[Gd(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O的晶体结构和生物活性

在水乙醇混合溶剂中，首次得到了2-羰基丙酸水杨酰腙、1，10-菲啰啉与硝酸钆形成的配合物[Gd(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]₂·phen·4H₂O，并测试了其单晶结构。该配合物属三斜晶系，空间群为P-1。每个配合物分子中有两个九配位的钆的结构单元，每个钆离子与两个三齿配体2-羰基丙酸水杨酰腙（分别以负一价和负二价形式）和三个水分子配位。每个钆单元在空间呈扭曲的单帽四方反棱柱。同时还有一个游离的1，10-菲啰啉存在于晶格中，通过氢键与配位水作用。生物活性试验表明该配合物对三种病原菌有一定的抑菌活性。     

[Hg2(μ‐bpe)(μ‐OAc)2(μ‐SCN)2]n,a New Two‐Dimensional Coordination Polymer Involving Three Simultaneously Bridging Ligands: 1,2‐Bis(4‐pyridyle)ethene,Acetate, and Thiocyanate

A new mercury(II) complex of 1,2‐bis(4‐pyridyle)ethene (bpe) with anionic acetate and thiocyanate ligands has been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. The single crystal X‐ray analysis shows that the complex is a two‐dimensional polymer with simultaneously bridging 1,2‐bis(4‐pyridyle)ethane, acetate and thiocyanate ligands and basic repeating dimeric [Hg₂(μ‐bpe)(μ‐OAc)₂(μ‐SCN)₂] units. The two‐dimensional system forms a three‐dimensional network by packing via π‐π stacking interactions.     

Synthesis,Crystal Structure,and Magnetic Property of New Trispin Ln(III)‐Nitronyl Nitroxide Complexes

Four Ln(III) complexes based on a new nitronyl nitroxide radical have been synthesized and structurally characterized: {Ln(hfac)₃[NITPh(MeO)₂]₂} (Ln = Eu( 1 ), Gd( 2 ), Tb( 3 ), Dy( 4 ); NITPh(MeO)₂ = 2‐(3′,4′‐dimethoxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide; hfac = hexafluoroacetylacetonate). The single‐crystal X‐ray diffraction analysis shows that these complexes have similar mononuclear trispin structures, in which central Ln(III) ion is eight‐coordinated by two O‐atoms from two nitroxide groups and six O‐atoms from three hfac anions. The variable temperature magnetic susceptibility study reveals that there exist ferromagnetic interactions between Gd(III) and the radicals, and antiferromagnetic interactions between two radicals (J_Gd‐Rad = 3.40 cm^?1, J_Rad‐Rad = ?9.99 cm^?1) in complex 2 . Meanwhile, antiferromagnetic interactions are estimated between Eu(III) (or Dy(III)) and radicals in complexes 1 and 4 , and ferromagnetic interaction between Tb(III) and radicals in complex 3 , respectively.     

Rhenium(II) nitrosyl complexes: synthesis,characterization, DFT calculations and DNA nuclease activity

The rhenium(II) dinitrosyl and mononitrosyl complexes, i.e. [Re(NO)₂(CN)₄]·(Phen)₂·2H₂O (1) and PhenH[Re(NO)(CN)₄(H₂O)]·(Phen)·3H₂O (2) have been isolated and characterized. The X-ray crystal structure of 2 reveals that Re(II) is octahedrally coordinated with one nitrosyl, four cyanides, and one water, with one phenanthroline protonated to compensate the charge of the Re(II) center. The crystal structure shows chemically significant non-covalent interactions like hydrogen bonding involving the uncoordinated water and π–π interactions between phenanthrolinium and phen. The structures of both complexes have been optimized by DFT. Absorption and emission spectral studies and viscosity measurements indicate that both 1 and 2 interact with calf thymus DNA through partial intercalation of DNA bases. The intrinsic-binding constants, obtained from UV–vis spectroscopic studies, are 1.2?×?10⁴ and 7.2?×?10⁴?M^?1 for 1 and 2, respectively. Both 1 and 2 are capable of inducing cleavage of plasmid DNA in the presence of H₂O₂ to form the supercoiled form to nicked circular form. The spectroscopic results of DNA binding are supported by molecular docking studies.     

