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1.
The direct mixing of CoCl2, sodium 2,6‐pyridinedicarboxylate (Na2(2,6‐pda)), KSCN, and 1,2‐bis(4‐pyridyl)ethane (bpye) in water at the ambient temperature afforded purple crystals readily. The crystal structure, as determined by X‐ray diffraction crystallography, consists of discrete inorganic [Co23‐2,6‐pda)2(μ‐SCN)2(H2O)2] and organic bpye molecules. Adjacent dicobalt molecules are connected via intermolecular hydrogen bonds, to form one‐dimensional hydrophobic channels in the solid state, which serve as a host framework to incarcerate bpye guests inside. Every organic molecule attaches to four adjacent inorganic species via arene‐arene interactions. The facile approach in assembling the dicobalt and bpye molecules together into an inorganic clathrate is demonstrated.  相似文献   

2.
Three pyridyl functionalized bis(pyrazol‐1‐yl)methanes, namely 2‐[(4‐pyridyl)methoxyphenyl] bis(pyrazol‐1‐yl)methane (L1), 2‐[(4‐pyridyl)methoxyphenyl]bis(3,5‐dimethylpyrazol‐1‐yl)methane (L2) and 2‐[(3‐pyridyl)methoxyphenyl]bis(pyrazol‐1‐yl)methane (L3) have been synthesized by the reactions of (2‐hydroxyphenyl)bis(pyrazol‐1‐yl)methanes with chloromethylpyridine. Treatment of these three ligands with R2SnCl2 (R = Et, n‐Bu or Ph) yields a series of symmetric 2:1 adducts of (L)2SnR2Cl2 (L = L1, L2 or L3), which have been confirmed by elemental analysis and NMR spectroscopy. The crystal structures of (L2)2Sn(n‐Bu)2Cl2·0.5C6H14 and (L3)2SnEt2Cl2 determined by X‐ray crystallography show that the functionalized bis(pyrazol‐1‐yl)methane acts as a monodentate ligand through the pyridyl nitrogen atom, and the pyrazolyl nitrogen atoms do not coordinate to the tin atom. The cytotoxic activity of these complexes for Hela cells in vitro was tested. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

3.
A new 3D hemidirected mixed‐ligand lead(II) coordination polymer with the ligand 1,2‐di(4‐pyridyl)ethane bpa) and the two metal coordinated anions nitrate and thiocyanate, [Pb2(bpa)2(SCN)3(NO3)]n ( 1 ), has been synthesized and characterized by CHN elemental analysis, IR‐, 1H‐ and 13C NMR spectroscopy. The single crystal X‐ray data of compound 1 show that the complex is a three‐dimensional coordination polymer with two different Pb atoms with stereoactive electron lone pairs and six‐ and five‐coordinate hemidirected geometries, respectively.  相似文献   

