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1.
Three new heterometallic coordination compounds, namely, [KCu(I3)(L)2(H2O)2]n(1), [KCu(I3)(L)2(H2O)]n(2) and [CuK4(I3)2(L′)4]n(3), were prepared and characterized(HL=5-methylpyrazine-2-carboxylic acid, HL′=p-tolylacetic acid). Structural studies revealed that 1 and 2 exhibit 3D frameworks with rectangular channels occupied by triiodide ions. Both compounds can be symbolized as a 5-connected net with pcu topology. In compound 3, a one-dimensional polyhedral chain is connected by hexanuclear mask like clusters [Cu2K4O8]. These chains are further linked each other via rare(1,1,3,3)-triiodide ion-bridging units to generate a 3D(4,5,6)-connected net with the point symbol of {12}2{4·122}4{46}{48·62}4{49·66}4. It is noteworthy that water-induced reversible dissolution/reorganization processes occur between 1/2 and [Cu(L)2(H2O)]n·3nH2O. The thermal and photoluminescence properties of compounds 1, 2, and 3 were investigated as well.  相似文献   

2.
Fourteen bis(citrato)germanates(IV) and bis(citrato)stannates(IV) were prepared, in particular, [M(H2O)6][Ge(HCit)2] · 4H2O (M = Mg (I), Mn (II), Fe (III), Co (IV), Ni (V), Cu (VI), Zn (VII)) and [M(H2O)6][Sn(HCit)2] · nH2O (M = Mg, n = 4 (VIII); Mn, n = 2 (IX); Fe, n = 4 (X); Co, n = 4 (XI); Ni, n = 4 (XII); Cu, n = 4 (XIII); Zn, n = 3 (XIV)) (H4Cit is citric acid). The purity and the composition of the products were determined by a set of physicochemical methods including elemental analysis, thermogravimetry, and IR spectroscopy. The structures of I, II, IV, VI, VII, VIII, XI, and XII were determined by X-ray diffractometry. All eight crystals composed of centrosymmetrical octahederal [M(H2O)6]2+ cations, [Ge(HCit)2]2? (or [Sn(HCit)2]2?) anions, and crystal water molecules are isostructural. The structural units in I, II, IV, VI, VII, VIII, XI, and XII are connected by systems of hydrogen bonds to form a three-dimensional framework.  相似文献   

3.
Two new Co(II) complexes, [Co2(H2O)(Bipy)2(Bript)2] n (I) and [Co(H2O)(Phen)(Bript)] · H2O (II), where H2Bript = 4-bromoisophthalic acid, Bipy = 2,2??-bipyridine, and Phen = 1,10-phenanthroline, have been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Complex I has binuclear units in which two Co2+ ions are bridged by two carboxylate groups and a coordinaiod-water molecule, and the binuclear units are connected by Bript to generate a 1D helical chain. These 1D helical chains are further linked by ????? stacking interactions to form a 3D supramolecular network, while complex II has a 2D layer motif. In I and II, there exists extensive hydrogen bonding interactions. The thermal behavior of the two corresponding complexes have briefly been investigated.  相似文献   

4.
Four coordination polymers associated with bent bis(imidazole) 1,3-bis(imidazol-l-yl-methyl)benzene (mbix) and isophthalic acid (H2ip) or 5-methylisophthalic acid (H2mip) ligands, formulated as {[Cd(mbix)(mip)]·H2O} n (1), {[Co(mbix)(mip)]·0.4H2O} n (2) [Ni(mbix)(mip)H2O] n (3) and [Ni(mbix)(ip)] n (4), were synthesized under hydrothermal conditions and characterized by physico-chemical and spectroscopic methods. Complexes 1 and 2 are isomorphous and exhibit a 1D loop-like chain. Complex 3 features a 2D (4,4) layer, which further extends into an unusual 2D (3,5)-connected 3,5L2 double-layered supramolecular network via classical O–H···O hydrogen bonding interactions. Complex 4 is a 3D network, which shows a rare binodal (3,5)-connected 3,5T1 framework. Moreover, the luminescence and catalytic properties of the complexes for the degradation of methyl orange by sodium persulfate in a Fenton-like process are reported.  相似文献   