Preparation,structure and magnetic study of a new linear 1-D Cu(II)–Gd(III) coordination polymer

A carboxylate-bridged Cu(II)–Gd(III) complex, [GdCu(CH₂CH(CH₃COO)₄(H₂O)₄] _n (NO₃) _n , was prepared and characterized. Single crystal X-ray analysis reveals the complex as a carboxylate-bridged 1-D Cu(II)–Gd(III) coordination polymer. The magnetic measurement showed this complex exhibiting weak ferromagnetic behavior.     

Structure, stability and relaxivity of trinuclear triangular complexes

The self-assembly of a carbonylpyridine-based heptadentate ligand with Ln(III) results in the formation of triangular trinuclear europium complexes, which exhibit interesting luminescent properties in the solid state and in solution. With a view to developing multimodal responsive systems, we report here the preparation and characterisation of analogous complexes with Gd(III). The X-ray crystal structure of Gd(3)L2(3) indeed reveals the isostructurality with the Eu(III) complexes. A combination of (1)H NMRD and variable temperature studies yields the parameters elucidating the exchange of coordinated water and relaxivity properties. Conveniently, the competitive spectrophotometric titrations with EDTA and NTA are used to determine the thermodynamic stability constants of the europium complexes in aqueous media. In addition, the exchange reaction with EDTA is monitored with NMR and fluorimetry. The interactions of the Eu(III) trinuclear complex with some potentially interfering ligands are qualitatively investigated by means of luminescence titrations.     

Synthesis,Crystal structure and Fluorescence properties of a Binuclear Terbium(Iii) complex of N-(2-Pyridinyl)Ketoacetamide

A binuclear terbium(III) complex of N-(2-pyridinyl)ketoacetamide (HL) was synthesized and its crystal structure determined. Each terbium(III) binds to one N,O-bidentate HL, one O,O-bidentate L and two N,μ-O,O-tridentate bridging L ligands; the coordination polyhedron is a distorted square antiprism. The pyridine N and keto O atoms of the binucleating ligand are coordinated to each Tb with the amide O acting as a bridging atom. The adjacent [Tb₂(HL)₂L₄]²⁺ units are bridged by double C(R)NH…ONO₂…HN(R)C hydrogen bonds to form an infinite 1-D chain, and a 2-D layer structure results from a rare near face-to-face π,π-stacking interaction between the pyridine rings of the adjacent chains. The crystal structure analysis reveals that the ligands completely shield the Ln(III) ions. Excited by the absorption band at 370?nm, the Tb(III) complex displays characteristic metal-centered fluorescence while the ligand fluorescence is completely quenched, showing that efficient ligand-to-metal energy transfer (antenna effect) occurs.     

Synthesis,characterization, and crystal structure determination of palladacycles of para-substituted 2-thiobenzylazobenzenes

Bichelated neutral palladacycles (1–3), [Pd(L)Cl], were synthesized from reaction of the new potential tridentate (C,N,S) ligands, 2-thiobenzylazobenzene (L₁), 4′-methyl-2-thiobenzylazobenzene (L₂), and 4′-chloro-2-thiobenzylazobenzene (L₃) with sodium tetrachloropalladate(II), Na₂[PdCl₄], in ethanol. The compounds were characterized by elemental analysis, FT-IR, ¹H NMR, UV–visible, and thermogravimetric analysis. The crystal structures of L₂ and 1–3 were determined by single-crystal X-ray diffraction. In 1–3, the geometry around palladium remains almost square planar, coordinated to carbon, nitrogen, and sulfur of the ligand forming a bichelated cyclopalladate complex. The C–H…Cl type intermolecular hydrogen bonds, weak π…π, C–H…π, and van der Waals interactions are believed to be the stabilizing forces for the crystal packing of these palladacycles.     

A copper(II) complex of benzimidazole-based ligand: synthesis,structure, redox aspects and fluorescence properties

Employing 1-(2-methoxybenzyl)-2-(2-methoxyphenyl)-1H-benzimidazole (bpb) as a monodentate ligand, a new greenish-blue copper(II) complex, [Cu(bpb)₂(NO₃)₂] (1a), has been synthesized. 1a has been characterized analytically and spectroscopically. The X-ray crystal structure of 1a reveals that it adopts a cis disposition with respect to the ligands. The solid state structure of 1a is stabilized by intramolecular offset face-to-face π–π stacking. Non-covalent supramolecular edge-to-face C–H?π interactions with neighboring molecules give 1-D supramolecular chains that further lead to the formation of an assembled 3-D supramolecular metal-organic framework via hydrogen bonding interactions. 1a shows blue fluorescence most likely due to intramolecular offset face-to-face π–π stacking. At room temperature, 1a is one-electron paramagnetic. It shows a rhombic EPR spectrum with g₁ = 2.12, g₂ = 2.42, and g₃ = 2.52 in the solid state at liquid nitrogen temperature. In cyclic voltammetry, 1a displays a one-electron oxidative Cu(II)/Cu(III) couple. Our DFT calculations, corroborate the observed experimental results of 1a.     

