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1.
Four coordination polymers, [Zn(o-bdc)(bth)0.5(H2O)] n (1), [Cd(o-bdc)(bth)0.5(H2O)] n (2), [Zn(m-bdc)(bth)] n (3), and [Cd(p-bdc)(bth)?·?(H2O)2] n (4) (where o-bdc?=?1,2-benzenedicarboxylate, m-bdc?=?1,3-benzenedicarboxylate, p-bdc?=?1,4-benzenedicarboxylate, and bth?=?1,6-bis(triazol)hexane), have been hydrothermally synthesized and structurally characterized. Both 1 and 2 are isostructural, featuring two binodal architectures: (63)(65·8) topology in terms of o-bdc and ZnII/CdII as three- and four-connected nodes. Complex 3 shows a 2-D (4,4) network with the Zn?···?Zn?···?Zn angle of 57.84°, whereas 4 exhibits planar 2-D (4,4) network. These 2-D networks of 3 and 4 are extended by supramolecular interactions, such as CH?···?π/π–π stacking and hydrogen-bonding into 3-D architecture. A structural comparison of these complexes demonstrates that the dicarboxylate building blocks with different dispositions of the carboxyl site play a key role in governing the coordination motifs as well as 3-D supramolecular lattices. Solid-state properties such as photoluminescence and thermal stabilities of 14 have also been studied.  相似文献   

2.
Four coordination polymers, [Ag(L1)](m-Hbdc) (1), [Ag(L1)]2(p-bdc)?·?8H2O (2), [Ag(Hbtc)(L1)][Ag(L1)]?·?2H2O (3) and [Ag2(L2)2](OH-bdc)2?·?4H2O (4), where L1?=?1,1′-(1,4-butanediyl)bis(imidazole), L2?=?1,2-bis(imidazol-1-ylmethyl)benzene, m-H2bdc?=?1,3-benzenedicarboxylic acid, p-H2bdc?=?1,4-benzenedicarboxylic acid, H3btc?=?1,3,5-benzenetricarboxylic acid, and OH–H2bdc?=?5-hydroxisophthalic acid, were synthesized under hydrothermal conditions. Compound 1 contains a–Ag-L1–Ag-L1–chain and a hydrogen-bonding interaction induced–(m-Hbdc)-(m-Hbdc)–chain. Compound 2 consists of two independent–Ag-L1–Ag-L1–chains. P-bdc anions are not coordinated. Hydrogen bonds form a 3D supramolecular structure. A novel (H2O)16 cluster is formed by lattice water molecules in 2. Compound 3 contains a–Ag-L1–Ag-L1–and a–Ag(Hbtc)-L1–Ag(Hbtc)-L1–chain. The packing diagram shows a 2D criss-cross supramolecular structure, with?π?···?π?and C–H ···?π?interactions stabilizing the framework. Compound 4 contains a [Ag2(L2)2]2+ dimer with hydrogen-bonding,?π?··· π, and Ag ··· O interactions forming a 3D supramolecular framework. The luminescent properties for these compounds in the solid state are discussed.  相似文献   

3.
A 3-D metal-organic framework [Cd3(L)2(DMF)2]?·?2H2O?·?2DMF (1) (H3L?=?2-(dimethylcarbamoyl)biphenyl-5,2′,5′-tricarboxylic acid, DMF?=?N,N-dimethylformamide) with trinuclear Cd(II) units has been prepared. Complex 1 is a (3,?6)-connected (42?·?6)2(44?·?62?·?88?·?10) coordination net, which results from the solvothermal in situ formation of a new asymmetric ligand, 2-(dimethylcarbamoyl)biphenyl-5,2′,5′-tricarboxylic acid (H3L), through amidation of biphenyl-2,5,2′,5′-tetracarboxylic acid (H4bptc). Additionally, the luminescence of 1 has been investigated.  相似文献   