4.
Self‐assembly of Zn (II) or Cd (II) nitrates, flexible bis (pyridyl)‐diamine, as well as arenesulfonic acids, leads to the formation of ten coordination polymers, namely, [Zn(L1)(H2O)3]·2(p‐TS)·2H2O ( 1 ), [Zn(L1)(H2O)2]·2(p‐TS)·2H2O ( 2 ), [Zn(L1)2(p‐TS)2] ( 3 ), [Zn(H2L1)(H2O)4]·2(1,5‐NDS)·2H2O ( 4 ), [Zn(H2L2)(H2O)4]·2(1,5‐NDS)·4MeOH ( 5 ), [Cd(L1)(p‐TS)(NO3)]·H2O ( 6 ), [Cd(L1)(1,5 ‐NDS)0.5(H2O)]·0.5(1,5‐NDS)·H2O ( 7 ), [Cd(L2)(H2O)2]·(p‐TS)·(NO3)·3H2O ( 8 ), [Cd(L2)(1,5‐NDS)] ( 9 ) and [Cd(L2)(1,5‐NDS)]·MeOH ( 10 ) (L1 = N,N′‐bis (pyridin‐4‐ylmethyl) ethane‐1,2‐diamine, L2 = N,N′‐bis (pyridin‐3‐ylmethy l)ethane‐1,2‐diamine, p‐HTS = p‐toluenesulfonic acid, 1,5‐H2NDS = 1,5‐naphthalene disulfonic acid), which have been characterized by elemental analysis, IR, TG, PL, powder and single‐crystal X‐ray diffraction. Complexes 1 , 4 , 5 and 6 present linear or zigzag chain structures accomplished by the interconnection of adjacent M (II) cations through L1 ligands or protonated H2L12+/H2L22+ cations, while complexes 2 , 3 and 8 show similar (4,4) layer motifs constructed from the connection of M (II) cations through L1 and L2. The same coordination modes of L1 and L2 in complexes 7 and 9 join adjacent Cd (II) cations to form double chain structures, which are further connected by bis‐monodentate 1,5‐NDS2? dianions into different (6,3) and (4,4) layer motifs. The L2 molecules in complex 10 join adjacent Cd (II) cations together with 1,5‐NDS2? dianions to form 3D network with hxl topology. Therefore, the diverse coordination modes of the bis (pyridyl) ligand with chelating spacer and the feature of different arenesulfonate anions can effectively influence the architectures of these complexes. Luminescent investigation reveals that the emission maximum of these complexes varies from 374 to 448 nm in the solid state at room temperature, in which complexes 4 , 5 , 7 , 9 and 10 show average luminescence lifetimes from 7.20 to 14.82 ns. Moreover, photocatalytic properties of complexes 7–10 towards Methylene blue under Xe lamp irradiation are also discussed.  相似文献   

5.
Six mono/double‐layered 2D and three 3D coordination polymers were synthesized by a self‐assembly reaction of Zn (II) salts, organic dicarboxylic acids and L1/L2 ligands. These polymeric formulas are named as [Zn(L1)(C4H2O4)0.5 (H2O)]n·0.5n(C4H2O4)·2nH2O ( 1 ), [Zn2(L2)(C4H2O4)2]n·2nH2O ( 2 ), [Zn(L1)(m‐BDC)]n ( 3 ), [Zn2(L2)(m‐BDC)2]n·2nH2O ( 4 ), [Zn3(L1)2(p‐BDC)3(H2O)4]n·2nH2O ( 5 ), [Zn2(OH)(L2) (p‐BDC)1.5]n ( 6 ), [Zn2(L1)(p‐BDC)2]n·5nH2O ( 7 ), [Zn2(L2)(p‐BDC)2]n·3nH2O ( 8 ) and [Zn2(L1)(C4H4O4)1.5(H2O)]n·n(ClO4nH2O ( 9 ) [L1 = N,N′‐bis (pyridin‐4‐ylmethyl)propane‐1,2‐diamine, L2 = N,N′‐bis (pyridin‐3‐ylmethyl)propane‐1,2‐ diamine, m‐BDC2? = m‐benzene dicarboxylate, p‐BDC2? = p‐benzene dicarboxylate]. Meanwhile, these polymers have been characterized by elemental analysis, infrared, thermogravimetry (TG), photoluminescence, powder and single‐crystal X‐ray diffraction. Polymers 1–6 present mono‐ and double (4,4)‐layer motifs accomplished by L1/L2 ligands with diverse conformations and organic dicarboxylates, and the layer thickness locates in the range of 5.8–15.0 Å. In three 3D polymers, the L1 and L2 molecules adopt the same cis‐conformations and join adjacent Zn (II) cations together with p‐BDC2? or succinate, giving rise to different binodal (4,4)‐c nets with (4.52.83)(4.53.72) ( 7 ), pts ( 8 ) topology and twofold interpenetrated binodal (5,5)‐c nets with (32.44.52.62)(3.43.52.64) ( 9 ). Therefore, the diverse conformations of the two bis (pyridyl)‐propane‐1,2‐diamines and the feature of different organic dicarboxylate can effectively influence the architectures of these polymers. Powder X‐ray diffraction patterns demonstrate that these bulk solid polymers are pure phase. TG analyses indicate that these polymers have certain thermal stability. Luminescent investigation reveals that the emission maximum of these polymers varies from 402 to 449 nm in the solid state at room temperature. Moreover, 1 , 3 and 5–8 show average luminescence lifetimes from 8.81 to 16.30 ns.  相似文献   

