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1.
Two Ni(II) metal–organic frameworks, [Ni(INAIP)(DMF)]·0.5DMF and [Ni(INAIP)(H2O)]·2H2O, have been synthesized by the reaction of 5-(isonicotinamido)isophthalic acid (H2INAIP) with NiSO4·6H2O using different reaction solvents. Single-crystal X-ray diffraction analysis indicates that [Ni(INAIP)(DMF)]·0.5DMF has a twofold interpenetrated three-dimensional (3D) framework with sra topology, while [Ni(INAIP)(H2O)]·2H2O has a two-dimensional (2D) network structure with a 4-connected (43·63) topology. In addition, the magnetic and adsorption properties of the complexes were explored.  相似文献   

2.
Using an octadentate ligand, namely tetrakis[(3,5-dicarboxyphenoxy)methyl] methane (H8L), four coordination polymers, [Ni3L(OH)2(H2O)2][NH2(CH3)2]4·5H2O (1), [Co4L(H2O)4]·9H2O (2), [Zn4L(H2O)4]·DMF·11H2O (3) and [Li4(H4L)(H2O)4] (4) (DMF = N,N-dimethylformamide), have been solvothermally synthesized and structurally characterized by X-ray crystallography. Complex 1 is an anionic three-dimensional open framework built from tricluster {Ni3(COOR)8} and square planar L ligands to give a uninodal 6-connected pcu network. Complexes 2 and 3 are isostructural, possessing a non-interpenetrated three-dimensional network with rare (4,8)-connected scu topology. Complex 4 consists of 4-connecting {Li2(COOR)4} clusters which form a 2D Shubnikov tetragonal plane net with sql topology. Complexes 1–3 all have large solvent accessible voids, but only complex 3 possesses permanent porosity as confirmed by N2, H2, CO2 and CH4 gas adsorption measurements. In addition, complex 3 shows strong photoluminescent emissions at room temperature with a peak at 365 nm, owing to a ligand-centered excited state. The emission intensities of 3 varied upon contact with different solvents or analytes.  相似文献   

3.
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   

4.
ZnII and CdII coordination polymers with dicarboxylate and imidazole‐containing ligands, namely, [Cd (2,3‐PDC)(L)]n ( 1 ) and {[Zn(3,4‐PDC) (L)0.5] · H2O}n ( 2 ), [2,3‐H2PDC = 2,3‐pyridine dicarboxylate, 3,4‐H2PDC = 3,4‐pyridine dicarboxylate, and L = 1,4‐bis(2‐methylimidazol‐3‐ium‐1‐yl)biphenyl], were prepared and characterized by elemental analysis, IR spectroscopy, and X‐ray diffraction. Complex 1 shows a three‐dimensional (3D) structure with threefold interpenetrating diamond topology. Complex 2 features a 3D framework with twofold interpenetrating dmc topology. Moreover, the luminescent properties of complexes 1 and 2 were also investigated.  相似文献   

5.
A cadmium(II) 3-D porous metal–organic framework, (Me2NH2)4[Cd2(TTCA)2Cl2]·7DMF·2Diox·6H2O (1) (TTCA = triphenylene-2,6,10-tricarboxylate, DMF = N,N-dimethylformamide, diox = 1,4-dioxane), has been synthesized through solvothermal conditions. Single-crystal X-ray analysis reveals that the structure of 1 has a two-fold interpenetrating framework with a large solvent-accessible volume of 52% per unit cell. The result of topological analysis shows that 1 is a (3,3)-connected 3-D network with {103} topology. Luminescence tests illustrate that 1 can selectively sense nitroaromatic explosives via a luminescence quenching mechanism.  相似文献   

