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1.
One of most interesting systems of coordination polymers constructed from the first‐row transition metals is the porous ZnII coordination polymer system, but the numbers of such polymers containing N‐donor linkers are still limited. The title double‐chain‐like ZnII coordination polymer, [Ag2Zn(CN)4(C10H10N2)2]n, presents a one‐dimensional linear coordination polymer structure in which ZnII ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each ZnII ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1‐benzyl‐1H‐imidazole (BZI) ligands, giving a five‐coordinated ZnII ion. Interestingly, there are strong intermolecular AgI…AgI interactions between terminal and bridging dicyanidoargentate(I) units and C—H…π interactions between the phenyl rings of BZI ligands of adjacent one‐dimensional linear chains, providing a one‐dimensional linear double‐chain‐like structure. The supramolecular three‐dimensional framework is stabilized by C—H…π interactions between the phenyl rings of BZI ligands and by AgI…AgI interactions between adjacent double chains. The photoluminescence properties have been studied.  相似文献   

2.
In the title coordination compound, [Zn(C12H6O4)(C14H14N4)]n, the two ZnII centers exhibit different coordination environments. One ZnII center is four‐coordinated in a distorted tetrahedral environment surrounded by two carboxylate O atoms from two different naphthalene‐1,4‐dicarboxylate (1,4‐ndc) anions and two N atoms from two distinct 1,4‐bis(imidazol‐1‐ylmethyl)benzene (1,4‐bix) ligands. The coordination of the second ZnII center comprises two N atoms from two different 1,4‐bix ligands and three carboxylate O atoms from two different 1,4‐ndc ligands in a highly distorted square‐pyramidal environment. The 1,4‐bix ligand and the 1,4‐ndc anion link adjacent ZnII centers into a two‐dimensional four‐connected (4,4) network. The two (4,4) networks are interpenetrated in a parallel mode.  相似文献   

3.
We present two ZnII‐ and CdII‐based coordination polymers (CPs), L ‐Zn and L ‐Cd , offering H‐bonding‐based cavities of varying dimensions. Both CPs were used for the highly selective detection of S2O72? and Fe3+ ions where H‐bonding based cavities played an important role. Fluorescence quenching, competitive binding studies and binding parameters substantiated significant recognition of S2O72? and Fe3+ ions by both CPs.  相似文献   

4.
Herein, a mechanism of stepwise metal‐center exchange for a specific metal–organic framework, namely, [Zn4(dcpp)2(DMF)3(H2O)2]n (H4dcpp=4,5‐bis(4′‐carboxylphenyl)phthalic acid), is disclosed for the first time. The coordination stabilities between the central metal atoms and the ligands as well as the coordination geometry are considered to be dominant factors in this stepwise exchange mechanism. A new magnetic analytical method and a theoretical model confirmed that the exchange mechanism is reasonable. When the metathesis reaction occurs between CuII ions and framework ZnII ions, the magnetic exchange interaction of each pair of CuII centers gradually strengthens with increasing amount of framework CuII ions. By analyzing the changes of coupling constants in the Cu‐exchanged products, it was deduced that Zn4 and Zn3 are initially replaced, and then Zn1 and Zn2 are replaced later. The theoretical calculation further verified that Zn4 is replaced first, Zn3 next, then Zn1 and Zn2 last, and the coordination stability dominates the Cu/Zn exchange process. For the Ni/Zn and Co/Zn exchange processes, besides the coordination stability, the preferred coordination geometry was also considered in the stepwise‐exchange behavior. As NiII and CoII ions especially favor octahedral coordination geometry in oxygen‐ligand fields, NiII ions and CoII ions could only selectively exchange with the octahedral ZnII ions, as was also confirmed by the experimental results. The stepwise metal‐exchange process occurs in a single crystal‐to‐single crystal fashion.  相似文献   

