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1.
The reaction of [Cu(sac)2(H2O)4] · 2H2O with 2-methylpyrazine (mpyz) leads two complexes, concomitant crystallization of a mononuclear complex [Cu(sac)2(mpyz)(H2O)2] (1) and a polymeric complex [Cu(sac)2(μ-mpyz)]n (2). Both complexes have been characterized by elemental analyses, magnetic measurements, FT-IR and ESR, TG-DTA and single-crystal X-ray diffraction analyses. Single-crystal X-ray analyses show that complex 1 consists of discrete molecules in which the copper(II) ions exhibits a square-pyramidal coordination geometry. The individual molecules of 1 are connected into a hydrogen-bonded chain structure, which is further assembled to form a three-dimensional network by ππ stacking interactions. Complex 2 is an 1D coordination polymer in which copper(II) centers are bridged by the mpyz ligand. The chains are further assembled to form two-dimensional frameworks by ππ and C–H···π stacking interactions.  相似文献   

2.
A novel 2D sheet-like copper(II) complex formulated [Cu6(trans-oxen)33-OH)2(H2O)2]n-(ClO4)4n.2nH2O (1), where H2oxen is N,N’-bis(2-aminoethyl)oxamide, has been synthesized and characterized by elemental analysis, IR and UV–visible spectroscopy, and single-crystal X-ray diffraction. 1 crystallizes in triclinic space group P-1 with crystallographic data: a = 10.299(2) ?, b = 10.833(2) ?, c = 11.781(2) ?, α = 69.95(3)°, β = 81.10(3)°, γ = 62.44(3)°, and Z = 2. In the crystal structure, the cation [Cu6(trans-oxen)33-OH)2(H2O)2]n4n+ exhibits a two-dimensional sheet-like structure for Cu(II) ions bridged both by trans-oxen and hydroxyl groups. Each Cu(II) ion is located in a slightly distorted square-pyramidal environment. The hydroxyl group bridges three [Cu(oxen)Cu]2+ dications in which one oxen2− is μ2-bridge while the other two act as never before reported μ4-bridge. Perchlorate anions and H2O molecules are inserted between the sheets and bridge the 2D cations via N–H···O and O–H···O hydrogen bonds to form an infinite three-dimensional system. The cyclic voltammetric behavior of 1 and the influence of counter ions on structure are preliminarily investigated.  相似文献   

3.
Cobalt(II) and zinc(II) succinato (suc) coordination polymers with nicotinamide (nia), {[Co(μ-suc)(H2O)2(nia)2] · 2H2O} n (1) and {[Zn(μ-suc)(H2O)2(nia)2] · 2H2O} n (2) have been synthesized and characterized by elemental analyses, magnetic moments, IR and TG-DTA. Single-crystal X-ray analyses of 1 and 2 reveal that these complexes are isostructural and crystallize in triclinic space group Complexes 1 and 2 are 1-D coordination polymers, in which the metal(II) ions exhibit an octahedral geometry with two suc, two nia and two aqua ligands. The nia ligand is N-bonded, while the suc ligand bridges the metal centers through the carboxylate groups. The 1D chains are further assembled to form 3D networks by strong N–H···O and OW–H···O hydrogen bonds. IR spectra confirm the coordination modes of both suc and nia ligands, while TG-DTA data are in agreement with the crystal structures. Fluorescent analysis in the solid state shows that all complexes display intraligand (π–π*) emissions of nia.  相似文献   

4.
Abstract  Two Ag+ complexes [Ag(HL)2(PF6)] (1) and [(AgL) n  · n(CH2Cl2) · n(0.5H2O)] (2) (HL = 5-methyl-2-phenyl-4-[(2-o-tolylamino)-phenylmethylene]pyrazol-3(2H)-one) were synthesized and structurally characterized by EA analysis, IR spectra and X-ray crystallography. The result shows that two expected coordination modes (Modes I and III in Scheme 1) of the HL ligand, can be observed in its Ag+ complexes, while not in other transition metal ions (Ni2+, Co2+ or Cu2+) complexes whether deprotonation or not for the HL ligand. Graphical Abstract  Three possible coordination modes (Modes I, II or III in Scheme 1) of the selected HL (HL = 5-methyl-2-phenyl-4-[(2-o-tolylamino)-phenylmethylene]pyrazol-3(2H)-one) ligand, can be adopted, in which Modes I and III can be observed in its two Ag+ complexes [Ag(HL)2(PF6)](1) and [(AgL) n  · n(CH2Cl2) · n(0.5H2O)] (2), while Mode II just observed in its transition metal ions (Cu2+, Ni2+, or Co2+) complexes, resulting from the deprotonatd form of the HL ligand and the coordination characters of transition metal ions.   相似文献   