6.
Reactions of 1,4-naphthalenedicarboxylic acid (1,4-H2nda) and a bent dipyridyl co-ligand 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (4bpt) with CoII, ZnII, or CdII acetate afford four coordination polymers, [Co(1,4-nda)(4bpt)(H2O)]n (1), {[Co(1,4-nda)2(4bpt)(H2O)2][Co(4bpt)(H2O)4](H2O)1.5}n (2), {[Zn(1,4-nda)2(4bpt)(H2O)2][Zn(4bpt)(H2O)4](H2O)1.5}n (3), and {[Cd2(1,4-nda)2(4bpt)2(H2O)2](DMF)1.5(H2O)3}n (4). In the structure of the CoII complex 1, the polycatenation of inclined 2-D (4,4) coordination layers leads to the formation of a 3-D supramolecular framework, whereas two types of 1-D polymeric chains are observed in another CoII coordination species 2, which are interconnected via H-bonding to result in an unusual 3-D host–guest lattice. Notably, complexes 1 and 2 have been prepared under similar hydrothermal conditions and their structural discrepancy can only be ascribed to a subtle change of basicity for the reaction solution. The ZnII complex 3 is isostructural to 2, and the CdII complex 4 displays a 2-fold parallel interpenetrating array of undulating (4,4) coordination layers. By using the conventional solvent evaporation method, two PbII naphthalenedicarboxylates [Pb(1,4-nda)(DMF)]n (5) and {[Pb2(2,6-nda)2(DMF)2](DMF)}n (6) have also been prepared (2,6-nda = 2,6-naphthalenedicarboxylate). Complex 5 has a unique 5-connected 3-D coordination architecture, whereas 6 represents a 3-fold interpenetrating framework of 4-connected diamond topology. Their structural difference suggests the significant isomeric effect of the naphthalenedicarboxylate tectons on structural assemblies. Thermal stability of these crystalline materials has been investigated by thermogravimetric and differential thermal analysis (TG–DTA) technique and solid-state luminescent properties of the ZnII, CdII, and PbII complexes have also been explored.  相似文献   

7.
Four metal complexes of N,N′-bis(salicyl)-2,6-pyridine-dicarbohydrazide ligand (H6L), [CoII(H4L)(H2O)2]·2DMF (1), [ZnII(H4L)(H2O)2]·2DMF (2), [CdII(H4L)(Py)2]·DMF·Py (3), and [CoIICo2III(H4L)4(H2O)4]·DMF·H2O (4), were synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction analysis. Structural studies revealed that complexes 13 present discrete mononuclear structures and complex 4 displays a centrosymmetric mixed-valence trinuclear structure. All four complexes are further extended into interesting two- or three-dimensional supramolecular frameworks. The luminescent properties of 2 and 3 were studied, which show emissions with maxima at 485 nm upon excitation at 396 nm for 2 and 476 nm upon excitation at 397 nm for 3, respectively.  相似文献   

8.
The flexible ditopic ligand 1,2-bis(3-(4-pyridyl)pyrazol-1-yl)ethane (L4Et) displays remarkable versatility in the complexes that it forms with transition metals with products ranging from 1D chains to interpenetrating 3D networks. The L4Et ligand itself crystallises in the space group P21, adopting a helical twist, although it is found in a variety of other conformations in its complexes. Coordination polymers containing the L4Et ligand vary from almost straight, parallel 1D chains of [Ag2(L4Et)2(ClO4)2(DMF)]·DMF (1), through interdigitating helical complexes containing tetrahedral Zn(II), [Zn(NCS)2(L4Et)]·DMF·H2O (2) to 2D sheets of [Cu(L4Et)2(H2O)2](PF6)2·xH2O (3) and the three-fold interpenetrating 3D network of [Co(L4Et)2(NCS)2] (4). The 3D network adopts an unusual 3D 4-connected dmp (65.8) topology. Dimensionality can be limited by the use of chelating co-ligands, demonstrated by the formation of the dinuclear complex [{Cu(py-2,6-CO2)(H2O)}2(L4Et)] (5).  相似文献   

9.
The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with CuI and/or CuII cations that show a remarkable range of framework topologies and structures. Complex [CuI 4CuII 1.5(L1)3(CN)6]·CN·n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu3(L2)4(H2O)3]·6(OTf)·n(DMSO) 2 and [Cu2(L3)2Br2(H2O)(DMSO)]·2Br·n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (43.123)(42.122) topology or a coordination chain. Complex [Cu2(L1)2(OTf)2(NMP)2(H2O)2]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.62.8)(62.8)(4.62.82) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF4·2(CH3CN)·H2O 5 features a 2D network of 63 topology while the CuII analogue [Cu2(L1)2(NMP)(H2O)]·4BF4·12NMP·1.5H2O 6 has an interpenetrating (10,3)-b type structure and complex [Cu2(L2)2Br3(DMSO)]·Br·n(DMSO) 7 has a 2D network of 4.82 topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C60 through soaking the crystals in a toluene solution.  相似文献   