4.
Two new erbium compounds, [Er2(BDC)3(DMF)2] (1) and [Er2(CQC)3(DMF)3(H2O)]?·?DMF?·?H2O (2), where BDC stands for 1,4-benzenedicarboxylate, CQC for 2-(4-carboxyquinolin-2-yl)quinoline-4-carboxylate, and DMF for N,N-dimethylformamide, have been synthesized through pre-heating and cooling-down crystallization. In 1 the Er(III) is seven-coordinate with oxygen atoms from six BDC and one DMF, forming a three-dimensional open-framework structure. Compound 2 possesses a 2D structure based on dinuclear Er(III) building units. The photoluminescence of 1 has also been investigated.  相似文献   

5.
The reaction of [Ni3(dpa)4(ClO4)2] with 1,4-benzenedicarboxylate through diffusion of layered-solution led to the precipitation of 1, {[Ni3(dpa)4(1,4-bdc)]?·?0.5H2O]}n, where dpa? is 2,2′-dipyridylamido anion, which was characterized by IR, elemental analysis, MS, fluorescence spectrum, TG analysis, and magnetic measurement. Extension of the metal string complex by assembly of [Ni3(dpa)4]2+ and 1,4-bdc2? gives a 1-D polymeric structure, in which the axial 1,4-bdc2? influences the Ni?···?Ni distances, fluorescence emission, and magnetism.  相似文献   

6.
Two new ZnII complexes, {[Zn(L)(phen)(H2O)]?·?H2O} (1) and {[Zn(L)(4bpy)(H2O)]?·?H2O} (2) (L?=?5,6-dihydro-1,4-dithiin-2,3-dicarboxylate, phen?=?1,10-phenanthroline, and 4bpy?=?4,4′-bipyridine), have been prepared by in situ reaction of Zn(ClO4)2?·?6H2O with 5,6-dihydro-1,4-dithiin-2,3-dicarboxylic anhydrate in the presence of lithium hydroxide, together with incorporating chelating phen or bridging 4bpy as co-ligands. Their structures were determined by single-crystal X-ray diffraction. Complex 1 takes a 1-D helical structure that is further assembled into a 2-D network by O–H?···?O, C–H?···?O hydrogen bonds, and weak S?···?S interactions, and then an overall 3-D supramolecular framework was formed by π?···?π stacking interactions. Complex 2 possesses a 2-D (4,4)-layered structure. The structural difference between 1 and 2 can be attributed to the different N-donor auxiliary co-ligands. Both 1 and 2 are photoluminescent materials whose emission properties are closely related to their intrinsic structure.  相似文献   

7.
[Co2(TTBT)4(1,2-BDC)2] n ?·?4nH2O (1), [Pb2(TTBT)2(1,3-BDC)2] n ?·?nTTBT?·?2nH2O (2), [Fe(TTBT)(1,4-BDC)(H2O)] n (3), and [Zn(TTBT)(1,4-BDC)(H2O)] n (4) have been hydrothermally synthesized by self-assembly of TTBT (TTBT?=?10,11,12,13-tetrahydro-4,5,9,14-tetraaza-benzo[b]triphenylene), benzene-dicarboxylic acid ligands 1,2-H2BDC, 1,3-H2BDC or 1,4-H2BDC (1,2-H2BDC?=?1,2-benzenedicarboxylic acid, 1,3-H2BDC?=?1,3-benzenedicarboxylic acid, 1,4-H2BDC?=?1,4-benzenedicarboxylic acid), and various metal salts. Compound 1 has dinuclear cluster units, four dimeric Co2 units connected to form a 32-membered ring via weak offset π–π interactions, which are further stacked via strong π–π interactions to form a 3-D supramolecular framework. Complex 2 contains 2-D layers with rhombohedral grids, which are connected to a 3-D structure by π–π interactions. 3 and 4 feature 1-D infinite chains, which are further extended by strong π–π interactions and O–H···O hydrogen bonds resulting in 3-D supramolecular architectures. The photoluminescent properties of 2 and 4 have also been investigated.  相似文献   