6.
Five examples of unsymmetrical 1,2‐bis (arylimino) acenaphthene ( L1 – L5 ), each containing one N‐2,4‐bis (dibenzocycloheptyl)‐6‐methylphenyl group and one sterically and electronically variable N‐aryl group, have been used to prepare the N,N′‐nickel (II) halide complexes, [1‐[2,4‐{(C15H13}2–6‐MeC6H2N]‐2‐(ArN)C2C10H6]NiX2 (X = Br: Ar = 2,6‐Me2C6H3 Ni1 , 2,6‐Et2C6H3 Ni2 , 2,6‐i‐Pr2C6H3 Ni3 , 2,4,6‐Me3C6H2 Ni4 , 2,6‐Et2–4‐MeC6H2 Ni5 ) and (X = Cl: Ar = 2,6‐Me2C6H3 Ni6 , 2,6‐Et2C6H3 Ni7 , 2,6‐i‐Pr2C6H3 Ni8 , 2,4,6‐Me3C6H2 Ni9 , 2,6‐Et2–4‐MeC6H2 Ni10 ), in high yield. The molecular structures Ni3 and Ni7 highlight the extensive steric protection imparted by the ortho‐dibenzocycloheptyl group and the distorted tetrahedral geometry conferred to the nickel center. On activation with either Et2AlCl or MAO, Ni1 – Ni10 exhibited very high activities for ethylene polymerization with the least bulky Ni1 the most active (up to 1.06  ×  107 g PE mol?1(Ni) h?1 with MAO). Notably, these sterically bulky catalysts have a propensity towards generating very high molecular weight polyethylene with moderate levels of branching and narrow dispersities with the most hindered Ni3 and Ni8 affording ultra‐high molecular weight material (up to 1.5  ×  106 g mol?1). Indeed, both the activity and molecular weights of the resulting polyethylene are among the highest to be reported for this class of unsymmetrical 1,2‐bis (imino)acenaphthene‐nickel catalyst.  相似文献   

7.
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 ππ stacking interactions.  相似文献   

8.
The 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) undergoes hydrolysis in the presence of VO(SO4) in an alkaline solution, affording mainly the bis(2‐pyridyl carbonyl)amid ) VO2 complex, designated as [VO2(bpca)]. Single‐crystal X‐ray crystallography revealed that the coordination of V in complex is a distorted square‐pyramid coordinated with three nitrogen of bis(2‐pyridyl carbonyl)amid ) ligand and two binding oxygen atoms. The prepared complex which successfully supported on modified Fe3O4 nanoparticles using tetraethylorthosilicate (TEOS) and (3‐aminopropyl)trimethoxysilane(APTMS)was designated as Fe3O4@SiO2@APTMS@[VO2(bpca)] complex (nanocatalyst). The complex and nanocatalyst were characterized by means of FT‐IR, XRD, VSM, SEM and TEM. The catalytic activity of [VO2(bpca)] complex and Fe3O4@SiO2@APTMS@complex as catalysts 1 and 2 were evaluated by the epoxidation of geraniol , 3‐methyl‐2‐buten‐1‐ol , trans‐2‐hexen‐1‐ol and 1‐octen‐3‐ol with 70–98% conversions and 95–100% selectivities. Based on the obtained results, the heterogeneity and reusability of the catalyst seems promising. In addition, the in vitro antibacterial activity of [VO2 (bpca)] complex have also been evaluated and compared to the activities of other vanadium complexes, tptz ligand and two standard antibacterial drugs, Nalidixic acid and Vancomycin.  相似文献   