5.
Two new complexes, [Cd2(4-4′-bpy)2(pa)4] n ·0.25H2O (1) (pa = phenylacetate), and [Mn(4-4′-bpy)2(pa)(H2O)3]ClO4·2H2O, (2), have been obtained from hydrothermal reaction of Cd(NO3)2·4H2O and Mn(ClO4)2·6H2O with a mixture of the ligands, 2-phenylmalonic acid (2-phmalH2) and 4-4′-bipyridine (4-4′-bpy). The pa is formed in situ by decarboxylation of phenylmalonic acid. These complexes have been characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis and single-crystal X-Ray diffraction. The Cd(II) center is seven-coordinate and linked via pa ligands to form a binuclear complex in the asymmetric unit of 1. A ladder-like 1D chain of binuclear units is formed by Cd(II)–N coordination bond through 4-4′-bpy ligands. Complex 2 consists of a mononuclear manganese center based on a distorted octahedral geometry and exhibits a supramolecular structure containing hydrogen bonds and extensive π···π and C–H···π interactions.  相似文献   

6.
The heteronuclear complex, {[Cu(4(5)-Meim)4][Ni(CN)4] · H2O}n (1), (4(5)-Meim = 4(5)-methylimidazole) was synthesized and characterized by FT-IR spectroscopy, single crystal X-ray diffraction, thermal analysis and elemental analysis. The Cu(II) ion has a distorted square planar geometry, extended to (4 + 2) weak coordination by two nitrogen atoms of the cyano group. The coordination sphere around the Ni(II) ion should be described as a 4 + 2 geometry with the four cyano groups and the axial coordination site is located at the imidazole ring though a weak Ni···π interaction. The coordination bond is much stronger than the Ni···π interactions and it is expected that the formation of the coordination bond will affect more significantly the position of the absorption bands associated with the vibrations of the ligand. In addition, the out-of-plane modes of 4(5)-Meim are shifted to higher frequencies relative to free ligand. We propose that these shifts are indicative of the weak CH∙∙∙π and Ni∙∙∙π interactions, according to the crystallographic and spectroscopic data.  相似文献   

7.
Nano-wires and nano-rods of a new three-dimensional cadmium(II) coordination polymer, {[Cd3(3-pyc)4(NCS)2(H2O)4]·2H2O} n (1); 3-Hpyc = 3-pyridinecarboxilic acid, were synthesized by a sonochemical method in two different concetrations. The morphology of the nano-structures depend strongly on reactants’ concentration. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, elemental analyses and IR spectroscopy. Compound 1 was structurally characterized by single-crystal X-ray diffraction and is a three-dimensional polymer with two types of Cd(II) coordination environments.  相似文献   

8.
A new one-dimensional polymeric copper(II) complex, [Cu2(heae)(SCN)2] n  · nH2O [H2heae is N,N′-bis(N-hydroxyethylaminoethyl)oxamide], has been synthesized and characterized by elemental analysis, molar conductivity measurement, IR and electronic spectra studies, and single-crystal X-ray diffraction. The structure of the complex exhibits a neutral one-dimensional polymeric copper(II) zigzag chain [Cu2(heae)(SCN)2] n constructed by μ-trans-heae and double μ-1,3-thiocyanate ligands. The environment about copper can be described as a square-pyramid. The neighboring second building units (SBUs), [Cu(trans-heae)Cu]2+, are unequal with Cu···Cu separations of 5.287 and 5.273 ? for Cu1···Cu1i and Cu2···Cu2ii, respectively. The double thiocyanate ligands function as μ(1,3)-bridges to link these unequal SBUs thereby forming zigzag chains with a Cu1···Cu2 separation of 5.454 ?. The hydrogen bonds in the crystal structure self-assemble the one-dimensional chains into a three-dimensional supramolecular structure. The interaction of the polymeric copper(II) complex with herring sperm DNA (HS-DNA) has been investigated by using absorption and emission spectra, electrochemical techniques and viscometry. The results reveal that the polymeric copper(II) complex interacts with HS-DNA via a groove binding mode with the intrinsic binding constant of 1.38 × 104 M−1. To the best of our knowledge, this is the first example about the structure and DNA-bonding studies of a one-dimensional polymeric copper(II) complex that is bridged alternately by trans-oxamidate and double-thiocyanate ligands.  相似文献   