8.
Three new complexes, [Ni2(dpc)2(L1)2(H2O)2]?·?4H2O (1), [Ni(dpc)(L2)1.5] n (2), and {[Ni(dpc)(L3)1.5]?·?2H2O} n (3), where H2dpc?=?dipicolinic acid, L1?=?1,4-bis(2-methylimidazol-1-yl)butane, L2?=?4,4′-bis(2-methylimidazol-1-ylmethyl)biphenyl, and L3?=?1,4-bis(benzimidazol-1-yl)-2-butylene, have been synthesized by hydrothermal methods and characterized by elemental analyses, infrared spectra, thermogravimetric analysis, and X-ray crystallography. The common structural characteristic of the three complexes is that the Ni2+ is coordinated by tridentate dipicolinate through nitrogen of pyridine and oxygen of carboxylate, serving as a terminal ligand. In 1, two L1 link two [Ni(dpc)(H2O)] units to a discrete binuclear metallomacrocycle with a 22-membered ring, which is assembled through multiple O–H?···?O hydrogen bonds to form a 3-D supramolecular framework. Complex 2 exhibits a 1-D ladder-like chain structure constructed by cis/trans-conformation L2 linking metal centers; 3 displays a 2-D (6,3) topology, being constructed from the linking of [Ni(pdc)] by L3. These results indicate the merits of flexible bis(imidazole) ligands as building blocks with dipicolinate for the construction of complexes with diverse structural motifs.  相似文献   

9.
Two new complexes, [Mn(H2bptc)(2,2′-bpy)2]?·?2H2O (1) and [Mn3(Hbptc)2(2,2′-bpy)3(H2O)8]?·?2H2O (2) (H4bptc?=?biphenyl-2,5,2′,5′-tetracarboxylic acid, 2,2′-bpy?=?2,2′-bipyridine), have been synthesized under hydrothermal conditions. Their structures have been characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, powder X-ray diffraction, and thermogravimetric analyses. Complexes 1 and 2 are both linked into 3-D supramolecular networks by non-covalent interactions (O–H?···?O, C–H?···?O, C–H?···?π, and π?···?π). Complexes 1 and 2 exhibit weak antiferromagnetic interactions.  相似文献   

10.
A mixed-ligand compound, [Ni2(BPTC)(pyz)?·?2H2O] n (0.5H2O) n (BPTC?=?3,3′,4, 4′-benzophenone-tetracarboxylate, pyz?=?pyrazine), has been prepared hydrothermally by assembly of BPTC, NiCl2·6H2O and pyz. X-ray diffraction analysis of a single crystal reveals the three-dimensional framework assembled from pyz-pillared two-dimensional sheets. Three types of channels in one direction are established inside the structure. The third-order nonlinear optical (NLO) properties in DMF have been studied by Z-scan technique using an 8?ns laser at 532?nm. The results reveal that the new compound exhibits strong NLO absorption and self-focusing refractive performance (n 2?=?2.7?×?10?17?m2?W?1).  相似文献   

11.
A new oxamido-bridged dinuclear compound [Cu2(µ-pmox)(DMF)4]?·?2ClO4 (1) (H2pmox?=?N,N′-bis-(2-methylpyridyl)oxalamide, DMF?=?dimethylformamide) was synthesized and structurally characterized. The five-coordinate Cu(II) is bridged by oxamido groups and further cross-linked by C–H···O hydrogen bonds between the uncoordinated oxygen of perchlorate and methyl of DMF. The complex was also characterized by infrared spectroscopy and magnetic measurement. The copper complex exhibits strong antiferromagnetic interactions via the trans oxamido bridge with J of ?414?cm?1, where J is the exchange parameter in the isotropic Hamiltonian H?=??JS1S2.  相似文献   