10.
《Polyhedron》1999,18(8-9):1317-1322
The controlled nucleophilic halide displacement reaction of [NEt4][Fe(bpc)Cl2] [H2bpc=4,5-dichloro-1,2-bis(pyridine-2-carboxamido) benzene] with AgClO4 in MeCN afforded a crystalline iron(III) complex Fe(bpc)Cl·H2O 1. The mixed chloro-dimethylformamide (DMF) axially ligated complex [Fe(bpc)Cl(DMF)] (obtained during recrystallization of 1 from DMF; however, it loses DMF quite readily to revert back to 1) has been structurally characterized. It belongs to only a handful of mononuclear high-spin iron(III) complexes having deprotonated picolinamide ligand. The iron(III) centre is co-ordinated in the equatorial plane by two pyridine nitrogens and two deprotonated amide nitrogens of the ligand, and two axial sites are co-ordinated by a chloride ion and a DMF molecule. The metal atom has a distorted octahedral geometry. Reaction of 1 with [nBu4N][OH] in MeOH afforded a μ-oxo-bridged diiron(III) complex, [Fe(bpc)]2O·DMF·2H2O, 2. The spin state and the co-ordination environment of the iron(III) centres in 1 and 2 have been determined by temperature-dependent (25–300 K) magnetic susceptibility measurements in the solid state (Faraday method) and Mössbauer spectral studies at 300 K. Complex 1 behaves as a perfect S=5/2 system, in the solid-state as well as in DMF solution. The two iron(III) centres in 2 are antiferromagnetically coupled (J=−117.8 cm−1) and the bridged dimeric structure is retained in DMF solution. Bridge-cleavage reactions of 2 have been demonstrated by its ready reaction with mineral acids such as HCl and MeCO2H to generate authentic S=5/2 complexes, [Fe(bpc)Cl2] and [Fe(bpc)(O2CMe)2], respectively.  相似文献   

11.
Five coordination polymers, namely [Cd(L3)2]·H2O (1), [Zn(L3)2] (2), [Co(L3)2] (3), [Ni(L3)2] (4) and [Cu2(L3)2]·3H2O (5), where L3 = 3,5-bis(pyridin-3-ylmethoxy)benzoic acid, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. Compound 1 is a binodal (3,4)-connected net with (63)(66) topology. Compounds 24 are isostructural and described by the uninodal (4,4)-connected net with (44 · 62) Schläfli symbol. The structure of 5 is a 2D binodal (6,3) net. In addition, the luminescent properties of compounds 1 and 2 have been studied in the solid state at room temperature.  相似文献   

12.
Three metal–organic coordinate complexes based on 3-nitrophthalic acid (H2NPA), namely Cd2(H2O)(OH)2(NPA) (1), Cd2(Im)4(NPA)2 (2) and Cd2(Bim)4(H2O)(NPA)2 (3) (Im = imidazole, Bim = benzimidazole), have been obtained by hydrothermal method and characterized by X-ray single crystal structure determination. Structural analysis reveals that complex 1 exhibits 2D layers constructed by polyhedral aggregates. Complex 2 exhibits a dinuclear cadmium structural unit and assembles by hydrogen bonds into a 2D supramolecular architecture. Complex 3 is assembled by NPA2? into layers of a (3,4)-connected dinodal net topology of (4·52)(4·53·72). The fluorescent properties of complexes 13 have been investigated.  相似文献   

13.
Three novel coordination polymers, [Ni2(tib)2(btec)]·2H2O (1), [Co2(tib)2(btec)]·2H2O (2) and [Zn4(tib)2(btec)Cl4]·2H2O (3), have been synthesized by using mixed ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) under hydrothermal conditions. Complexes 1 and 2 have the same structure and are rare three-dimensional (3D) self-penetrating (3,4,5)-connected nets, while complex 3 is an unprecedented (3,4)-connected 3D net. The different structures of 1 (2) and 3 are ascribed to the distinct coordination geometry of the metal centers. The thermal stability and photoluminescence property of the complexes were investigated.  相似文献   

14.
Two coordination polymers, namely [Ni(L1)-(ndc)(H2O)] n (1) and [Cu(L2)0.5(ndc)] n (2) (L1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, L2 = 1,4-bis(2-methylbenzimidazole)butane, H2ndc = 2,6-naphthalenedicarboxylic acid) have been synthesized and characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and elemental analysis. Complex 1 features a 2D 3-connected hcb network with 63 topology, which is further extended into a 3D supramolecular framework by O–H···O hydrogen bonding interactions. Complex 2 possesses a 3D threefold interpenetrating (4,5)-connected xah topological network, and its Schläfli symbol is (42.62.82)(46.64). Both complexes exhibit intense luminescence emissions in the solid state and promising catalytic activities for the degradation of Congo red azo dye in a Fenton-like process.  相似文献   