9.
In mononuclear [Zn(C10H9N3)2(N3)2]·H2O, the zinc atom has an approximate octahedral geometry, coordinated with four pyridyl nitrogen atoms derived from two bis(2‐pyridyl)amine molecules and two terminal nitrogen donors of the azide anions. Hydrogen‐bonding interactions extend this structure to form a double‐layer architecture. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

10.
Two noble metal complexes involving ancillary chloride ligands and chelating 2,2′‐bipyridylamine (Hdpa) or its deprotonated derivative (dpa), namely [bis(pyridin‐2‐yl‐κN)amine]tetrachloridoplatinum(IV), [PtCl4(C10H9N3)], and [bis(pyridin‐2‐yl‐κN)aminido]dichloridogold(III), [AuCl2(C10H8N3)], are presented and structurally characterized. The metal atom in the former has a slightly distorted octahedral coordination environment, formed by four chloride ligands and two pyridyl N atoms of Hdpa, while the metal atom in the latter has a slightly distorted square‐planar coordination environment, formed by two chloride ligands and two pyridyl N atoms of dpa. The difference in conjugation between the pyridine rings in normal and deprotonated 2,2′‐dipyridylamine is discussed on the basis of the structural features of these complexes. The influence of weak interactions on the supramolecular structures of the complexes, providing one‐dimensional chains of [PtCl4(C10H9N3)] and dimers of [AuCl2(C10H8N3)], are discussed.  相似文献   

11.
A unique 3‐D PbII coordination polymer containing ligands 1,2‐bis(4‐pyridyl)ethylene (bpe) and 3‐sulfobenzoate (3‐sb), [Pb(3‐sb)(bpe)0.5]n ( 1 ) has been synthesized by hydrothermal reaction and characterized by elemental analysis, IR, TGA, 1H NMR, powder X‐ray analysis, and fluorescent spectrum. The single‐crystal X‐ray analysis shows that eight coordination bonds can be divided as five primary bonds and three secondary bonds. The secondary bonds largely enhance the solid stability and provide a high‐dimensional network assembly. The complex also displays strong fluorescent property.  相似文献   

12.
The zinc(II) pseudohalide complexes {[Zn(L334)(SCN)2(H2O)](H2O)2}n ( 1 ) and [Zn(L334)(dca)2]n ( 2 ) were synthesized and characterized using the ligand 3,4‐bis(3‐pyridyl)‐5‐(4‐pyridyl)‐1,2,4‐triazole (L334) and ZnCl2 in presence of thiocyanate (SCN) and dicynamide [dca, N(CN)2] respectively. Single‐crystal X‐ray structural analysis revealed that the central ZnII atoms in both complexes have similar octahedral arrangement. Compound 1 has a 2D sheet structure bridged by bidentate L334 and double μN,S‐thiocyanate anions, whereas complex 2 , incorporating with two monodentate dicynamide anions, displays a two‐dimensional coordination framework bridged by tetradentate L334 ligand. Structural analysis demonstrated that the influence of pseudohalide anions plays an important role in determining the resultant structure. Both complexes were characterized by IR spectroscopy, microanalysis, and powder X‐ray diffraction techniques. In addition, the solid fluorescence and thermal stability properties of both complexes were investigated.  相似文献   

13.
Four ligands of 1,3‐bis(4‐pyridyl)propane and two water molecules are coordinated to the zinc(II) atom so that the coordination geometry closely resembles a trans‐N4O2 octahedral environment. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