12.
This article describes supramolecular interactions induced in a high molecular weight dithiocarbamate, padtc, by its design. Synthesis, spectral studies involving zinc, cadmium and mercury, padtc, and adducts with tmed, such as [Zn(padtc)2] (1), [Zn(padtc)2(tmed)]?·?C6H5CH3?·?0.5(H2O) (2), [Cd(padtc)2] (3), [Cd(padtc)2(tmed)]?·?C6H5CH3?·?0.36(H2O) (4), [Hg(padtc)2]?·?H2O (5), [Hg(padtc)2(2,2′-bipy)]?·?H2O (6), [Hg(padtc)2(1,10-phen)]?·?H2O (7), and [Hg(padtc)2(oxine)]?·?H2O (8) (where padtc??=?N,N′-(iminodiethylene)bisphthalimidedithiocarbamate, 1,10-phen?=?1,10-phenanthroline, tmed?=?tetramethylethylenediamine, 2,2′-bipy?=?2,2′-bipyridine, oxine?=?8-hydroxyquinoline) along with the single crystal X-ray structural analysis of [Zn(padtc)2(tmed)]?·?C6H5CH3?·?0.5(H2O) (2) and [Cd(padtc)2(tmed)]?·?C6H5CH3?·?0.36(H2O) (4) are reported. All the complexes were characterized by IR, NMR (1H and 13C), and thermogravimetric study. The IR spectra of the complexes show the contribution of the thioureide form to the structures. In 13C NMR spectra, the most important thioureide (N13CS2) carbon signals are observed at 210–212?ppm. Single crystal X-ray structural analyses of 2 and 4 show the presence of extensive supramolecular interactions stabilizing the solid-state structure. Both zinc and cadmium are in a distorted octahedral environment with MS4N2 chromophores. VBS of Zn and Cd are 1.76 and 1.98, respectively, supporting the correctness of the determined structure and the valence of the central metal ions.  相似文献   

13.
Five lanthanide(III) coordination polymers with 2-methyl-1H-imidazole-4,5-dicarboxylic acid (H3MIDC) and ammonium oxalate, {[(Ln1)2(HMIDC)2(C2O4)(H2O)3]?·?3H2O} n (Ln1?=?Nd (1), Sm (2)), {[Eu2(HMIDC)2(C2O4)(H2O)3]?·?0.5EtOH?·?3H2O} n (3), {[Ce2(HMIDC)2(C2O4)(H2O)3]?·?EtOH?·?3H2O} n (4), and {[Gd2(HMIDC)2(C2O4)(H2O)3]?·?MeOH?·?3H2O} n (5), have been prepared and structurally characterized. Single-crystal X-ray diffraction analyses reveal that 1 and 2 are isostructural, as are 3, 4, and 5. Each exhibits a 3-D open framework, which is built by a regular 2-D grid connected by HMIDC2? and Ln(III). The luminescence and thermal properties of these complexes have been investigated as well.  相似文献   

14.
Three Cu(II) complexes, Cu2(bpy)(H2O)(Clma)2 (1), Cu2(bpe)(H2O)2(Clma)2 (2), and Cu(bpp)(Clma) (3), were synthesized (HClma = (R)-2-Chloromandelic acid, bpy?=?4,4′-dipyridine, bpe?=?1,2-di(4-pyridyl)ethylene, bpp?=?1,3-di(4-pyridyl)propane). Complexes 1, 2, and 3 are constructed from 1-D coordination arrays generated from Cu2(H2O)(Clma)2, Cu2(H2O)2(Clma)2, and Cu2(Clma)2 moieties and linked through bpy, bpe, and bpp co-ligands, respectively. 1 and 2 are assembled into 3-D supramolecular networks via O–H?O hydrogen bonds with topology of (63)(69·8) and (412·63), respectively, and 3 is assembled into a 3-D architecture through C–H?O hydrogen bonds with topology of (43·63)(43)(44·65·8)(46·66·83). Compounds 1, 2, and 3 crystallized in acentric space groups P21, P1, and P21, which exhibit significant ferroelectricity (remnant polarization Pr?=?0.008?μC?cm?2, coercive field Ec?=?21.4?kV?cm?1, the spontaneous saturation polarization Ps?=?0.167?μC?cm?2 for 1, Pr?=?0.183?μC?cm?2, Ec?=?1.69?kV?cm?1, and Ps?=?0.021 μC?cm?2 for 3). Results from infrared and thermal analyses are also discussed.  相似文献   