9.
A novel ligand L, 4-(1-hydroxy-3-oxo-3-phenylpropenyl)-1-methylpyridinium was synthesized and identified by NMR spectra and X-ray single crystal structure analysis from L · CH3SO4 (1L). Through self-assembling reactions, two new CuII/LaIII-organic complexes, [CuL2(SCN)][SCN] · H2O (2Cu) and [LaL2(SO4)Cl2] · (toluene) (3La), have been synthesized and characterized by X-ray crystallography. Structural analysis of 1L revealed that L and HSO4 coexist in a unit cell. For 2Cu, Cu(II) ion show a five-coordinated structure with a highly compressed square pyramid configuration; For 3La, each La(III) ion has an eight-coordinated structure with a distorted capped pentagonal bipyramidal geometry. It should be mentioned that supramolecular framework was formed via a number of hydrogen bonding interactions. Here, intramolecular C–H···O hydrogen bonding interactions stabilized and restricted the distortion between different rings. On the contrary, intermolecular hydrogen bond, e.g. C–H···O dual hydrogen bond interactions (1L), O5-involving triple C–H···O/O–H···O(N) hydrogen bond (2Cu) and triple C–H···Cl hydrogen bonding(3La), greatly affect geometric distortion between rings from ligand. Finally, we believe that the cooperative effect plays more important roles in supramolecular self-assembly.  相似文献   

10.
Four novel divalent transitional metal succinates (suc) with nicotinamide (nia), {[M(μ-suc)(H2O)2(nia)2]·2H2O} n [M = Mn (1), Ni (2)], [Cu(suc)(nia)2] (3) and [Ni(H2O)4(nia)2](suc)·(H2suc) (4), have been synthesized and characterized by elemental analyses, IR and TG-DTA. X-ray analyses of 2 and 4 reveal that they crystallize in a triclinic space group P[`1]. P\bar{1}. Complex 2 is a 1-D coordination polymer, in which the metal(II) ions exhibit an octahedral geometry with two suc, two nia and two aqua ligands. The nia ligand is N-bonded, while the suc ligand bridges the metal centres through the carboxylate groups. 4 contains the [Ni(H2O)4(nia)2]2+ complex cations, uncoordinated suc and H2suc species, which are connected into a two-dimensional layered structure by the combination of N–H⋯O and OW–H⋯O hydrogen bonds. This is one of the scarce examples encountered in coordination chemistry, which contains uncoordinated suc and H2suc at the same time. The spectroscopic and structural analysis, luminescent and magnetic properties and the antimicrobial activities of the synthesized complexes were investigated.  相似文献   

11.
Bilayered diffusion and hydrothermal synthetic methods using pyridine (py) and 2,6-dimethylpyrazine (dmpz) as weak bases and small terminal ligands generated two Cd(II) and Co(II) 1D coordination polymers with dinuclear metal clusters as secondary building units (SBUs) from an organic bridging ligand, 1,1′-biphenyl-3,3′-dicarboxylic acid (H2 L). They are {[Cd2(L)2(py)4] (py)(CH3OH)} n (1) and [Co2(L)2(dmpz)4(H2O)] n (2). Compounds 1 crystallizes in the monoclinic space group P2(1)/c, while 2 crystallizes in the triclinic space group P-1. Especially, compound 2 possesses the 1D chain structure that contains two linked left-handed and right-handed helices. Fluorescent measurements for 1 display strong blue light emissions with the maximum emission at 396 nm with the excitation of 320 nm. Magnetization study shows the existence of weak antiferromagnetic coupling for 1 with the negative −E 2/k value of −1.3 K.  相似文献   

12.

Abstract  

A new chiral Cu(II) complex, Cu3(phen)3(H2O)(BTA)2·13H2O (1) (H3BTA = benzene-1,3,5-triacetate acid and phen = phenanthroline) has been prepared by solvothermal synthesis and structurally characterized by IR, elemental analysis, and single crystal X-ray diffraction. This complex crystallizes in the chiral space group C2 and has similar one-dimensional chains, which are further bridged by μ 2-H2O to form a two-dimensional layer structure. The nonlinear optical property and magnetic property were investigated.  相似文献   