5.
Two new metal–organic coordination polymers {[Co(L1)(nip)]·H2O} n (1) and [Co(L2)(ip)] n (2) (H2ip = isophthalic acid, L1 = 1,3-bis(benzimidazol-1-ylmethyl)benzene, L2 = 1,4-bis(5-methylbenzimidazol-1-ylmethyl)benzene, H2nip = 5-nitroisophthalic acid) have been synthesized under hydrothermal conditions and characterized by physicochemical and spectroscopic methods as well as single-crystal X-ray diffraction analysis. The analysis reveals that complex 1 has a 1D double chain structure connected by L1 and nip2? ligands, which is further assembled into a 3D bbf (moganite network) supermolecular framework via two types of C–H···O hydrogen bond interactions. Complex 2 possesses a 3D MOF with a four-connected cds (CdSO4 network) topology. The fluorescence and catalytic properties of the complexes for the degradation of Congo red have been investigated.  相似文献   

6.
Based on 5-mercapto-1H-tetrazole-1-methanesulfonic acid disodium salt (Na2mtms) and 4,4′-bipyridine (bpy) as ligands, four new transition metal complexes, namely {[Cd2(mtms)(bpy)2(OAc)2]·H2O} n (1), {[Cd(mtms)(bpy)2(H2O)2]2·bpy·4H2O} n (2), {[Zn2(μ 2-OH)(mtms)(bpy)3(H2O)]·ClO4·H2O} n (3), and {[Co(mtms)2(bpy)(H2O)2]·[Co(bpy)2(H2O)4]·H2O} n (4), have been synthesized and characterized by single-crystal X-ray diffraction. Complex 1 features a pillared-layer coordination architecture linked by acetate, mtms, and bridging bpy ligands. Complex 2 has a 1D polymeric structure with [Cd(mtms)(bpy)2(H2O)2] as the repeating unit; these infinite chains are further connected into a 3D supramolecular framework through π–π stacking of bpy ligands. In complex 3, the mtms ligand combined with μ 2-OH bridges two Zn atoms to form a dimer structure, which is different from that of complex 2. Complex 4 shows a 3D supramolecular network containing infinite [Co(mtms)2(bpy)(H2O)2]2? anionic chains and free [Co(bpy)2(H2O)4]2+ cationic components. The luminescence properties of 1 and 2 and the electrochemical properties of 3 are reported.  相似文献   

7.
The hydrothermal reactions of nitrate or chloride salts of Co(II), Zn(II), Cd(II), Hg(II) and Ag(I) with an unsymmetrical benzotriazole derivative 1H-1,2,3-benzotriazole-1-propionic acid (Hbtap) afforded five new metal–organic coordination polymers with formula of [M(btap)2(H2O)2] n (M = Co 1, Zn 2, Cd 3), [Hg(btap)Cl] n (4) and {[Ag(btap)]·H2O} n (5), which were characterized by X-ray diffraction and spectroscopic methods. The anionic btap? ligands in these complexes assume the same anti conformation, but show different coordination behaviors toward transition metal ions. Complexes 1, 2 and 3 are isostructural and reveal infinite one-dimensional (1D) looped-chain structures constructed by hexacoordinated metal centers and 2-connected btap? bridges. Complex 4 features 1D zigzag polymeric arrays, which are interlinked with each other resulting in a chiral three-dimensional (3D) 4-connected framework. In complex 5, the 3-connected ligands join Ag(I) atoms into a 1D ribbon motif. The photoluminescence spectra of three d10 metal complexes 2, 3 and 4 were measured at room temperature. The emission peaks of these complexes resemble that of the free ligand and can be ascribed to the intraligand π–π* transitions.  相似文献   

8.
Four homochiral coordination polymers incorporating two chiral reduced Schiff base ligands, namely, [Cu(L1)(H2O)]·H2O (1), [Zn2(L2)2] (2), [Co(L2)(H2O)] (3), and [Ni(L2)(H2O)] (4) (H2L1 = N-(4-carboxyl)benzyl-l-alanine, H2L2 = N-(4-carboxyl)benzyl-l-leucine) have been obtained by hydrothermal methods and characterized by physico-chemical and spectroscopic methods. X-ray crystallographic analysis reveals that complex 1 exhibits a chain structure with 1D channels. Complexes 24 all are 3D network structures with 1D channels in which the isobutyl group of the ligand points toward to the channel. Complex 2 displays strong photoluminescent emission in the purple region.  相似文献   