15.
Two coordination polymers, {[Zn(NiL)(DMA)(H2O)2] (DMA)(H2O)} n (1) (DMA?=?N,N-dimethylacetamide) and {[Zn2(NiL)2(DMF)(H2O)4]?·?3DMF} n (2) (DMF?=?N,N-dimethylformamide), have been prepared by reactions of Zn(NO3)2?·?6H2O and NiL in CH2Cl2-DMA–H2O and CH2Cl2-DMF–H2O, respectively. H2L denotes dimethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo-9,10-benzo-[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate. Single-crystal X-ray diffraction analyses reveal that coordination geometries around Ni(II) are identical with slightly distorted square planar and all Ni–N bonds are very short. Complex 1 shows 1-D zigzag chain structure, while 2 has 1-D double-zigzag chains. The chains, which are packed parallel in 1 and 2, are interconnected by lattice solvent through O–H···O and C–H···O hydrogen bonds to form 3-D supramolecular networks. We discuss solvent effects on assembly of the two coordination polymers. The results reveal that coordinated solvent has influence on the assembly procedure.  相似文献   

16.
Three supramolecular complexes, [VO(phen)(C2O4)(H2O)]·CH3OH (1) [(VO)2(u2-C2O4)(C2O4)2(H2O)2]·L·H2O (2), and [(4,4′-bipyH2)0.5]+[VO2(2,6-dipic)]?·2H2O (3) (phen?=?1,10-phenanthroline 4,4′-bipy?=?4,4′-bipyridine, 2,6-dipic?=?2,6-pyridinedicarboxylic, L?=?1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene), have been prepared and characterized by elemental analysis, IR, and UV–vis spectroscopy and single-crystal diffraction analysis. Structural analysis shows that the three complexes all contain carboxylate and V=O moiety; vanadium of 1 and 2 are six coordinate with distorted octahedral geometry with N2O4 and O6 donor sets, respectively, while 3 is five coordinate with distorted trigonal bipyramidal geometry with a NO4 donor set. The complexes exhibit catalytic bromination activity in the single-pot reaction for the conversion of phenol red to bromophenol blue in H2O–DMF at 30?±?0.5?C with pH 5.8, indicating that they can be considered as functional model vanadium-dependent haloperoxidases. In addition, electrochemical behaviors are also studied.  相似文献   

17.
Three transition metal coordination complexes, {[Co(2,4-DCP)2(μ 2-H2O)(H2O)2]?·?(H2O)2} n (1), [Zn(2,4-DCP)(IN)] n (2), and [Mn2(2,4-DCP)3(DMPY)2(μ 2-H2O)(H2O)]?·?(2,4-DCP)?·?0.2(H2O) (3) (2,4-DCP?=?2,4-dichlorophenoxyacetate, IN?=?isonicotinate, DMPY?=?5,5′-dimethyl-2,2′-bipyridine), have been prepared under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Complex 1 displays a 1-D chain through cobalt and bridging water molecules with Co?···?Co distance of 4.028(2)?Å. Complex 2 shows a 2-D (4,4) net, which is extended into a 3-D supramolecular framework by weak hydrogen-bonding interactions. Complex 3 consists of discrete dinuclear cations, 2,4-DCP counter ions and free water molecules, which are assembled into a packing structure through π?···?π stacking of inversion-related DMPY ligands and hydrogen bonds. Magnetic susceptibility measurements show weak antiferromagnetic interactions in 1. The photoluminescence and lifetime of 2 in the solid state have also been studied.  相似文献   