14.
Three dinuclear copper(I) complexes, [Cu2(µ‐Cl)2(1,2‐(PPh2)2‐1,2‐C2B10H10)2]·2CH2Cl2 ( 1 ), [Cu2(µ‐Br)2(1,2‐(PPh2)2‐1,2‐C2B10H10)2]·2THF ( 2 ) and {Cu2(µ‐I)2[1,2‐(PPh2)2‐1,2‐C2B10H10]2} ( 3 ) have been synthesized by the reactions of CuX (X = Cl, Br and I) with the closo ligand 1,2‐(PPh2)2‐1,2‐C2B10H10. All these complexes were characterized by elemental analysis, FT‐IR, 1H and 13C NMR spectroscopy and X‐ray structure determination. Single crystal X‐ray structure determinations show that every complex contained di‐µ‐X‐bridged structure involving a crossed parallelogram plane formed by two Cu atoms and two X atoms (X = Cl, Br, I). The geometry at the Cu atom was a distorted tetrahedron, in which two positions were occupied by two P atoms of the PPh2 groups connected to the two C atoms of carborane (Cc), and the other two resulted from two X atoms which bridged the other Cu atom at the same time. To the best of our knowledge, this is the first example of copper(I) complexes with 1,2‐diphenylphosphino‐1,2‐dicarba‐closo‐dodecaborane as ligand characterized by X‐ray diffraction. The catalytic property of the complex 3 for the amination of iodobenzene with aniline was also investigated. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

15.
Hydrothermal reactions of Zn(NO3)2•6H2O with 1,2-di(4-pyridyl)ethylene (dpe) and 1,4-benzenedicarboxylate (1,4-BDC) or 1,3-benzenedicarboxylate (1,3-BDC) in water gave rise to two new metal-organic coordination polymers, [Zn(1,4-BDC)(dpe)]n (1) and [Zn4O(1,3-BDC)3(dpe)]n (2). Both compounds were characterized by elemental analysis and IR spectroscopy, and their structures were determined by single crystal X-ray diffraction. 1 displays a rare 5-fold interpenetrating 66-diamondoid framework while 2 possesses an interlocked 3D network formed by inclined interpenetration of 2D (4,4) networks that are constructed by μ4-oxo tetrazinc Zn4O cores and the bridging dpe and 1,3-BDC ligands. Thermal and photoluminescent properties of 1 and 2 were also investigated.  相似文献   

16.
Three copper(II) complexes, [Cu2(OAc)4L2] · 2CH3OH ( 1 ), [CuBr2L′2(CH3OH)] · CH3OH ( 2a ), and [CuBr2L′2(DMSO)] · 0.5CH3OH ( 2b ) {L = N‐(9‐anthracenyl)‐N′‐(3‐pyridyl)urea and L′ = N‐[10‐(10‐methoxy‐anthronyl)]‐N′‐(3‐pyridyl)urea} have been synthesized by the reaction of L with the corresponding copper(II) salts. Complex 1 shows a dinuclear structure with a conventional “paddlewheel” motif, in which four acetate units bridge the two CuII ions. In complexes 2a and 2b , the anthracenyl ligand L has been converted to an anthronyl derivative L′, and the central metal ion exhibits a distorted square pyramidal arrangement, with two pyridyl nitrogen atoms and two bromide ions defining the basal plane and the apical position is occupied by a solvent molecule (CH3OH in 2a and DMSO in 2b ).  相似文献   

17.
A novel one‐dimensional coordination polymer, Catena‐poly [bis(4‐cyano‐pyridyl) copper(II)‐di‐thiocyanate], 1 [CuII‐(cypy)2N.S‐SCN)2] (cypy = 4‐cyano‐pyridyl), was synthesized in a solution reaction of Cu(NO3)2·3H2O, 4‐cyano‐pyridine and KSCN in mole ratio of 1:2:2 at room temperature. Its crystal structure was determined by single‐crystal X‐ray diffraction. The crystal belongs to monoclinic crystal system, space group P21/c with cell parameters a = 1.0719(2), b = 1.8441(4), c =0.9144(2) nm, β = 110.49(3)° and Z = 4. A full‐matrix least‐squares refinement gave R1 = 0. 0393 and wR2= 0.0916 for 1554 reflections having 1 >2σ(I). The crystal is thermally stable up to approximately 170 °C.  相似文献   