9.
Two coordination polymers, [Co(L1)(IPA] n (1) and {[Ag(L2)(HMIPA)]·H2O} n (2) (H2IPA = isophthalic acid, L1 = 1,2-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, H2MIPA = 5-methylisophthalic acid, L2 = 1,6-bis(5,6-dimethylbenzimidazol-1-yl)hexane, have been synthesized and characterized by physicochemical and spectroscopic methods, as well as single-crystal X-ray diffraction. In 1, six-coordinated cobalt centers are bridged by L1 and IPA2? ligands to generate a (4,4) two-dimensional layer. However, complex 2 features a 1D chain structure, which is further extended by O–H···O hydrogen bonding interactions into a 2D supramolecular layer with (63) topology. The fluorescence and thermal gravimetric analysis of both complexes were also explored. Furthermore, the complexes 1 and 2 exhibit remarkable catalytic properties for the degradation of methyl orange dyes in a Fenton-like process.  相似文献   

10.
Two novel coordination complexes, namely, [Cd(2-NOA)2(TBZ)2] (1) and [Mn(2-NOA)2(H2O)2]n (2) (2-NOAH = 2-naphthoxyacetic acid), have been hydrothermally synthesized through the reaction of 2-naphthoxyacetic acid with or without N-donor ancillary coligand (thiabendazole, TBZ) in the presence of divalent transition-metal salts. Complex 1 is a zero-dimensional (0D) molecule, and the self-complementary C–H···O hydrogen bonds extend these molecules into a 2D supramolecular framework. In polymer 2, 2-NOA ? acts as a bridging ligand to bind Mn(II) ions to form a 2D supermolecular assembly. Also, IR spectra, powder X-ray diffraction, fluorescence properties and thermal decomposition process of complexes were investigated. The effect of the TBZ base ligand and the complex 1 on the antimicrobial activity against Candida albicans was studied.  相似文献   

11.
Three new cobalt complexes, {[Co5(tci)2(bimb)33-O)2(H2O)2]·3DMF·4H2O} n (1), {[Co3(tci)2(bib)]·2DMF·2H2O} n (2) and {[Co(Htci)(bpea)0.5]·H2O} n (3) (H3tci = tris(2-carboxyethyl)isocyanurate, bimb = 4,4′-bis(imidazol-1-yl)biphenyl, bib = 1,4-bis(imidazol-1-yl)benzene, bpea = 1,2-bis(4-pyridyl)ethane, DMF = N,N′-dimethylformamide), have been successfully synthesized through the assembly of Co(II) ions, H3tci and different N-donor ligands, respectively. All complexes were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray powder diffraction (XRPD). Complex 1 exhibits a 3D three-fold parallel interpenetrated 3D → 3D structure with (65·8) CdSO4 topology. Complex 2 is built from [Co32-Ocarboxyl)2(CO2)4] clusters and linear bib ligands, displaying a two-fold parallel interpenetrated (3,8)-connected (43)2(46·618·84) topology, while complex 3 is a 3D pillar-layered structure involving an infinite -Co-(µ2-Ocarboxyl)(CO2)-Co-chain. The diverse structures of the three complexes indicate that the skeletons of different N-donor ligands play an important role in the assembly of such different frameworks. In addition, magnetic investigation indicates that besides spin-orbit coupling of Co(II) ions, there exist antiferromagnetic exchange interactions in Co5 and Co3 clusters of 1 and 2, respectively.  相似文献   