13.
Two new complexes, [M2(L)2(bpy)2](ClO4)2 [L = methyl salicylate, bpy = 2,2′-bipyridine, M = Cu (1) and Zn (2)] have been synthesized and structurally characterized by X-ray structure analyses. The centrosymmetric dimeric structure consists of a binuclear unit, in which M (M = Cu or Zn) atoms are bridged by two phenol oxygen atoms as a μ 2-bridged. The neighboring binuclear units interact with each other by two kinds of weak contacts: one kind is π–π stacking by π–σ attraction with an edge-to-face C–H···π interaction, and the second type is a H-bonding interaction, which extends the binuclear unit into a 3D network. Magnetic measurements confirm that 1 presents a very strong intradinuclear ferromagnetic coupling between the copper(II) ions.  相似文献   

14.
The synthesis of neutral dinuclear iron–nickel unsymmetrical Schiff base complexes 3 and 4 was achieved via a template reaction involving equimolar amounts of alkyl or aryl “half-unit” precursors, respectively, Fc–C(O)CH=C(CH3)N(H)R (1: R = CH2CH2NH2; 2: R = o-C6H4NH2; Fc = CpFe(η5-C5H4); Cp = η5-C5H5), 5-bromosalicylaldehyde and nickel(II) acetate tetrahydrate in a refluxing CH2Cl2/MeOH (1:1) mixture. The ionic trinuclear unsymmetrical complex 5 was prepared by reacting its dinuclear precursor 3 with the arenophile source, [Cp*Ru(NCCH3)3]PF6 (Cp* = η5-C5(CH3)5), in refluxing CH2Cl2 for 2 h, whereas the trinuclear species 6 was formed upon regioselective π-complexation of the 5-bromosalicylidene ring of 4 by [Cp*Ru]+ at room temperature overnight. All the new compounds were adequately characterized by analytical and spectroscopic techniques and, in addition, the crystal and molecular structures of the “half-unit” 1, the binuclear complex 4 and its hemisolvate adduct 4 · 0.5CH3OH, the trinuclear Schiff base compound 5 · 2(CH3)2CO, and the mixed sandwich metalloligand 7 have been determined by X-ray crystallography. Both organometallic–inorganic hybrids 5 and 6 contain the neutral electron-releasing ferrocenyl group, and the cationic electron-withdrawing ruthenium mixed sandwich, linked through the unsymmetrical tetradentate Schiff base complex {Ni(ONNO)}. UV–vis, 1H and 13C NMR as well as electrochemical data clearly indicate a mutual donor–acceptor electronic influence between the organometallic termini. Furthermore, X-ray crystal structure analysis of 5 · 2(CH3)2CO reveals the partial delocalization of bonding electron density throughout the dinucleating nickel Schiff base ligand. Dedicated to Prof. Didier Astruc, a true friend, an outstanding lecturer and scientist, in honor of his pioneering research efforts and accomplishments in the fields of organometallic chemistry, dendrimers and their applications in nanocatalysis.  相似文献   

15.
Two 3D coordination polymers, [Cd(BDC)(Medpq)·H2O]n 1, and [Co(BDC)(Medpq)·H2O] n 2 (BDC = terephthalic acid, Medpq = 2-Methyldipyrido[3,2-f:2′,3′-h]quinoxaline), have been synthesized by self-assembly. The structure analyses show that both of the two coordination polymers are formed by 1D infinite chains through non-covalent interactions, and both of them are based on 1D zigzag ones. The photoluminescent study of the coordination polymer [Cd(BDC)(Medpq)·H2O] n shows that it exhibit fluorescent emission bands at 567.7 nm.  相似文献   

16.
Three types of di- and trimethyltin(IV) polymers [Me2Sn(C9H4N2O4)]n · 4H2O 1, [(Me3Sn)2(C9H4N2O4)]n · H2O 2 and [(Me3Sn)2(C9H4N2O4)]n · CH3OH 3 have been synthesized by the reaction of trimethyltin chloride with benzimidazole-5,6-dicarboxylic acid under three different experimental conditions. All the complexes were characterized by elemental analysis, IR, NMR (1H, 13C, 119Sn) spectroscopy and X-ray crystallography diffraction analysis. The structure analyses reveal that complex 1 has a 1D helical chain in which benzimidazole-5,6-dicarboxylic acid act as a tetradentate (O,O-chelation) ligand coordinating to dimethyltin (IV) ions, two water molecules take part in the coordination giving seven-coordinated tin centers in the component. Complex 2 and 3 are 2D and 3D corrugated polymers in which the deprotoned acid as tetradentate ligand affords by three oxygen atoms and a nitrogen atom.  相似文献   

