Synthesis and Structure of a Ladder-like Co-crystal Cu~ICl with 3,5-Dipropyl-4-amino-1,2,4-triazole

Redox reaction of a mixture of CuCl2·2H2O, H3PO3 and dpatrz(3,5-dipropyl-4-amino-1,2,4-triazole) at room temperature yields one new compound, [Cu(Ⅰ)(μ2-dpatrz)2Cu(Ⅰ)Cl2], with two independent cis- and trans-propyl side chain molecules. Compound 1 crystallizes in monoclinic, space group P21/c with a = 7.474(1), b = 17.807(1), c = 18.851(1) , β = 108.32(1)o, V = 2381.7(2) 3, Z = 4, C16H32Cl2Cu2N8, Mr = 534.48, Dc = 1.491 g·cm-3, μ = 2.03 mm-1, F(000) = 1104, GOOF = 1.050, the final R = 0.0445 and w R = 0.1162 for 3162 observed reflections(Ⅰ 2δ(Ⅰ)). Compound 1 shows discrete dimeric structures(A and B) containing inversion centers and the Cu(Ⅰ) ions are coordinated in triangle geometries. The isomers are connected by N–H···Cl hydrogen bonds, chains with graph-set C(7) and rings R22(14) and C–H···π interactions into stair-step chains(Tapes A and B) running parallel to the [01–1] direction. The N–H···Cl hydrogen bonds result in chain and cyclic structures with graph-sets C22(17) and R34(18) linking tapes A and B to form two-dimensional networks along the [031] direction. Packing of crystal 1 is stabilized by rings R34(18) and weak C–H···Cl hydrogen bonds parallel to the [01–2] direction. Bond valence sum(BVS) and UV-Vis absorption spectra support the existence of Cu(Ⅰ) ions. Compound 1 exhibits extensive green blue phosphorescence in the solid state at room temperature.     

邻氨基酚Schiff碱钴、镍双核配合物:合成、结构和抗癌活性及量化计算

分别采用水热法和溶剂挥发法合成了一个五配位的钴双核配合物[Co2(H_2O)2(L1)2(4,4′-bipy)](1)和一个镍双核配合物[Ni2(L2)2(4,4′-bipy)](2)(H2L1=邻氨基酚缩5-溴水杨醛,H2L2=邻氨基酚缩水杨醛),并经红外光谱和紫外光谱以及热重分析进行了表征。X射线单晶衍射分析表明1的晶体结构属三斜晶系P1空间群;2属于三方晶系R3空间群。采用MTT法初步研究了配体和配合物的体外抗癌活性,结果表明,1和2对人肝肿瘤细胞HEPG2和人结肠癌细胞SW620均具有增殖抑制作用。同时利用量子化学计算对配合物2进行了理论计算。     

Synthesis and structure of the first water-soluble chiral monomeric MnIV complex: [Δ-MnIV(biguanide)3] (ClO4)4·H2O

The reaction of KMnO₄ with alkaline biguanide sulfate solution, followed by acidification of the resulting stable filtrate with concentrated HClO₄, led to the title complex, 1. The crystal structure of the [Δ-Mn^IV(bigH)₃](ClO₄)₄·H₂O (1, bigH: biguanide, C₂H₇N₅) has a tetragonal chiral P4 ₁ 2 ₁ 2 space group with a = b = 11.416(3) ?, c = 20.742(7) ?, Z = 4. The complex consists of one chiral [Δ-Mn^IV(bigH)₃] tetracation, four ClO₄ ⁻ anions, and one water molecule. In the tetracation, six N atoms from three neutral biguanide chelate coordinate to the Mn^IV cation, forming an octahedron with Δ-optical activity. The [Δ-Mn^IV(bigH)₃] tetracation interconnects each other by numerous hydrogen bonds with N–H···O and O–H···O between biguanide moieties of the [Δ-Mn^IV(bigH)₃] tetracations and counter-anions as well as water molecules, to construct a three-dimensional network.     

Ni(Ⅱ)与Hbbimp配合物的合成、表征及晶体结构

A new complex with binuclear nickel(Ⅱ) complex [Ni₂(bbimp)(CH₃CH₂OH)₂Cl₂]Cl·4H₂O (bbimp=2，6-bis[bis(2-benzimidazolylmethyl)]aminomethyl-4-methylpheno)(o)had been synthesized and characterized by ele-mentary analysis， IR and UV. The molecular structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is monoclinic， space group P2₁/n with a=20.803(2)?， b=30.708(3)?， c=20.959(2)?， β=105.776(2)°， Z=8， V=12885(2)?³， D_x=1.132Mg·m^-3， μ=0.755mm^-1， F(000)=4592， R₁=0.1267， S=1.376. It was showed that the nickel(Ⅱ) cation is the central ion of a distorted octahedral coordination with two N belonging to benzimidazole， a bridging phenolate O， a N of tertiary amine， a Cl anion， and an O of an ethanol molecule. Two nickel(Ⅱ) cations in a molecular structure had the same coordinated environment. CCDC： 197601.     

Studies on the Interaction of Dinitratobis（phen） Cadmium Complex with DNA

DNA-binding properties of the dinitratobis（phen） cadmium complex [Cd（phen）2（NO3）2] （where phen = 1,10-phenanthroline） have been investigated with absorption titration, fluorescence spectroscopy, viscosity measurement, molecular modeling and density functional theory （DFT） calculations. The results indictate DNA-binding mode of the complex to be weak groove binding rather than partial intercalative interaction expected of the extended planar aromatic phen ring. In addition, the DNA cleavage study was carried out by gel electrophoresis experiment. The results showed that the complex both hardly cleaves pBR322 DNA in the absence and present ascorbate. So it is suggested that the formation of cadmium complex can decrease cadmium toxicity to some extents.     

