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1.
Three new coordination compounds, [Pb(HBDC‐I4)2(DMF)4]( 1 ) and [M(BDC‐I4)(MeOH)2(DMF)2]n (M = ZnII for 2 and MnII for ( 3 ) (H2BDC‐I4 = 2, 3, 5, 6‐tetraiodo‐1, 4‐benzenedicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X‐ray single crystal structure analysis. Single‐crystal X‐ray diffraction reveals that 1 crystallizes in the monoclinic space group C2/c and has a discrete mononuclear structure, which is further assembled to form a two‐dimensional (2D) layer through intermolecular O–H ··· O and C–H ··· O hydrogen bonding interactions. The isostructural compounds 2 and 3 crystallize in the space group P21/c and have similar one‐dimensional (1D) chain structures that are extended into three‐dimensional (3D) supramolecular networks by interchain C–H ··· π interactions. The PbII and ZnII complexes 1 and 2 display similar emissions at 472 nm in the solid state, which essentially are intraligand transitions.  相似文献   

2.
A novel two‐dimensional (2D) ZnII coordination framework, poly[[μ‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene](μ‐5‐nitrobenzene‐1,3‐dicarboxylato)zinc(II)], [Zn(C8H3NO6)(C14H14N4)]n or [Zn(NO2‐BDC)(1,3‐BMIB)]n [1,3‐BMIB is 1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene and NO2‐H2BDC is 5‐nitrobenzene‐1,3‐dicarboxylic acid], has been prepared and characterized by IR, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. Single‐crystal X‐ray diffraction analysis revealed that the compound is a new 2D polymer with a 63 topology parallel to the (10) crystal planes based on left‐handed helices, right‐handed helical NO2‐BDC–Zn chains and [Zn2(1,3‐BMIB)2]n clusters. In the crystal, adjacent layers are further connected by C—H…O hydrogen bonds, C—H…π interactions, C—O…π interactions and N—O…π interactions to form a three‐dimensional structure in the solid state. In addition, the compound exhibits strong fluorescence emissions in the solid state at room temperature.  相似文献   

3.
Three coordination polymers, namely [Co(BDC)( L )] · H2O ( 1 ), [Co(NPH)( L )] · H2O ( 2 ), and [Ni(NPH)( L )(H2O)3] · H2O ( 3 ) [H2BDC = 1, 3‐benzenedicarboxylic acid, H2NPH = 3‐nitrophthalic acid, L = N,N′‐bis(3‐pyridyl)‐terephthalamide] were hydrothermally synthesized by self‐assembly of cobalt/nickel chloride with a semi‐rigid bis‐pyridyl‐bis‐amide ligand and two aromatic dicarboxylic acids. Single crystal X‐ray diffraction analyses revealed that complexes 1 and 2 are two‐dimensional (2D) coordination polymers containing a one‐dimensional (1D) ribbon‐like Co‐dicarboxylate chain and a 1D zigzag Co‐ L chain. Although the coordination numbers of CoII ions and the coordination modes of two dicarboxylates are different in complexes 1 and 2 , they have a similar 3, 5‐connected {42.67.8}{42.6} topology. In complex 3 , the adjacent NiII ions are linked by L ligands to form a 1D polymeric chain, whereas the 1D chains does not extend into a higher‐dimensional structure due to the ligand NPH with monodentate coordination mode. The adjacent layers of complexes 1 and 2 and the adjacent chains of 3 are further linked by hydrogen bonding interactions to form 3D supramolecular networks. Moreover, the thermal stabilities, fluorescent properties, and photocatalytic activities of complexes 1 – 3 were studied.  相似文献   

4.
The structure of {[Zn2(1,2,4,5‐btc)(pz)(H2O)4]·2(H2O)}n (1,2,4,5‐btc = 1, 2, 4, 5‐benzenetetracarboxylate, pz = pyrazine) is a two‐dimensional coordination network. The zinc(II) center is in a distorted octahedral NO5 coordination environment that is defined by one nitrogen atom of pyrazine, three oxygen atoms of carboxyl groups from 1,2,4,5‐benzenetetracarboxylate tetraanions and two water molecules. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

5.
The zinc(II) atom in the crystal structure of the title coordination polymer, [Zn(p‐BDOA)·2H2O]n (p‐BDOA2? = benzene‐1,4‐dioxyacetate), exists in a distorted trigonal prismatic geometry. Adjacent zinc(II) ions are linked by the p‐BDOA2? ligands to furnish a one‐dimensional (1‐D) zigzag chain. A three‐dimensional (3‐D) network structure is stabilized by extended hydrogen bonds. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