17.
Three chromium(III) coordination supramolecules, [CrQ2(H2O)Cl]·H2O 1, [Cr(Pic)2(phen)]·NO3·2.5H2O 2, [Cr(ATA)(phen)]·CH3OH·3H2O 3 (HQ = Quinoline 2-acid, HPic = Picolinic 2-acid, H3ATA = Ammonia triacetic acid, phen = 1,10-Phenanthroline), have been synthesized solvothermally and characterized by single-crystal X-ray diffraction, IR spectra, UV-Vis absorption spectra and elemental analysis. The surface electron behavior of chromium complexes have been studied emphatically by surface photovoltage spectroscopy (SPS). Structural analyses indicate that the three complexes are all molecular complexes with the ligands of carboxylate groups; and, they are further connected into supramolecules by hydrogen bonds and π–π interactions. The results of SPS show that there are positive photovoltage response bands within 300–800 nm, which indicate that they all possess obvious photoelectric conversion properties. Energy-band theory for semiconductors and crystal field theory have been combined to analyze and assign the SPS bands. There are three types of band-to-band transitions in the SPS of the complexes; i.e., LMCT bands for Cl → Cr, O → Cr, N → Cr. The similarities and differences between the SPS and UV-Vis absorption spectra for the three complexes were compared and reasonably explained. There was a good correlation between the SPS and UV-Vis absorption spectra.  相似文献   

18.
Three M(II)-squarate complexes, [Co(sq)(H2O)(Nmim)4] (1), [Zn(μ1,3-sq)(H2O)2 (Nmim)2] n (2) and [Cd(μ1,3-sq)(H2O)2(Nmim)2] n (3) (sq = squarate, Nmim = N-methylimidazole) have been synthesized and characterized by elemental, spectral (IR and UV–Vis.) and thermal analyses. The molecular structures of the complexes have been investigated by single crystal X-ray diffraction technique. The squarate ligand acts as two different coordination modes as a monodentate (in 1) and bis(monodentate) (O 1– O 3 ) bridging ligand (in 2, 3). The Co(II) atom has a distorted octahedral geometry with the basal plane comprised of three nitrogen atoms of Nmim ligands and a oxygen atom of squarate ligand. The axial position is occupied by a nitrogen atom of Nmim and one aqua ligand. The crystallographic analysis reveals that the crystal structures of 2 and 3 are one-dimensional linear chain polymers along the c and b axis, respectively. The configuration around each metal(II) ions are distorted octahedral geometry with two nitrogen atoms of trans-Nmim, two aqua ligands and two oxygen atoms of squarate-O1,O3 ligand. These chains are held together by the C–H···π, π···π and hydrogen-bonding interactions, forming three-dimensional network.  相似文献   

19.
Ligand L (H3L = Glycylglycine, N-[1-(2-hydroxy,5-bromophenyl)propylidene]) has been prepared which contain flexible dipeptide group and substituted phenol group. The ligand react with Cu(NO3)2 to give the metallo-ligand [CuL], in which L acting as quadridentate ONNO chelate, coordinate to Cu(II) ion. The metallo-ligand [CuL] is rigid and has multifunctional groups. Reaction of metallo-ligand with Sr(NO3)2 leads to the formation of the title complexes [Sr(H2O)4(CuL)2]· (CuL)·2.25H2O (1). This heteronuclear compound has been characterized by elemental analyses, spectroscopic analyses, and single crystal diffraction. Structural analyses reveal that the complex was crystallized in triclinic space group P-1 and has intricate 2D net-structure, which contain an infinite 1D [Sr(H2O)4(CuL)2]+ ladder-like structure. In addition ESR (electron spin resonance) property and thermogravimetric analysis of 1 are discussed in detail.  相似文献   

20.
Three novel one-dimensional (1D) coordination polymers with general formula {[M(μ-sq)2(amp)2]·H2O}n [M=Cu(II) (1), Zn(II) (2)] and [Cd(μ-sq)2(amp)2]n (3) [sq: Squarate; amp:2-aminomethylpyridine] have been prepared and spectroscopically studied. Each metal (II) ion in 13 is octahedrally coordinated by two sq and two amp ligands. The amp ligands are N,N′ coordinated, while the sq ligands bridge the metal centers forming 1D linear chain structure. The individual chains are linked by O–H···O hydrogen bonds involving the hydrogens of water molecules (12), amino hydrogens and squarate O atoms (13). The hydrogen bonded layers are further assembled into three-dimensional supramolecular networks by weak aromatic π–π interactions. EPR results indicate that the ground state of the paramagnetic electron in 1 and Cu2+ doped complexes 23 is dx2 - y2 d_{{x^{2} - y^{2} }} . Magnetic measurements reveal that complex 1 shows paramagnetic behavior.  相似文献   

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