12.
Two new coordination polymers, formulated as [Co(L1)(btec)0.5] n (1) and {[Co(L2)(bdc)]·H2O} n (2) (L1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2bdc = 1,3-benzenedicarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylic acid, L2 = 1,3-bis(benzimidazol-1-ylmethyl)benzene), have been hydrothermally synthesized and characterized by physicochemical and spectroscopic methods as well as single-crystal X-ray diffraction. The cobalt atoms present different environments, with a trigonal pyramidal geometry in 1 and a distorted octahedral configuration in 2. Complex 1 shows a 2D (4,4) network linked by L1 and btec4? anions, giving an uninodal 4-connected sql topology with a point symbol of {42·62}, while complex 2 displays a 1D ladder-like chain structure, which is further assembled into a 3D supramolecular architecture via C–H···π hydrogen bonding interactions. The fluorescence properties of both complexes have been investigated in the solid state.  相似文献   

13.
Copper(II) salts were reacted with various quinoline aldehyde chalcogensemicarbazones to yield compounds formulated as Cu(HL)X2 · nH2O (I: HL = quinoline aldehyde thiosemicarbazone (HL1), X = ClO4, n = 2; II: HL = quinoline aldehyde 4-C2H5-thiosemicarbazone (HL1a), X = NO3, n = 0; III: HL = quinoline aldehyde semicarbazone (HL2), X = ClO4, n = 3 and IV: HL = quinoline aldehyde 4-Ph-semicarbazone (HL2a), X = NO3, n = 1). Regardless of the reagent ratio, the products were compounds having the metal: ligand ratio of 1: 1, where the organic ligand was coordinated tridentate in a molecular form. Single-crystal X-ray diffraction showed that, depending on the chalcogen atom in the organic ligand (S or O), the substituent in the 4th position (at the terminal nitrogen atom), and the specifics of the acido ligand, complexes I–IV had appreciably differing molecular structure organizations. The structures of I and III are formed by a 1D charged coordination polymer, ClO 4 ? anions, and water molecules and may be described by the formula [Cu(HL)(H2O)(ClO4)] n (ClO4) n · nH2O. Copper(II) coordination polyhedra in I and II are (4 + 2) and (4 + 1 + 1) tetragonal bipyramids, respectively. In II and IV, the structures are monomeric and can be described as [Cu(HL1a)(NO3)2] with the metal coordination polyhedron shaped as a (4 + 1) tetragonal pyramid in II and as [Cu(HL2a)(H2O)(NO3)](NO3) with the metal coordination polyhedron shaped as a (3 + 2) trigonal bipyramid in IV. The structure of II is built of molecular complexes, each comprising, apart from ligand HL1a, two monodentate coordinated NO 3 ? groups. The oxygen atom of one anion together with the NNS donor atom set of ligand HL1a form the base, and the oxygen atom of the other anion is in the apex of the coordination polyhedron. In IV, the structure is ionic and built of NO 3 ? anions and [Cu(HL2a)(H2O)(NO3)]+ complex cations, where a cationic coordination polyhedron has a trigonal-bipyramidal configuration with organic ligand HL2a positioned along the long edge. The bipyramidal base is made up by the oxygen atoms of the coordinated water molecule and monodentate nitrato group and the nitrogen atom N2 of the azomethyne group.  相似文献   

14.
Using Cu(II), Mn(II) or Co(II) salt and the flexible ligands, N-[(4-carboxyphenyl)-sulfonyl]glycine (H3L1) and N-[(3-carboxyphenyl)-sulfonyl]glycine (H3L2), a series of new coordination polymers, [Mn(phen)(H2O)4][HL1] (1), [Co3(L1)2(bipy)3(H2O)6]n·8nH2O (2), [Cu4(L1)2(OH)2(bipy)4]n·12nH2O (3), [Na(H2L1)(H2O)]n (4), [Mn2(HL2)2(dpe)3(H2O)2]n·ndpe (5), (phen = 1,10-phenanthroline, bipy = 4,4′-bipyridine, dpe = 1,2-di(4-pyridyl)ethylene), varying from 0D to 3D, have been synthesized and structurally characterized. Compound 1 has a [Mn(phen)(H2O)4]2+ cation and a HL12− anion. Compound 2 features a new 1D triple chain, based on octahedral cobalt atoms bridged by bipy molecules and terminally coordinated by two H3L1 ligands. Compound 3 has a 2D layered structure, constructed from new alternating chains where H3L1, hydroxyl and water molecules simultaneously act as bridging ligands. Compound 4 possesses a bilayer structure in which two adjacent layers are pillared by H3L1 ligands into a 2D bilayer network. Compound 5 is a unique 3D coordination polymer in which each Mn center binds two trans-located dpe molecules. The thermal stability as well as magnetic properties of 5 was also studied. This work and our previous work indicate that the positional isomer of the anionic N-[(carboxyphenyl)-sulfonyl]glycine is important in the construction of these network structures, which are also significantly regulated by the metal centers.  相似文献   