6.
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   

7.
The three‐dimensional (3D) coordination polymer [Zn6(btc)4(4,4′‐bipy)5]n ( 1 ) (btc = 1,2,4‐benzenetricarboxylate; 4,4′‐bipy = 4,4′‐bipyridine) has been prepared hydrothermally. The zinc(II) centers in 1 are bridged by btc ligands to form a trinuclear subunit, which is further linked by 4,4′‐bipy and btc ligands to construct the 3D coordination architecture. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

8.
Two coordination polymers based on 1, 6‐bis(2‐methyl‐imidazole‐1‐yl)‐hexane (bimh), namely {[Zn3(BTC)2(bimh)] · (bimh)}n ( 1 ) and {[Zn(IPA)(bimh)] · (CH3CH2OH)0.5}n ( 2 ) (H3BTC = trimesic acid, H2IPA = isophthalic acid), were synthesized through hydrothermal reactions. In compound 1 , the zinc(II) ions are bridged by BTC3– ligands to form an undulating infinite two‐dimensional (2D) polymeric network. The 3D networks of 1 show a twofold interpenetrating net. In compound 2 , zinc(II) ions are bridged by IPA2– ligands to form one‐dimensional (1D) helical structures. The 2D structures of 2 are further assembled into 3D networks through aromatic π–π stacking interactions. Both compounds exhibit strong photoluminescence at room temperature and may be good candidates for potential luminescence materials.  相似文献   

9.
The title compound, {[Zn4(C8H4O4)3(OH)2(C12H6N2O2)2]·2H2O}n, has been prepared hydrothermally by the reaction of Zn(NO3)2·6H2O with benzene‐1,4‐dicarboxylic acid (H2bdc) and 1,10‐phenanthroline‐5,6‐dione (pdon) in H2O. In the crystal structure, a tetranuclear Zn4(OH)2 fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN2O4] octahedron and a [ZnO4] tetrahedron bridged by a μ3‐OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN2O4] octahedron. The two crystallographically independent bdc2− ligands are fully deprotonated and adopt μ3‐κOO′:κO′′ and μ4‐κOO′:κO′′:κO′′′ coordination modes, bridging three or four ZnII cations, respectively, from two Zn4(OH)2 units. The Zn4(OH)2 fragment connects six neighbouring tetranuclear units through four μ3‐bdc2− and two μ4‐bdc2− ligands, forming a three‐dimensional framework with uninodal 6‐connected α‐Po topology, in which the tetranuclear Zn4(OH)2 units are considered as 6‐connected nodes and the bdc2− ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn4(OH)2 unit and are connected to it through hydrogen‐bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π–π interactions between the pdon and μ4‐bdc2− ligands.  相似文献   

10.
Ligands based on polycarboxylic acids are excellent building blocks for the construction of coordination polymers; they may bind to a variety of metal ions and form clusters, as well as extended chain or network structures. Among these building blocks, biphenyltetracarboxylic acids (H4bpta) with C 2 symmetry have recently attracted attention because of their variable bridging and multidentate chelating modes. The new luminescent three‐dimensional coordination polymer poly[(μ5‐1,1′‐biphenyl‐2,2′,4,4′‐tetracarboxylato)bis[μ2‐1,4‐bis(1H‐imidazol‐1‐yl)benzene]dizinc(II)], [Zn2(C16H6O8)(C12H10N4)]n , was synthesized solvothermally and characterized by single‐crystal X‐ray diffraction, elemental analysis and IR spectroscopy. The crystal structure contains two crystallographically independent ZnII cations. Both metal cations are located on twofold axes and display distorted tetrahedral coordination geometries. Neighbouring ZnII centres are bridged by carboxylate groups in the syn anti mode to form one‐dimensional chains. Adjacent chains are linked through 1,1′‐biphenyl‐2,2′,4,4′‐tetracarboxylate and 1,4‐bis(1H‐imidazol‐1‐yl)benzene ligands to form a three‐dimensional network. In the solid state, the compound exhibits blue photoluminescence and represents a promising candidate for a thermally stable and solvent‐resistant blue fluorescent material.  相似文献   

