydrogen bond and one short contact. Zn is five-coordinated by one tridentate hydrazone ligand, one imidazole, and one water molecule. The coordination polyhedron around Zn(II) described as a distorted square-pyramid. In addition, antibacterial activities of the complex against coliform were investigated by turbidimetry/spectrometry.

A series of transition metal complexes of the general formula M(HL)2 (where H2L=2′-(4-dimethylaminobenzylidene)-2-hydroxybenzoylhydrazide, M=Ni, Cu, Zn, Cd) were prepared and characterized by elemental analysis, spectroscopic (IR, UV–vis) and the Ni(HL)2 was structurally characterized by X-ray crystallography. Single-crystal X-ray diffraction results suggest that Ni(II) central atom situated in a distorted square planar geometry is four-coordinated. The DNA-binding properties of these complexes with calf thymus DNA were also investigated by electronic absorption titration (UV spectroscopy) and fluorescence emission titration. The results showed that these complexes bind to DNA mainly via intercalative mode.

A new series of complexes of transition metal (Cu, Zn, Ni) perchlorate with imidazole have been synthesized and characterized by elemental analysis, infrared (IR), UV-Vis spectroscopy, and single-crystal X-ray diffraction. Based on elemental and spectral data, the complexes are M(C3H4N2)(x)(ClO4)(2) (M = Cu, Zn, x = 4; M Ni, x = 6; C3H4N2 = imidazole). The crystal structures of Cu(C3H4N2)(4)(ClO4)(2) (1) and Zn(C3H4N2)(4)(ClO4)(2) (2) show metals surrounded by four nitrogens of imidazole, while the nickel complex Ni(C3H4N2)(6)(ClO4)(2) (3) has six nitrogens of imidazole. Intra-and inter-molecular hydrogen bonds exist between hydrogen of imidazole and oxygen of perchlorate. The thermal stabilities of 1, 2, and 3 at different heating rates (beta = 5 degrees Cmin(-1), 10 degrees Cmin(-1), and 15 degrees Cmin(-1)) show that all the complexes exhibit two thermal decomposition stages; the sequence of thermal stability is 2 > 1 > 3. 1, 2, 3, and imidazole display DNA binding ability, ascertained by UV-Vis titration.

Two complexes, [Cd-2(Im)(HL)(2)(CH3OH)(3)(H2O)(2)] (1) and [Ni(HL)(Im)(2)(H2O)]center dot[Ni(H2L)(Im)(2)(OH)]center dot 4H(2)O (2) (H3L = N-(2-propionic acid)-salicyloyl hydrazone, Im imidazole), have been synthesized and characterized by infrared and single-crystal X-ray diffraction. The bioactivity of 1 was studied by the turbidimetry/spectrometry method and DNA-binding properties of 2 were studied. The result showed that the inhibitory rate of 1 was very good and 2 binds to calf-thymus DNA by the groove-binding mode.

A novel binuclear praseodymium(III) complex with N-(2-propionyl)salicyloylhydrazone (C10H10N2O4, H3L) and p-hydroxybenzoic acid (C7H6O3, Phba) was prepared in a H2O-C2H5OH mixed solution, and the crystal structure of [Pr2(H2L)2(Phba)4(H2O)2] · 2H2O (I) was determined by X-ray single crystal diffractometry. Complex I crystallizes in the monoclinic system, space group P21/c, a = 1.1050(4), b = 1.9534(7), c = 1.2376(4) Å, β = 94.955(7)°, and Z = 4. In the structure each Pr3+ ion lies in a single capped square antiprism geometry coordinated by carboxyl O and acyl O atoms and azomethine N atom of one ligand (H2L− form), which coordinates via the keto form, four carboxyl O atoms from two Phba, and O atoms of two water molecules. In each molecule, two tridentate ligands were coordinated by the H2L− form, and each Pr3+ ion was chelated by the carboxyl group from Phba. The carboxyl groups of H2L− and other two Phba were coordinated via μ2-bridging form and bidentate bridging form, respectively. Complex I and ligands Phba and H3L were also searched for biological activity against Valsa mali by the growth rate method. The result showed that the inhibitory rate of ligands Phba and H3L is better than complex I, especially Phba.