5.
Two new ZnII coordination polymers (CPs), [Zn2(SA)2(L)2]n ( 1 ) and [Zn(AA)(L)]n ( 2 ) [L = 1,6‐bis(benzimidazol‐1‐yl)hexane, H2SA = succinic acid, H2AA = adipic acid], were synthesized via hydrothermal method and characterized by elemental analysis, infrared spectroscopy, and single‐crystal X‐ray diffraction. CP 1 possesses a sql network, which is further extended into a 3D supramolecular skeleton by non‐classical C–H ··· O hydrogen bonding interactions. CP 2 exhibits a 1D linear chain, which is further assembled into a 2D supramolecular layer by π ··· π stacking interactions. The solid state fluorescence properties of two ZnII CPs were investigated. Both CPs present high photocatalytic activities for the degradation of methylene blue (MB) under UV light irradiation. The photodegradation efficiency using CP 1 as catalyst is 91.3 % and using CP 2 as catalyst is 85.0 %, respectively.  相似文献   

6.
In the title complex, [Zn(C12H6O4)(H2O)]n, a ZnII polymer based on naphthalene‐1,8‐dicarboxylate (1,8‐nap), the ZnII atoms adopt an elongated octahedral coordination geometry. A zigzag chain is formed by μ2‐aqua ligands and μ2‐carboxylate groups of the 1,8‐nap ligands. Adjacent parallel chains are further linked by 1,8‐nap ligands, forming a twisted two‐dimensional layer structure along the (100) plane.  相似文献   

7.
The synthesis is reported of the tricarboxylic acid 3‐(3,5‐dicarboxybenzyloxy)benzoic acid (H3L) and the product of its reaction under solvothermal conditions with ZnII cations, namely poly[[μ6‐3‐(3,5‐dicarboxylatobenzyloxy)benzoato](dimethylformamide)‐μ3‐hydroxido‐dizinc(II)], [Zn2(C16H9O7)(OH)(C3H7NO)]n, the formation of which is associated with complete deprotonation of H3L. Its crystal structure consists of a single‐framework coordination polymer of the organic L3− ligand with ZnII cations in a 1:2 ratio, with additional hydroxide and dimethylformamide (DMF) ligands coordinated to the ZnII centres. The ZnII cations are characterized by coordination numbers of 5 and 6, being bridged to each other by hydroxide ligands. In the polymeric framework, the carboxylate‐ and hydroxy‐bridged ZnII cations are arranged in coordination‐tessellated columns, which propagate along the a axis of the crystal structure, and each L3− ligand links to seven different ZnII centres via Zn—O bonds of two different columns. The coordination framework, composed of [Zn2(L)(OH)(DMF)]n units, forms an open architecture, the channel voids within it being filled by the zinc‐coordinating DMF ligands. This report provides the first structural evidence for the formation of coordination polymers with H3L via multiple metal–ligand bonds through its carboxylate groups.<!?tpb=21.5pt>  相似文献   

8.
Reaction of group 12 metal dihalides with 2‐acetylpyridine‐N‐oxide 4N‐methylthiosemicarbazone (H4MLO) in ethanol afforded compounds [M(H4MLO)X2] (M = ZnII, CdII, HgII; X = Cl, Br, I), the structures of which were characterized by elemental analysis and by IR and 1H and 13C NMR spectroscopy. In addition, the complexes of ZnBr2 and ZnI2 were analysed structurally by X‐ray diffractometry. In [Zn(H4MLO)Br2] the ligand is O,N,S‐tridentate and the metal is pentacoordinated, while in [Zn(H4MLO)I2] the thiosemicarbazone is S,O‐bis‐monodentate and the ZnII cation has a distorted tetrahedral coordination polyhedron. In assays of antifungal activity against Aspergillus niger and Paecilomyces variotii, only the mercury compounds showed any activity, and only [Hg(H4MLO)Cl2] and [Hg(H4MLO)I2] were competitive with nystatin against A. niger.  相似文献   