11.
An unusual zinc(II) coordination polymer [Zn5(OH)2(bbtz)2(bdc)4]n ( 1 ) [bbtz?1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene, bdc?1,2‐benzenedicarboxylate] was synthesized and characterized. 1 contains an unusual 2D network based on pentanuclear zinc(II) cluster [Zn5(OH)2]. Two adjacent pentanuclear Zn(II) clusters are bridged by four bdc ligands and extend to form the one‐dimensional chain. The bbtz ligands further link the one‐dimensional chains, resulting in a two‐dimensional coordination network. The luminescence and thermal stability were investigated.  相似文献   

12.
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   

13.
Three new compounds based on H2BDC and PyBImE [H2BDC = 1,4‐benzenedicarboxylatic acid, PyBImE = 2‐(2‐pyridin‐4‐yl‐vinyl)benzimidazole], namely, [Co(PyBImE)(BDC)(H2O)2] ( 1 ), [Co(PyBImE)2(HBDC)(BDC)0.5] ( 2 ), and [(HPyBImE)+ · (BDC)20.5 · (H2BDC)0.5] ( 3 ), were synthesized by hydrothermal methods and characterized by single‐crystal X‐ray diffraction. Compound 1 is a one‐dimensional chain bridged by terephthalate in a bis(monodentate) fashion. In the complex the nitrogen atom from NBIm and the coordination water molecule complete the coordination sphere. In complex 2 , the dinuclear cobalt units are bridged by terephthalate in a bis(bidentate) fashion into a one‐dimensional chain, but different from complex 1 , the nitrogen atom from NPy and the oxygen atom from hydrogenterephthalate complete the coordination sphere. Complex 3 is a co‐crystal with PyBImE and H2BDC in a 1:1 ratio and the transfer of hydrogen atoms leads the complex into a salt. Interesting supramolecular structures are shown due to the hydrogen bonding as well as π ··· π interactions in the three complexes. Thermal and magnetic properties of 1 and 2 were also studied.  相似文献   

14.
Zinc(II) carboxylates with O‐, S‐ and N‐donor ligands are interesting for their structural features, as well as for their antibacterial and antifungal activities. The one‐dimensional zinc(II) coordination complex catena‐poly[[bis(2,4‐dichlorobenzoato‐κO)zinc(II)]‐μ‐isonicotinamide‐κ2N1:O], [Zn(C7H3Cl2O2)2(C6H6N2O)]n, has been prepared and characterized by IR spectroscopy, single‐crystal X‐ray analysis and thermal analysis. The tetrahedral ZnO3N coordination about the ZnII cation is built up by the N atom of the pyridine ring, an O atom of the carbonyl group of the isonicotinamide ligand and two O atoms of two dichlorobenzoate ligands. Isonicotinamide serves as a bridge between tetrahedra, with a Zn...Zn distance of 8.8161 (7) Å. Additionally, π–π interactions between the planar benzene rings contribute to the stabilization of the extended structure. The structure is also stabilized by intermolecular hydrogen bonds between the amino and carboxylate groups of the ligands, forming a two‐dimensional network. During thermal decomposition of the complex, isonicotinamide, dichlorobenzene and carbon dioxide were evolved. The final solid product of the thermal decomposition heated up to 1173 K was metallic zinc.  相似文献   

15.
A novel three‐dimensional (3D) ZnII coordination polymer, namely, poly[[[1,4‐bis(pyridin‐4‐yl)benzene](μ3‐3,3′‐{[1,3‐phenylenebis(methylene)]bis(oxy)}dibenzoato)zinc(II)] 1,4‐bis(pyridin‐4‐yl)benzene], {[Zn(C22H16O6)(C16H12N2)]·C16H12N2}n or {[Zn(PMBD)(DPB)]·DPB}n, 1 , where H2PMBD is 3,3′‐{[1,3‐phenylenebis(methylene)]bis(oxy)}dibenzoic acid and DPB is 1,4‐bis(pyridin‐4‐yl)benzene, has been synthesized by self‐assembly using zinc nitrate, a semi‐rigid dicarboxylic acid and a nitrogen‐containing ligand. The single‐crystal X‐ray structure determination indicates that 1 possesses an intriguing 3D architecture with a 4‐connected uninodal cds topology, which is constructed from dinuclear {Zn2} clusters and V‐shaped PMBD2? linkers. Compound 1 exhibits excellent photocatalytic activity on the degradation of the organic dyes Rhodamine B (RhB), Rhodamine 6G (Rh6G) and Methyl Red (MR).  相似文献   