18.
Product distribution and kinetic studies on the hydrosilylation of phenylacetylene by Ph3SiH, Ph2MeSiH, PhMe2SiH and Et3SiH were performed using bis‐[1,2‐diphenylphosphinoethane]norbornadienerhodium(I) hexafluorophosphate, 1, as catalyst. Pre‐equilibration of the catalyst with the acetylene produced hydrosilylations, pre‐equilibration with the silane did not. The catalyst showed a pronounced selectivity for cis‐addition to form β‐products, t‐PhCH­CHSiR3, unlike most hydrosilylation catalysts. The kinetic studies showed a hydrosilylation reaction that is zero order with respect to both acetylene and the silane, with a dependency upon catalyst concentration. The kobs value is directly influenced by the substituents on the silane: k(PhMe2SiH) > k (Et3SiH > k (Ph2MeSiH) > k (Ph3SiH). Intercalation of the catalyst in hectorite was not useful, since either no reaction occurred in non‐polar solvents, or extraction of the catalyst occurred in polar solvents to produce the same product distributions. Copyright © 2000 John Wiley & Sons, Ltd.  相似文献   

19.
The supramolecular coordination polymers (SCP); 3[Cu (CN)2(Me3Sn)(pyz)], pyrazine-trimethyltin-bis (cyanide) copperI SCP 1 , [Cu2(CN)3(Ph3Sn)(pyz)], pyrazine-triphenyltin-tris (cyanide) dicopperI SCP 3 and [Cu2(CN)4(Ph3Sn)(Pyz2caH)2], bis-pyrazine-2-carboxylic acid- triphenyltin-tetrakis (cyanide) dicopperI SCP 4 and the coordination complex (CC), [CuII (Pyz2-ca)2(H2O)2]; diaquo-bis-(pyrazine-2-carboxylato) copper(II) complex: CC 2 , are synthesized by self-assembly method at ambient conditions. Single crystal X-ray structures of SCP 1 and CC 2 indicate the presence of CuI and CuII which adopt tetrahedral and octahedron geometry, respectively. The structures of SCP 3 and SCP 4 are solved by the density functional theory (DFT) calculations and spectroscopic methods. The Cu centers acquire triagonal plane, linear and tetrahedral geometry, respectively. The CN-R3Sn-NC spacer and pyrazine or pyrazine-2-carboxylic acid ligands extend the structures to 3D-network. The tested compounds 1–4 are designed and synthesized to examine their effects on viability and proliferation of five human cancer cell lines. Also, they are tested for antioxidant activity using ABTS assay and rate erythrocyte hemolysis.  相似文献   

20.
Two new transition metal dicyanamide complexes [Co2(tppz)(dca)4]·CH3CN ( 1 ) [tppz=tetra(2‐pyridyl)pyrazine, dca=dicyanamide] and [Co(tptz)(dca)(H2O)](dca) ( 2 ) [tptz=2,4,6‐tri(2‐pyridyl)‐1,3,5‐triazine] were synthesized and characterized by single crystal X‐ray diffraction analysis. In 1 each cobalt(II) atom is coordinated to three dca anions and one tppz molecule to form a distorted octahedral geometry, the neigbour two cobalt(II) atoms are bridged by one tppz ligand to form a dimer, then the cobalt(II) atoms in each dimer are joined together to form a ladder chain structure. In 2 the coordination geometry around the central metal is also distorted octahedral, each cobalt(II) atom is coordinated by two dca anions, one tptz molecule and one water ligand to form a cationic part, and the cationic part is linked with the free dca anions via the electrostatic attraction to give an infinite chain structure. Magnetic susceptibility measurement in the range of 2–300 K indicates that there are antiferromagnetic couplings between adjacent metal ions in 1 (T>29 K, (=?9.78 K, C=4.92 cm3·K·mol?1) and ferromagnetic couplings in 2 (T>150 K, (=7.97 K, C=2.59 cm3·K·mol?1) respectively.  相似文献   

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