15.
Four new fluorochromatouranylates, namely, K[UO2(CrO4)F] · 1.5H2O (I), Rb[UO2(CrO4)F] · 1.5H2O (II), Rb[UO2(CrO4)F] · 0.5H2O (III), and Cs[UO2(CrO4)F] · 0.5H2O (IV), have been synthesized, and their crystallographic characteristics have been determined. All the compounds crystallize in monoclinic system, space group P21/c, with the unit cell parameters a = 13.1744(5) Å, b = 9.4598(3) Å, c = 13.0710(4) Å, β = 103.746(1)°, Z = 4, R = 0.0235 (I); a = 13.5902(7) Å, b = 9.5022(4) Å, c = 13.2271(6) Å, β = 102.914(2)°, Z = 4, R = 0.0247 (II); a = 24.7724(8) Å, b = 12.6671(4) Å, c = 9.4464(3) Å, β = 97.661(1)°, Z = 8, R = 0.0448 (III); a = 25.725(1) Å, b = 12.8261(5) Å, c = 9.4929(4) β = 97.208(1)°, Z = 8 (IV). The pairs of compounds I and II and compounds III and IV are isostructural. Crystals of compounds I–III have been subjected to complete X-ray diffraction study. It has been established that the structures of compounds I–III are built of [UO2(CrO4)F] n n? layers, which are parallel to the (100) plane and linked into a framework by alkali-metal cations located between layers, together with water molecules. The effect of topological and geometric isomerism on the structural features of 34 known uranyl compounds of the AT3M2 crystallochemical group, to which the studied compounds I–III also belong, is discussed.  相似文献   

16.
Four Ln(III) coordination polymers, [La2(HBidc)3(H2O)] n (I), [Pr2(HBidc)3(H2O)] n (II), [Sm2(HBidc)3(H2O)] n (III), and [Gd2(HBidc)3(H2O)] n (IV), were synthesized hydrothermally by treating Ln(NO3)3 · 6H2O, NaOH, and H3Bidc (H3Bidc = 1H-benzimidazole-5,6-dicarboxylic acid) at 180°C and characterized by elemental analysis, IR spectra, and single-crystal X-ray structure analyses. Complexes I–IV are isostructural, and each complex contains two crystallographically independent Ln(III), one is seven-coordinated, while the other is eight-coordinated. X-ray crystallography reveals that the complex consists of 3D frameworks with the (34·44·52·66·710·8·9)(3·4·5)(3·4·5) topology. Furthermore, the photoluminescence properties of III has been studied.  相似文献   

17.
Novel metal organic frameworks including {(pipzH2)[Mn(py-2,3-dc)2]·7.75H2O}n, 1, {(pipzH2)[Zn(py-2,3-dc)2]·4H2O}n, 2, [Cd(py-2,3-dc)(H2O)3]n, 3 and {(pipzH2)[Hg4Cl10]}n, 4, in which pipz is piperazine and py-2,3-dcH2 is pyridine-2,3-dicarboxylic acid were synthesized applying a proton transfer ion pair i.e. (pipzH2)(py-2,3-dcH)2 and corresponding metallic salts and studied by IR, 1H NMR, 13C NMR spectroscopy and single crystal X-ray diffractometry. The space group of compounds 1 and 4 are P21/c and C2/c of monoclinic system, respectively. The crystal dimensions are a = 20.108(2) Å, b = 19.910(2) Å, c = 12.997(1) Å, β = 94.354(2)° for 1 and a = 15.940(1) Å, b = 11.2690(9) Å, c = 11.1307(9) Å, β = 90.685(2)° for 4. The crystal structures of 2 and 3 have been reported previously. However, their solution studies are discussed here. The compounds had all polymeric structures. Although ZnII, CdII and HgII were elements of the same group, their behavior against the ion pair was essentially different. Various supramolecular interactions mainly hydrogen bonds of the type O-H?O, N-H?O, C-H?O, N-H…Cl and C-H?Cl were observed in the structures. There was an unusual and huge water cluster in the structure of compound 1. The solution states of compounds 1–4 were studied and reported. The protonation constants of pipz and py-2,3-dc, the py-2,3-dc/pipz proton transfer equilibrium constants and stoichiometry and stability of the system with Mn2+, Zn2+, Cd2+ and Hg2+ ions in aqueous solution were investigated by potentiometric pH titrations.  相似文献   