16.
Metal–organic frameworks (MOFs) based on multidentate N‐heterocyclic ligands involving imidazole, triazole, tetrazole, benzimidazole, benzotriazole or pyridine present intriguing molecular topologies and have potential applications in ion exchange, magnetism, gas sorption and storage, catalysis, optics and biomedicine. The 2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]‐1H‐benzimidazole (tmb) ligand has four potential N‐atom donors and can act in monodentate, chelating, bridging and tridentate coordination modes in the construction of complexes, and can also act as both a hydrogen‐bond donor and acceptor. In addition, the tmb ligand can adopt different coordination conformations, resulting in complexes with helical structures due to the presence of the flexible methylene spacer. A new three‐dimensional coordination polymer, poly[[bis(μ2‐benzene‐1,4‐dicarboxylato)‐κ4O1,O1′:O4,O4′2O1:O4‐bis{μ2‐2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl‐κN4]‐1H‐benzimidazole‐κN3}dizinc(II)] trihydrate], {[Zn(C8H4O4)(C10H9N5)]·1.5H2O}n, has been synthesized by the reaction of ZnCl2 with tmb and benzene‐1,4‐dicarboxylic acid (H2bdic) under solvothermal conditions. There are two crystallographically distinct bdic2− ligands [bdic2−(A) and bdic2−(B)] in the structure which adopt different coordination modes. The ZnII ions are bridged by tmb ligands, leading to one‐dimensional helical chains with different handedness, and adjacent helices are linked by bdic2−(A) ligands, forming a two‐dimensional network structure. The two‐dimensional layers are further connected by bdic2−(B) ligands, resulting in a three‐dimensional framework with the topological notation 66. The IR spectra and thermogravimetric curves are consistent with the results of the X‐ray crystal structure analysis and the title polymer exhibits good fluorescence in the solid state at room temperature.  相似文献   

17.
A two‐dimensional coordination polymer [Zn2(tp)2(pz)(H2O)2]n (tp = terephthalate, pz = pyrazine) has been synthesized by the hydrothermal reaction of zinc terephthalate and pyrazine. The Zinc(II) centre is in a distorted pyramidal geometry, being coordinated by one water molecule, one nitrogen atom from a bridging pz and two different bridging tp ligands, one chelating and the other monodentate. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

18.
Three novel 5‐R‐tetrazolato complexes (R = Me, Ph, 4‐Py), namely [Zn2(MeCN4)4(DMSO)2] ( 1 ), [Cu2(PhCN4)4(en)2] · 2DMSO ( 2 ), and [Cu(4‐PyCN4)2(DMSO)2] · 4DMSO ( 3 ), were isolated as unexpected products under attempts to prepare heterometallic tetrazolates using a direct synthesis strategy in the Cu0‐ZnO‐en‐RCN4H‐DMSO system (en = ethylenediamine). The prepared compounds were characterized by elemental, single‐crystal X‐ray, and thermal analyses, and IR spectroscopy. Variation of the 5‐substituent of the tetrazole ring causes different composition of complexes 1 – 3 and diverse coordination modes of 5‐R‐tetrazolato ligands. Complex 1 is a 3D coordination polymer due to N1, N4‐bridging of 5‐methyltetrazolato anions. Complex 2 , with en as a coligand, has a dinuclear structure with two copper atoms linked together by two 5‐phenyltetrazolato ligands by tetrazole N2, N3 bridges. Complex 3 represents a 2D coordination polymer, formed due to 5‐(4‐pyridyl)tetrazolato bridges between adjacent copper atoms (with the tetrazole and pyridine rings nitrogen atoms as coordination centers). DMSO molecules, included in all the compounds, are solvate and/or coordinated ones.  相似文献   

19.
Two novel zinc coordination polymers {[Zn(PhCOO)2(bmix)]}n 1 and {[Zn(ada)(bmix)]·(H2O)2}n 2 (bmix = 1,4‐bis(2‐methylimidazole‐1‐ylmethyl)benzene, H2ada = adipic acid), were obtained by the hydrothermal reactions of bmix and zinc acetate with two carboxylate anions, respectively. Structural analyses show that complex 1 possess a one‐dimensional helix chain structure, 2 takes two‐dimensional corrugated (4,4) layer motif. The structural differences of two complexes indicate that organic carboxylate anions play important roles in the formation of such zinc(II) coordination architectures.  相似文献   

20.
The structure of the title compound, [Zn2(btc)(DMF)2]n (btc = 1,2,4,5‐benzenetetracarboxylate, DMF = N,N‐dimethylformamide), shows that the octahedrally and tetrahedrally coordinated zinc atoms (present in the ratio 1:1) are linked by btc ligands to form a three‐dimensional network comprising cross‐linked channels occupied by coordinated DMF molecules. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

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