Synthesis,structures and Hirshfeld surface analysis of Ni(II) and Co(III) complexes with N2O donor Schiff base ligand

Two octahedral complexes [NiL(HL)]ClO₄.0.5CH₃OH and [CoL₂]ClO₄ have been synthesized with N₂O donor Schiff base ligand {((2-(phenylamino)ethyl)imino)methyl}phenol (HL) and characterized by spectroscopic techniques and single crystal X-ray diffraction studies. The molar conductivities data of the two complexes show that the complexes are 1:1 electrolyte. Single crystal X-ray diffraction data shows both Ni(II) and Co(III) complexes have distorted octahedral geometry and two ligands are coordinated to the metal centers and one ClO₄⁻ ion outside the coordination sphere. The intermolecular interactions in the complexes are evaluated by Hirshfeld surface analysis and revealed a significant contribution of non- or weakly polar interactions to the packing forces for both molecules, with crystal structure of Co(III) complex featuring short H/H contacts.     

Aqua­di­chloro­(di‐2‐pyridyl­di­azene)copper(II) monohydrate

The crystal structure of the mononuclear title complex, [CuCl₂(C₁₀H₈N₄)(H₂O)]·H₂O, shows an s‐cis/E/s‐trans‐configured di‐2‐pyridyl­diazene ligand, with the square‐pyramidal Cu^II ion coordinated to one pyridyl and one diazene N atom together with two Cl atoms and one aqua ligand. The crystal packing involves both hydrogen‐bonding and π–π interactions. The solvent water mol­ecule links three monomers to one another through hydrogen‐bonding interactions in which two monomers are linked via chloro ligands and the third via the aqua ligand. Face‐to‐face and weak slipped π–π interactions also occur between di‐2‐pyridyl­diazene moieties, and these interactions are responsible for the interchain packing.     

Synthesis and characterization of chloro-bis(quinoline-2-carboxylato-κ2N,O)gallium(III)

The preparation and characterization of a new gallium(III) complex with quinoline-2-carboxylate, of formula [Ga(quin-2-c)₂Cl], are described. The crystal structure of the complex has been determined by X-ray diffraction, crystallizing in monoclinic space group P2₁/n with Ga(III) adopting a distorted tetragonal pyramid. Gallium(III) coordinates two quinoline-2-carboxylates and one chloride with a Cl,N₂,O₂ donor set. In the crystal the 2-D supramolecular structure is generated by weak intermolecular interactions, C–H?···?O, C–H?···?Cl, and C–H?···?π. The cytotoxicity assays against several human cancer cell lines (Du145, A549, MCF-7, A498, HT-29) and against mouse fibroblasts (BALB/3T3) revealed moderate antiproliferative activity of the complex.     

Four tri-spin lanthanide–nitronyl nitroxide (LnIII = GdIII,DyIII, ErIII,and HoIII) complexes: syntheses,structures, and magnetic properties

Four radical–Ln(III)–radical complexes, [Ln(hfac)₃(NITPhSCH₃)₂] (Ln?=?Gd (1), Dy (2), Er (3), Ho (4); hfac?=?hexafluoroacetylacetonate; NITPhSCH₃?=?4′-thiomethylphenyl-4,4,5,5tetramethyl-imidazoline-1-oxyl-3-oxide), have been synthesized, and structurally and magnetically characterized. The X-ray crystal structures show that the structures of the four complexes are similar, consisting of isolated molecules in which Ln(III) ions are coordinated by six oxygen atoms from three hfac and two oxygen atoms from nitronyl radicals. The temperature dependencies of magnetic susceptibilities for the four complexes show that in the Gd(III) complex, ferromagnetic interactions between Gd(III)–radical and antiferromagnetic interactions between the radicals coexist with J _Rad–Gd?=?1.09?cm^?1, J _Rad–Rad?=??1.85?cm^?1.     