A novel cadmium(II) complex with N-(2-acetic acid)salicyloyl hydrazone (C 9 H 8 N 2 O 4 , H 3 L) and imidazole (Im) was prepared and characterized. The crystal structures of ligand H 3 L and cadmium(II) complex were determined by X-ray single-crystal diffractometry. The complex consists of three binuclear neutral unattached units. One of Cd 2+ is six-coordinated by the carboxylic O atom, acylic O atom, and azomethinic N atom of one ligand H 3 L (HL 2− form), carboxylic O atom from the other ligand H 3 L by the μ 2 -bridging form and N atoms from two imidazoles, but the other five Cd 2+ ions all are seven-coordinated more than an O atom from coordinated water molecule compared with six-coordinated Cd 2+ . HL 2− acts as tridentate ligand forming two stable five-numbered rings and sharing one side in the keto form for each ligand, and the carboxyl groups of two HL 2− ligands are coordinated via the μ 2 -bridging form. The coordination polyhedron around Cd 2+ was described as a octahedron or pentagonal bipyramidal. The inter- and intramolecular hydrogen bonds resulted in a three- dimensional network and provided extrastability for the structure. The complex exhibits good fluorescence properties. The complex was also searched for the interaction with CT-DNA by electronic absorption titration and emission titration. The results show that the complex is bound to calf thymus DNA mainly by intercalation.

A novel erbium (III) complex, [Er(H 2 L)(HL)(H 2 O)] 2 [Er(HL)(H 2 O) 4 (OH)]· (H 2 O) 3 , (H 3 L, being a aroylhydrazone ligand N-(2-propionic acid)-salicyloyl hydrazone) has been synthesized and the crystal structure has been determined by X-ray crystallography. The complex crystallizes in triclinic system, space group P-1 with unit cell parameters a = 7.735(3)Å, b = 14.734(5) Å, c = 17.957(7) Å, α = 101.984(6)°, β = 97.990(6)°, γ = 90.420(6)°, V = 1981.1(12) Å 3 and Z = 2. Single-crystal X-ray diffraction results suggest that the ligands have two different coordination styles in the crystalline state. It crystallizes with two independent molecules in the complex. Each erbium(III) atom is eight-coordinate and has a distorted dodecahedron geometry. Fluorescence property of the complex has been tested with an excitation wavelength 300 nm at room temperature.

Aim To study the complex crystal structure of La(III) and N-(2-propionic acid)-salicyloyl hydrazone and to test bioactivity of the complex.Methods The crystal is obtained by solvent pervasion method,the structure is determined by single crystal X-ray diffraction analysis,bioactivity is tested by potted plant method.Results The complex is a novelty binuclear single crystal.The crystal complex crystallizes in the triclinic system with space group P-1,and parameters a=0.908 19(19) nm,b=1.233 2(3) nm,c=1.325 1 nm,α=104.157(4)°,β=99.312(4)°,γ=108.911(3)°,Z=2,R1=0.040 1,wR2=0.106 2,GOF=1.016.The complex can excellently inhibit Puccinia striiformis Westendrop and Pseudoperonospora cubensis and also can advance crop′s upgrowth.Conclusion The new complex crystal of La(Ⅲ) and N-(2-propionic acid)-salicyloyl hydrazone adds new contents for coordination chemistry and bioinorganic chemistry.The well bioactivity of the complex affords an applied foundation on the agriculture.

Aim To study the complex crystal structure of La (Ⅲ) and N-(2-propionic acid)-salicyloyl hydrazone and to test bioactivity of the complex- Methods The crystal is obtained by solvent pervasion method, the structure is determined by single crystal X-ray diffraction analysis, bioactivity is tested by potted plant method. Results The complex is a novelty binuclear single crystal. The crystal complex crystallizes in the triclinic system with space group P-1, and parameters α=0.90819 (19) nm, b=1.2332 (3) nm, c=1.3251 nm, α=104.157(4)˚, β=99.312(4) ˚, γ=108.911(3)˚, Z=2, R1=0.0401, wR2=0.1062, GOF=1.016. The complex can excellently inhibit Puccinia striiformis Westendrop and Pseudoperonospora cubensis and also can advance crop's upgrowth. Conclusion The new complex crystal of La (Ⅲ) and N-(2-propionic acid)-salicyloyl hydrazone adds new contents for coordination chemistry and bioinorganic chemistry. The well bioactivity of the complex affords an applied foundation on the agriculture.

Complex 1 [Pr-2(H2L)(2)(HL)(2)(2,6-H(2)PDA)(H2O)(2)]center dot 2H(2)O and complex 2 [Eu-2(H2L)(2)(HL)(2)(2,6-H(2)PDA)(H2O)(2)]center dot 2H(2)O were obtained by reactions of N-(2-propionle acid)-salicyloyl hydrazone (C10H10N2O4, H3L), 2,6-pyridinedicarboxylic acid (2,6-H(2)PDA) and RE(NO3)(3)center dot nH(2)O (RE=Pr, Eu) at room temperature, and characterized by elemental analyses, IR, UV, and single crystal X-ray diffractometry. In addition, the DNA binding properties of the two complexes were Studied by means of UV absorption spectrum, emission spectroscopic spectrum, steady-state emission quenching and DNA competitive binding with ethidium bromide (EB). The results indicated that the two complexes bound to calf-thymus DNA in an intercalative mode.