9.
The synthesis of coordination polymers or metal–organic frameworks (MOFs) has attracted considerable interest owing to the interesting structures and potential applications of these compounds. It is still a challenge to predict the exact structures and compositions of the final products. A new one‐dimensional coordination polymer, catena‐poly[[[bis{1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole‐κN3}zinc(II)]‐μ‐hexane‐1,6‐dicarboxylato‐κ4O1,O1′:O6,O6′] monohydrate], {[Zn(C6H8O4)(C9H8N6)2]·H2O}n, has been synthesized by the reaction of Zn(Ac)2 (Ac is acetate) with 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole (bimt) and adipic acid (H2adi) at room temperature. In the polymer, each ZnII ion exhibits an irregular octahedral ZnN2O4 coordination geometry and is coordinated by two N atoms from two symmetry‐related bimt ligands and four O atoms from two symmetry‐related dianionic adipate ligands. ZnII ions are connected by adipate ligands into a one‐dimensional chain which runs parallel to the c axis. The bimt ligands coordinate to the ZnII ions in a monodentate mode on both sides of the main chain. In the crystal, the one‐dimensional chains are further connected through N—H…O hydrogen bonds, leading to a three‐dimensional supramolecular architecture. In addition, the title polymer exhibits fluorescence, with emissions at 334 and 350 nm in the solid state at room temperature.  相似文献   

10.
The coordination geometry of the ZnII atom in the title complex, [Zn2(NCS)4(C6H8N6)2], is that of a distorted tetra­hedron, in which the ZnII atom is coordinated by four N atoms from the triazole rings of two symmetry‐related 1,2‐bis­(1,2,4‐triazol‐1‐yl)ethane ligands and two thio­cyanate ligands. Two ZnII atoms are bridged by two organic ligands to form a dimer. The dimer lies about an inversion center.  相似文献   

11.
The novel title ZnII coordination polymer, poly[bis(μ‐6‐thioxo‐1,6‐dihydropyridine‐3‐carboxylato‐κ2S:O)zinc(II)], [Zn(C6H4NO2S)2]n, consists of two crystallographically independent zinc centers and two 6‐mercaptonicotinate (Hmna) ligands. Each ZnII atom is four‐coordinated and lies at the center of a distorted tetrahedral ZnS2O2 coordination polyhedron, bridged by four Hmna ligands to form a two‐dimensional (4,4)‐network. Each Hmna ion acts as a bridging bidentate ligand, coordinating to two ZnII atoms through the S atom and a carboxyl O atom. The metal centers reside on twofold rotation axes. The coordination mode of the S atoms and N—H...O hydrogen‐bonding interactions between the protonated N atoms and the uncoordinated carboxyl O atoms give the extended structure a wavelike form.  相似文献   

12.
The reaction of ZnII nitrate with maleic acid (H2mal) / fumaric acid (H2fum) and 4,4′‐dipyridyl disulfide (4‐pds) resulted under same conditions in two distinct interpenetrated compounds, namely [Zn(4‐dps)2(H2O)2]·2Hmal ( 1 ) and [Zn(4‐dps)(fum)] ( 2 ). In 1 , Hmal anion adopts bridging mode based on hydrogen bonding, affording a 2‐fold parallel interpenetrated 3D→3D α‐Po net hydrogen‐bonded framework, in which 1D double‐stranded chains are formed, and then extended to a 3D supramolecular architecture combining second‐sphere hydrogen‐bonded interactions. For 2 , fum dianion takes on bis‐dentate bridging coordination fashion, furnishing a 2‐fold interpenetrated 2D→2D (4,4) layered coordination network, in which the tetrahedral ZnII atoms are interlinked by 4‐dps and fum. Additionally, the compound 2 shows strong fluorescence in the solid state at room temperature.  相似文献   

13.
In the title compound, {[Zn(C8H4O5)(C12H10N2)]·0.5C12H10N2}n or {[Zn(HO‐BDC)(bpe)]·0.5bpe}n [HO‐H2BDC is 5‐hydroxyisophthalic acid and bpe is 1,2‐bis(pyridin‐4‐yl)ethene], the asymmetric unit contains a ZnII atom, one HO‐BDC ligand, one coordinated bpe ligand and half a noncoordinating bpe molecule with crystallographic inversion symmetry. Each ZnII centre is four‐coordinated by two O atoms from two distinct HO‐BDC ligands and two N atoms from two different bpe ligands in a ZnO2N2 coordination environment. The three‐dimensional topology of the title compound corresponds to a fourfold interpenetrating diamondoid coordination polymer network, with the uncoordinated bpe ligands located in the cavities, hydrogen bonded to the main network via the hydroxy group of the HO‐H2BDC ligand.  相似文献   