15.
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   

16.
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   

17.
Three cobalt(II) coordination polymers {[Co(L1)(nda)(H2O)2]·2H2O} n (1), [Co(L2)(tbi)(H2O)] n (2) and [Co(L2)(bpdc)(H2O)] n (3) (L1 = 1,3-bis(5,6-dimethylbenzimidazol-1-yl)-2-propanol, L2 = 1,3-bis(benzimidazol-1-yl)-2-propanol, H2nda = 2,6-naphthalenedicarboxylic acid, H2tbi = 5-tert-butyl isophthalic acid and H2bpdc = 4,4′-biphenyldicarboxylic acid) were synthesized and characterized by physicochemical and spectroscopic methods. Complex 1 exhibits a 1D loop-like structure, which is further extended into a 3D 3,3,4T31 network through two O–H···O hydrogen bonding interactions. Complex 2 displays a 1D ladder-like chain, arranged into a 2D supramolecular network with 3,3,4L34 topology via classical O–H···O hydrogen bonding interactions, whereas complex 3 features a 2D 3,4L13 layer structure and further assembles into a 3D framework with a twofold interpenetrating sqc65 topology through O–H···O hydrogen bonding interactions. The fluorescence and catalytic properties of these complexes for the degradation of Congo red in a Fenton-like process have been investigated.  相似文献   

18.
A novel cobalt–carboxylate framework constructed from secondary building units (SBUs), {[Co16(btca)8(H2O)40]·16H2O}n (1) (H4btca = 1,2,3,4-butanetetracarboxylic acid) has been hydrothermally synthesized and characterized by techniques of single-crystal X-ray diffraction analyses, elemental analyses, infrared spectra, powder X-ray diffraction and thermogravimetric analyses. The complex exhibits 2D 4-connected sql net with (44 × 62) topology symbol built from [Co2(COO)4(H2O)5] SBUs and is further extended into a 3D supramolecular architecture via strong O–H···O hydrogen bonds. Moreover, the magnetic measurements indicate complex 1 exhibit antiferromagnetic behavior.  相似文献   

19.
Four homotrinuclear linear coordination compounds with bridging ligand of (m-phenol)-1,2,4-triazole, [Mn3(L)6(H2O)6](ClO4)6 (1), [Ni3(L)6(H2O)6](BF4)6·4DMF (2), [Cd3(L)6(H2O)6](ClO4)6· 2H2O·2DMF·2EtOH (3), [Zn3(L)8(H2O)4](BF4)4(SiF6)·2EtOH·12H2O (4), have been synthesized and structurally determined. The structures consist of three metal ions in linear arrangements, linked to each other by two pairs of three N1, N2 bridging triazole ligands. The negative value of J suggests that antiferromagnetic interaction exists in 1. Green fluorescence of 2 and 4 with emissions at 518 nm for 2 and 524 for 4 is possibly assigned to LMCT. The energy gaps of the compounds 2 and 4 are 1.82 and 1.97 eV, respectively, which suggests that the two materials behave as semiconductors.  相似文献   

20.
Four new inorganic–organic hybrid frameworks [Mn(L)(H2O)2]n (1), {[Co(L)(H2O)3]·2H2O·CH3OH}n (2), {[Zn(L)(H2O)]·H2O}n (3) and [Cd(HL)2]n (4) [H2L = 4-(isonicotinamido)phthalic acid] have been synthesized and characterized by single-crystal X-ray diffraction analysis. Complex 1 has three-dimensional (3D) structure and topology related to SrAl2 (sra) with Schläfli symbol of (42·63·8). And 2 displays (3,3)-connected two-dimensional (2D) network with (4,82) topology, while 3 exhibits a uninodal (3,3)-connected (6,3) 2D network, which is further linked by N–H?O hydrogen bonding interactions to give 3D structure with hms topology and Schläfli symbol of (63)(69·8). Complex 4 with partial deprotonated HL ligands also has a 2D network structure. In addition, the magnetic property of 1, nonlinear optical property of 3 and photoluminescence of 3 and 4 were investigated.  相似文献   

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