Structural diversity,magnetic properties and luminescence of NiII,CoII and ZnII coordination polymers derived from 3,3′‐[(5‐carboxy‐1,3‐phenylene)bis(oxy)]dibenzoic acid and 1,10‐phenanthroline

Three novel coordination polymers (CPs), namely poly[[di‐μ‐aqua‐bis{μ₄‐3,3′‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoato‐κ⁵O¹:O^1′,O³:O⁵:O^5′}bis(1,10‐phenanthroline‐κ²N,N′)trinickel(II)] dimethylformamide 1.5‐solvate trihydrate], {[Ni₃(C₂₁H₁₁O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]·1.5C₃H₇NO·3H₂O}_n, (I), poly[[di‐μ‐aqua‐bis{μ₄‐3,3′‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoato‐κ⁵O¹:O^1′,O³:O⁵:O^5′}bis(1,10‐phenanthroline‐κ²N,N′)tricobalt(II)] diethylamine disolvate tetrahydrate], {[Co₃(C₂₁H₁₁O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₂H₇N·4H₂O}_n, (II), and catena‐poly[[aqua(1,10‐phenanthroline‐κ²N,N′)zinc(II)]‐μ‐5‐(3‐carboxyphenoxy)‐3,3′‐oxydibenzoato‐κ²O¹:O³], [Zn(C₂₁H₁₂O₈)(C₁₂H₈N₂)(H₂O)]_n, (III), have been synthesized by the reaction of different metal ions (Ni²⁺, Co²⁺ and Zn²⁺), 3,3′‐[(5‐carboxy‐1,3‐phenylbis(oxy)]dibenzoic acid (H₃cpboda) and 1,10‐phenanthroline (phen) under solvothermal conditions. All the CPs were characterized by elemental analysis, single‐crystal and powder X‐ray diffraction, FT–IR spectroscopy and thermogravimetric analysis. Complexes (I) and (II) have isomorphous structures, featuring similar linear trinuclear structural units, in which the central Ni^II/Co^II atom is located on an inversion centre with a slightly distorted octahedral [NiO₆]/[CoO₆] geometry. This comprises four carboxylate O‐atom donors from two cpboda^3? ligands and two O‐atom donors from bridging water molecules. The terminal Ni^II/Co^II groups are each connected to the central Ni^II/Co^II cation through two μ_1,3‐carboxylate groups from two cpboda^3? ligands and one water bridge, giving rise to linear trinuclear [M₃(μ₂‐H₂O)₂(RCOO)₄] (M = Ni²⁺/Co²⁺) secondary building units (SBUs) and the SBUs develop two‐dimensional‐networks parallel to the (100) plane via cpboda^3? ligands with new (3²·4)₂(3²·8³·9)₂(3⁴·4².8²·9⁴·10³) topological structures. Zinc complex (III) displays one‐dimensional coordination chains and the five‐coordinated Zn atom forms a distorted square‐pyramidal [ZnO₃N₂] geometry, which is completed by two carboxylate O‐atom donors from two distinct Hcpboda^2? ligands, one O atom from H₂O and two N atoms from a chelating phen ligand. Magnetically, CP (I) shows weak ferromagnetic interactions involving the carboxylate groups, and bridging water molecules between the nickel(II) ions, and CP (II) shows antiferromagnetic interactions between the Co²⁺ ions. The solid‐state luminescence properties of CP (III) were examined at ambient temperature and the luminescence sensing of Cr₂O₇^2?/CrO₄^2? anions in aqueous solution for (III) has also been investigated.     

邻氨基酚Schiff碱钴、镍双核配合物:合成、结构和抗癌活性及量化计算

分别采用水热法和溶剂挥发法合成了一个五配位的钴双核配合物[Co₂（H₂O）₂（L1）₂（4,4''-bipy）]（1）和一个镍双核配合物[Ni₂（L2）₂（4,4''-bipy）]（2）（H₂L1=邻氨基酚缩5-溴水杨醛,H₂L2=邻氨基酚缩水杨醛）,并经红外光谱和紫外光谱以及热重分析进行了表征。X射线单晶衍射分析表明1的晶体结构属三斜晶系P1空间群;2属于三方晶系R3空间群。采用MTT法初步研究了配体和配合物的体外抗癌活性,结果表明,1和2对人肝肿瘤细胞HEPG2和人结肠癌细胞SW620均具有增殖抑制作用。同时利用量子化学计算对配合物2进行了理论计算。     

一种CdⅡ-MOF作为传感Fe(Ⅲ)和Cr(Ⅵ)的多响应荧光探针

通过水热法合成了一种金属有机骨架[Cd₃(L)₂(H₂O)₉]·9H₂O (MOF 1),其中H₃L=5-(((4-羧基苯基)氧基)甲基)苯-1,3-二甲酸,并通过单晶X射线衍射、粉末X射线衍射和元素分析对其进行了表征。MOF 1表现为一个二维微孔结构,孔隙可利用体积为22.4%。荧光性能研究表明,MOF 1可以用作检测Fe(Ⅲ)和Cr(Ⅵ)的荧光传感器。它具有高选择性和低检测限,而且不受其他离子的干扰。此外,通过金属有机骨架主体和目标分析物客体的紫外可见吸收光谱研究了主体配合物的选择性荧光猝灭机制。这种荧光猝灭的可能机制是荧光共振能量转移。