14.
The title compound, [Zn2(C9H4O6)2(C6H6N4)2], consists of two ZnII ions, two 5‐carboxybenzene‐1,3‐dicarboxylate (Hbtc2−) dianions and two 2,2′‐bi‐1H‐imidazole (bimz) molecules. The ZnII centre is coordinated by two carboxylate O atoms from two Hbtc2− ligands and by two imidazole N atoms of a bimz ligand, in a distorted tetrahedral coordination geometry. Two neighbouring ZnII ions are bridged by a pair of Hbtc2− ligands, forming a discrete binuclear [Zn2(Hbtc)2(bimz)2] structure lying across an inversion centre. Hydrogen bonds between carboxyl H atoms and carboxylate O atoms and between imidazole H atoms and carboxylate O atoms link the binuclear units. These binuclear units are further extended into a three‐dimensional supramolecular structure through extensive O—H...O and N—H...O hydrogen bonds. Moreover, the three‐dimensional nature of the crystal packing is reinforced by the π–π stacking. The title compound exhibits photoluminescence in the solid state, with an emission maximum at 415 nm.  相似文献   

15.
Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene‐1,4‐dicarboxylic acid (H2BDC) and pyridine (py) with ZnII or CoII yielded two new coordination polymers, namely, poly[(μ4‐benzene‐1,4‐dicarboxylato‐κ4O:O′:O′′:O′′′)(pyridine‐κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena‐poly[aqua(μ3‐benzene‐1,4‐dicarboxylato‐κ3O:O′:O′′)bis(pyridine‐κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the ZnII cation is five‐coordinated by four carboxylate O atoms from four BDC2− ligands and one pyridine N atom in a distorted square‐pyramidal coordination geometry. Four carboxylate groups bridge two ZnII ions to form centrosymmetric paddle‐wheel‐like Zn22‐COO)4 units, which are linked by the benzene rings of the BDC2− ligands to generate a two‐dimensional layered structure. The two‐dimensional layer is extended into a three‐dimensional supramolecular structure with the help of π–π stacking interactions between the aromatic rings. Compound (II) has a one‐dimensional double‐chain structure based on Co22‐COO)2 units. The CoII cations are bridged by BDC2− ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC2− ligands, one water O atom and two pyridine N atoms. Interchain O—H…O hydrogen‐bonding interactions link these chains to form a three‐dimensional supramolecular architecture.  相似文献   

16.
Reaction of CdII and ZnII thiocyanate with 3‐acetylpyridine leads to the formation of the new CdII and ZnII coordination compounds [Cd(NCS)2(3‐acetylpyridine)4] ( 1A ), [Cd(NCS)2(3‐acetylpyridine)2]n ( 1B ), [Cd(NCS)2(3‐acetylpyridine)]n ( 1C ) and [Zn(NCS)2(3‐acetylpyridine)2] ( 2A ). Compound 1A consists of discrete complexes, in which the metal centers are octahedrally coordinated by four terminal bonded N‐donor co‐ligands and two terminal N‐bonded thiocyanato anions. In compound 2A the metal centers are only tetrahedrally coordinated by two terminal bonded N‐donor co‐ligands and two terminal N‐bonded thiocyanato anions. In compound 1B the CdII cations are octahedrally coordinated by two terminal bonded N‐donor co‐ligands and four thiocyanato anions. The metal centers are linked by μ‐1, 3 bridging thiocyanato anions into chains. In compound 1C the metal cations are octahedrally coordinated by two μ‐1, 5 bridging 3‐acetyl‐pyridine ligands and four μ‐1, 3 bridging thiocyanato anions building up a three‐dimensional coordination network. Investigations on the thermal degradation behavior of all compounds using simultaneous differential thermoanalysis and thermogravimetry as well as X‐ray powder diffraction and IR spectroscopy prove that on heating compound 2A decompose without the formation of 3‐acetylpyridine‐deficient intermediates. In contrast, for compound 1A a stepwise decomposition is observed, leading to the formation of the 3‐acetylpyridine‐deficient compound [Cd(NCS)2(3‐acetylpyridine)2]n ( 1B ) which decomposes on further heating  相似文献   