18.
Three new Cu(II)-Ln(III) heterometallic coordination polymers based on two N-heterocyclic carboxylic ligands, {[LnCu(L1)2(L2)(H2O)2]·mH2O} n (Ln = La(1), Nd(2), Gd(3), m = 2 (for 1), 1 (for 2, 3), H2L1 = quinolinic acid, HL2 = nicotinic acid), have been synthesized and characterized. 1 has a two-dimensional (2D) layer structure with a Schl?fli symbol of (44.62), while complexes 2 and 3 are isostructural and have three-dimensional (3D) structures with a Schl?fli symbol of (3.4.5)2(32.42.52.614.74.83.9)(32.63.7) of 3-nodal net. Magnetic investigations suggest that antiferromagnetic coupling exists between NdIII and CuII in 2, while weak ferromagnetic coupling between GdIII and CuII in 3. The difference of magnetic properties between 2 and 3 has been discussed.  相似文献   

19.
Three new cobalt(Ⅱ) coordination compounds,[Co(3,3’-Hbpt)2(H2pm)(H2O)2]·2H2O(1),[Co(4,4’-Hbpt)(pm)0.5(H2O)]·3H2O (2) and [Co(3,4’-Hbpt)(pm) 0.5 (H2O)3]·2H2O(3)(3,3’-Hbpt=3,5-bis(3-pyridyl)-1H-1,2,4-triazole;4,4’-bpt=3,5-bis(4-pyridyl)1H-1,2,4-triazole,3,4’-Hbpt=3-(3-pyridyl)-5-(4’-pyridyl)-1H-1,2,4-triazole and H4pm=pyromellitic acid) have been synthesized by hydrothermal reactions.Single-crystal X-ray diffraction reveals that compound 1 has a one-dimensional (1D) chain network,2 exhibits a four-connected three-dimensional (3D) structure with 1D open channels encapsulated by water molecules,while 3 displays a regular two-dimensional (2D) architecture connected through 1D metal helical chains.In addition,the efficacy of compounds 1-3 as additives to promote the thermal decomposition of ammonium perchlorate (AP) is explored by differential scanning calorimetry (DSC).  相似文献   

20.
Two new ionic complexes built on polyoxometalate anions of [CoW12O40]6? and Ln3+ (Ln = Ce, Nd) cations, namely [Ce(CoW12O40)(NMP)2(H2O)6][Ce(NMP)(H2O)8] · 3H2O · NMP (I) and [Nd(CoW12O40)(NMP)2(H2O)6][Nd(NMP)(H2O)8] · 7H2O (II) (NMP = N-methyl-2-pyrrolidone) have been synthesized. Single crystal X-ray crystallographic analyses (CIF files CCDC nos. 704837 (I) and 689561 (II)) revealed that the structures of two complexes were similar, which crystallize in the P21/n monoclinic space group. Complexes I and II were both ionic clusters and the coordination numbers of Ln3+ (Ln = Ce, Nd) were nine. The unit cell parameters for I: a = 17.551(4), b = 17.783(4), c = 26.729(5) Å, β = 101.33(3)°, V = 8180(3) Å3, Z = 4. The unit cell parameters for II: a = 17.571(3), b = 17.750(3), c = 28.989(9) Å, β = 115.42(2)°, V = 8166(3) Å3, Z = 4. Complex I was characterized by TG analysis. Variable-temperature magnetic susceptibility measurements showed that there exists a weak antiferromagnetic interaction of complex II.  相似文献   

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