(π)C—H···S, (allyl)C—H···C(π) and π···π intermolecular interactions: synthesis, characterization, and crystal structure of 2,2′-bipyridine bis(diallyldithiocarbamato)zinc(II)

A mixed-ligand Zn(II) complex formulated as [Zn(aldtc)₂(bipy)] (aldtc=diallyldithiocarbamate; bipy=2,2′-bipyridine) was synthesized and characterized by IR, ¹H and ¹³C NMR spectral measurements and X-ray crystallography. The crystal structure of this complex indicates that Zn has a distorted octahedral geometry. The Zn—N distances are invariant (2.168(2) Å), while those of the Zn—S are slightly different (2.5408(9) and 2.5440(9) Å). The N—Zn—N, S—Zn—S and N—Zn—S bond angles are in the range 75.35(13)–99.75(7)°, 70.48(3)–161.02(5)° and 95.26(7)–160.32(7)°, respectively. The crystal packing of the complex shows different motifs of supramolecularity resulting from both hydrophilic ((π)C—H···S) and hydrophobic ((allyl)C—H···C(π)) intermolecular interactions. These interactions result in a chain arrangement of molecules along crystallographic c axis and the chains are further connected via π···π stacking along with ((π)C—H···S along b axis leading to an overall crystal packing that can be regarded as layers of complexes along bc plane, which are held together through nonconventional hydrogen bonding and π···π stacking.     

Crystal Structure of Complex Tris（4,4,4—trifluoro—1—pheny1—1,3—butanedione）（1,10—phenanthroline）Europium（Ⅲ）

The complex Eu(btfa)₃ (phen) (btfa=4,4,4‐trifluoro‐1‐phenyl‐1, 3‐butanedione, phen = 1,10‐phenanthroline) has been prepared and characterized by elemental analysis, IR and UV spectroscopies. The crystal and molecular structures of the complex have been determined by X‐ray diffraction analysis. It belongs to the monoclinic crystal system, space group P2₁/c with a = 0.9700(2) nm, b = 3.7450(5) nm, c = 1.0917(3) nm, β = 92.51(2)°, V = 3.962(1) nm⁵, Z = 4, D_c = 1.639 g/cm³, μ = 1.676 mm^?1, F(000) = 1936, R₁, = 0.0388, wR₂ = 0.0775. Structure analysis shows that the europium(III) ion is coordinated to six oxygen atoms of β‐diketonate anions and two nitrogen atoms of phenanthroline molecule. The coordination polyhedron is an approximate square antiprism.     

Preparation, Crystal Structure and Enthalpy Change of Formation of the Reaction in Liquid Phase of a New Three- Dimensional Mixed-Ligand Holmium（Ⅲ）Coordination Polymer Based on Strong π-π Stacking Interactions

A new three-dimensional coordination polymer, [Ho（5-nip）（phen）（NO3）（DMF）] （5-nip=5-nitroisophthalic acid and phen=1,10-phenanthroline）, was prepared and characterized by single crystal X-ray diffraction, elemental analysis, IR spectrum and DTG-DSC techniques. The results show that the title complex crystallizes in space group P2/m with a= 1.0906（3） nm, b =1.2804 （3） nm, c= 1.6987（4） nm, β=91.400（5）°, Z=4, Dc= 1.931 Mg/m^3, F（000）= 1352. Each Ho（Ⅲ） ion is nine-coordinated by one chelating bidentate and two monodentate bridging carboxylate groups, one chelating bidentate NO3 anion, one DMF molecule and one 1,10-phenanthroline molecule. The complex is constructed with one-dimensional ribbons featuring dinuclear units and the one-dimensional ribbons are further assembled into two-dimensional networks by strong π-π stacking interactions with the distance of 0.327 nm, then the networks are arranged into three-dimensional structure according to ABAB fashion. The complex exhibits high stability up to 600 ℃. Its enthalpy change of formation of the reaction in liquid-phase in solvent DMF was measured using an RD496-Ⅲ type microcalorimeter with a value of （-11.016±0.184） kJ·mol^-1.     