18.
Four Cd(II)- and Cu(II)-containing coordination polymers (CPs) based on a multidentate N-donor ligand and varied dicarboxylate anions, [Cd(3,3′-tmbpt)(p-bdc)]·2.5H2O (1), [Cd(3,3′-tmbpt)(m-bdc)]·2H2O (2), [Cu(3,3′-tmbpt)(m-bdc)]·H2O (3), and [Cu(3,3′-tmbpt)(p-bdc)]·2H2O (4), where 3,3′-tmbpt = 1 ? ((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, p-H2bdc = 1,4-benzenedicarboxylic acid, and m-H2bdc = 1,3-benzenedicarboxylic acid, have been prepared hydrothermally. The structures of the compounds were determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra and elemental analyses. Compound 1 exhibits a 3-D twofold interpenetrating framework with a 65·8 CdSO4 topology. Compound 2 is a 2-D layer containing meso-helical chains with a 44·62 sql topology. Compound 3 shows a 1-D → 3-D interdigitated architecture while 4 displays a 2-D → 3-D interdigitated architecture. The structural differences of the compounds indicate that the dicarboxylate anions and the central metal ions play important roles in the resulting structures of CPs. Optical band gaps and solid-state photoluminescent properties have also been studied.  相似文献   

19.
Three new coordination polymers based on 2-ethyl-imidazole-4,5-dicarboxylate with 1,10-phenanthroline as ligands, Pb(HEIDC)(phen)2 (1), [Zn(EIDC)(phen)] n (2), and {[Ba(H2EIDC)2(phen)]?·?(phen)2?·?[Ba(H2EIDC)(HEIDC)(phen)]} n (3) (H3EIDC?=?2-ethyl-1-Himidazole-4,5-dicarboxylate; phen?=?1,10-phenanthroline), have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Complex 1 displays a tetranuclear square constructed of four Pb(II) centers, four HEIDC, and eight phen, resulting in a 3-D network with a 1-D open channel along the c-axis via C–H?···?O hydrogen bonds, C–H?···?π, and π–π stacking interactions. Complex 2 is an infinite zigzag chain resulting in the final 3-D supramolecular framework via C–H?···?O and π–π stacking interactions. Complex 3 is composed of two individual Ba chains, exhibiting a 3-D framework via O–H?···?O, O–H?···?N hydrogen bonds, and π–π stacking interactions. The photoluminescence spectra of 1 and 2 in the solid state have been investigated, 1 exhibits green photoluminescence in the solid state at room temperature.  相似文献   

20.
{[CdCl(2,2′-bipy)2(H2O)]+·[Cd(3-O?-2,7-NDS)(2,2′-bipy)2]?·3H2O} (1) and {[Cd(phen)3]2+·2[Cd(3-O?-2,7-NDS)(phen)2]?·8.5H2O} (2) (3-OH-2,7-NDS?=?3-hydroxy-2,7-naphthalenedisulfonate, phen?=?1,10-phenanthroline, and 2,2′-bipy?=?2,2′-bipydine) were prepared and characterized by X-ray single-crystal diffraction. Compound 1 contains a discrete coordination cation [CdCl(2,2′-bipy)2(H2O)]+ and a coordination anion [Cd(3-O?-2,7-NDS)(2,2′-bipy)2]?; 2 contains a discrete coordination cation [Cd(phen)3]2+ and two coordination anions [Cd(3-O?-2,7-NDS)(phen)2]?. There are numerous weak interactions among the coordination cation, coordination anion, and free water molecules, such as O–H?···?O hydrogen bonds, π?···?π stacking, and Cl??···?π interactions in 1 and π?···?π stacking and C–H?···?π interactions in 2. The cations and anions as building blocks are connected to construct different 3-D supramolecular architectures via weak intermolecular interactions. Particularly, the capsule structure of 1 was observed.  相似文献   

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