17.
Three MnII complexes have been synthesized under similar experimental conditions. Of these [Mn2(benzoate)4(L)2] (where L=4-styrylpyridine or 4spy, 1 and 2-fluoro-4′-styrylpyridine or 2F-4spy, 3 ) are paddlewheel complexes, but crystallized in different space groups. Whereas [Mn2(benzoate)4(3F-4spy)4] (3F-4spy=3-fluoro-4′-styrylpyridine), 4 is a dinuclear complex having different stoichiometry from 1 and 3 with two pairs of 3F-4spy ligands aligned in face-to-face manner. An irreversible phase transition occurs from the space group P21/c to C2/c when 1 was heated up to 125 °C to 2 in a single-crystal-to-single-crystal fashion or when ground 1 to powder. 2 is isomorphous and isostructural to 3 . Complimentary π–π interactions in head-to-tail alignment of the styrylpyridine ligands furnishes 1D aggregates in 1 – 3 which are congenial to undergo [2+2] cycloaddition reaction under UV light. Whereas, face-to-face alignment of the 4spy pairs in 4 is expected to provide a head-to-head photoproduct. All the MnII complexes are indeed found to be photoreactive. To our surprise, contrary to their ZnII analogues, 2 and 3 were not found to be photosalient. The percentage volume expansion during the photoreaction as determined from the density measurements, was found to be too low (3.2 and 4.6 % respectively for 2 and 3 ) to have this behavior.  相似文献   

18.
Nine new coordination compounds have been synthesized by the reaction of salts of bivalent metal ions (a=ZnII, b=CuII, c=NiII, d=CoII) with the bis(benzoylhydrazone) derivative of 4,6‐diacetylresorcinol (H4L). Three kinds of complexes have been obtained: homodinuclear compounds [M2(H2L)2]?nH2O ( 1 a , 1 b , 1 c , and 1 d ), homotetranuclear compounds [M4(L)2]?n(solv) ( 2 a and 2 c ), and heterotetranuclear compounds [Zn2M2(L)2]?n(solv) ( 2 ab , 2 ac , and 2 ad ). The structures of the free ligand H4L?2 DMSO and its complexes [Zn2(H2L)2(DMSO)2] ( 1 a* ), [Zn4(L)2(DMSO)6] ( 2 a* ), and [Zn0.45Cu3.55(L)2(DMSO)6]?2 DMSO ( 2 ab* ) were elucidated by single‐crystal X‐ray diffraction. The ligand shows luminescence properties and its fluorimetric behavior towards MII metals (M=Zn, Cu, Ni and Co) has been studied. Furthermore, the solid‐state luminescence properties of the ligand and compounds have been determined at room temperature. 1H NMR spectroscopic monitoring of the reaction of H4L with ZnII showed the deprotonation sequence of the OH/NH groups upon metal coordination. Heteronuclear reactions have also been monitored by using ESI‐MS and spectrofluorimetric techniques.  相似文献   

19.
Two new ZnII(μ‐4,4′‐bipy) coordination polymers with acetate anions, [Zn(4,4′‐bipy)(AcO)2] ( 1 ) and [Zn2(4,4′‐bipy)(AcO)4] ( 2 ), have been synthesized. The compounds were characterized with elemental analysis, IR‐, 1H NMR‐, 13C NMR spectroscopy and studied by thermal analysis, fluorescence measurements and x‐ray crystallography. The structural studies of compound 1 suggest the structure is a coordination polymer of zinc(II) consisting of linear double chains formed by bridging 4,4′‐bipy ligand and connection of the acetate‐bridged centrosymmetric [Zn2(OAc)2]2+ nodes.  相似文献   

20.
Synthesis and Structures of the Zinc‐ and Cadmium‐N‐Acylthiourea Complexes The synthesis and crystal structures of the N,N‐Diisobutyl‐N′‐benzoylthiourea complexes [Zn(Bui2btu)2] and [Cd(Bui2btu)2(HBui2btu)] are reported. The complexes of ZnII and CdII have different molecular structures. Whereas ZnII forms a bischelate with tetrahedral coordination, three ligands coordinate in a trigonal‐bipyramidal manner in the CdII complex.  相似文献   

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