A new two‐dimensional anionic cadmium(II) polymer constructed through thiocyanate coordination bridges

A new cadmium–thiocyanate complex, poly[4‐(dimethylamino)pyridin‐1‐ium [di‐μ‐thiocyanato‐κ²N:S;κ²S:N‐thiocyanato‐κN‐cadmium(II)]], {(C₇H₁₁N₂)[Cd(NCS)₃]}_n, was synthesized by the reaction of cadmium thiocyanate and 4‐(dimethylamino)pyridine hydrochloride in aqueous solution. In the crystal structure, each Cd^II ion is square‐pyramidally coordinated by three N and two S atoms from five different thiocyanate ligands, four of which are bridging. The thiocyanate ligands play different roles in the build up of the structure; one role results in the formation of [Cd₂(NCS)₂] building blocks, while the other links the building blocks and cations via N—H...S hydrogen bonds. The N—H...S hydrogen bonds and weak π–π stacking interactions are involved in the formation of both a two‐dimensional network structure and the supramolecular network.     

Synthesis,Structure, and Magnetic Studies of a New Wheel‐Shaped [LiMnIII6] Cluster

The synthesis, crystal structure, and magnetic properties of a new hexanuclear manganese(III) complex are reported. The complex [LiMn₆(L)₆]OH · 2MeCN · 4MeOH · 1.5H₂O (LiH₂L = lithium 2‐{[bis(2‐hydroxyethyl)amino]methyl}‐4‐methylphenate) ( 1 ), was obtained from the reaction of one equivalent of LiH₂L with Mn(OAc)₂ in MeCN/MeOH (v:v/1:1). Single‐crystal X‐ray diffraction shows that six octahedrally coordinated manganese(III) ions define a ring and are linked by twelve bridging oxygen atoms from alkoxo groups. The resulting [Mn₆(OCH₂)₁₂] skeleton has the remarkable property of acting as a host for a octahedrally coordinated lithium ion in the center of the ring. Variable‐temperature solid‐state magnetic susceptibility studies of 1 in the temperature range 2.0–300 K reveal that the complex has a S = 12 ground state spin, showing ferromagnetic exchange interactions between the constituent manganese(III) ions.     

New heteroleptic lanthanide complexes as multimodal drugs: Cytotoxicity studies,apoptosis, cell cycle analysis,DNA interactions,and protein binding

We report herein the synthesis and characterization of four new heteroleptic complexes of Sm(III), Eu(III), Gd(III), and Tb(III) with the natural flavonoid 5‐hydroxyflavone (primuletin) and 1,10‐phenanthroline. According to the physicochemical characterization, the mononuclear complexes correspond to the general formula [Ln(OH) ₂ L ₁ L ₂ ]·nH ₂ O , where L₁ = C₁₅H₉O₃ (deprotonated 5‐hydroxyflavone) and L₂ = C₁₂H₈N₂ (1,10‐phenanthroline), Ln is the lanthanide cation, and n = 4 for Sm(III), 3.5 for Eu(III), 2 for Gd(III), and 3 for Tb(III). A six‐coordinated distorted octahedron geometry was proposed for the complexes, and density functional theory (DFT) studies were used to calculate their optimized geometry. Cytotoxicity was studied using MTS assay on cervical, colorectal, colon, breast, and ovarian adenocarcinoma cell lines. Flow cytometry data were consistent with apoptotic cell death and disruption of the cell cycle in cervical and colon cancer cells. As a means to investigate the mechanism underlying the cytotoxic effects, the abilities of the complexes to interact with calf thymus DNA, human serum albumin, and transferrin have also been assessed. According to experimental and computational studies, the four lanthanide complexes act as DNA intercalators and bind strongly to serum proteins.     

Synthesis,characterization and magnetism of copper(II)‐lanthanide(III) heterobimetalic complexes with N,N'‐oxamidobis‐(benzoato)cuprate (II)

Seven new μ‐oxamido copper(II)‐lanthanide(III) heterobimetalic complexes described by the formula Cu(obbz) Ln‐(Ph‐phen)₂NO₃(Ln = La, Nd, Eu, Gd, Tb, Ho, Er), where obbz denotes the oxamidobis(benzoato) and Ph‐phen represents 5‐phenyl‐1, 10‐phenanthroline, have been synthesized and characterized by the elemental analyses, spectroscopic (IR, UV, ESR) studies, magnetic moments (at room temperature) and molar conductivity measurement. The temperature dependence of the magnetic susceptibility of Cu(obbz)Gd(Ph‐phen)₂NO₃ complex has been measured over the range 4.2–300 K. The least‐squares fit of the experimental susceptibilities based on the spin Hamiltonian operator, ? = ?2 J?₁·?₂, yielded J= +1.28 cm^?1, a weak ferromagnetic coupling, A plausible mechanism for a ferromagnetic coupling between Gd(III)‐Cu(II) is discussed in terms of spin‐polarization.