The cadmium(II) complexes [CdL1(m‐nba)2] ( 1 ), [CdL1(p‐nba)2] · C2H5OH ( 2 ), [CdL2(p‐nba)2] · CH3OH ( 3 ), and [CdL2(p‐nbat)2] ( 4 ) containing the ligands L1 and L2 [L1 = 2,6‐bis(benzimidazol‐2‐yl)pyridine, L2 = bis(2‐benzimidazolylmethyl)amine] were synthesized and characterized (m‐nba, p‐nba, and p‐nbat are the anions of p‐nitrobenzoic acid, m‐nitrobenzoic acid, and p‐nitrobenzeneacetic acid, respectively). The complexes were investigated by X‐ray single crystal diffraction, elemental analysis as well as IR and fluorescence spectroscopy. Compounds 1 – 3 contain a distorted pentagonal bipyramidal coordination sphere with CdII coordinated by two carboxylate ligands in bidentate‐chelating mode, whereas complex 4 exhibits a distorted octahedral arrangement with one carboxylate ligand in bidentate‐chelating and the other in monodentate coordination mode. 1 and 2 form a 1D chain interplayed by hydrogen bonding and strong π–π stacking interactions. 3 and 4 vary from 1D chain into 2D single‐layer and double‐layer networks because of more extensive hydrogen bonding interactions. The complexes show emission maxima in the blue region in the solid state and emission bands are red‐shifted compared to those of the free ligands. 相似文献
Three silver(I) coordination polymers namely, [Ag4(L1)2(1, 4‐ndc)2]n ( 1 ) {[Ag(L2)] · (1, 4‐Hndc) · H2O}n ( 2 ), and {[Ag(L3)(H2O)] · (1, 4‐Hndc)}n ( 3 ) [L1 = 1, 3‐bis(benzimidazol‐1‐ylmethyl)benzene, 1, 4‐H2ndc = 1, 4‐naphthalenedicarboxylic acid, L2 = 1, 3‐bis(5, 6‐dimethylbenzimidazole‐1‐ylmethyl)benzene, L3 = 1, 4‐bis(5, 6‐dimethylbenzimidazole)butane], were hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction analysis, elemental analysis, IR spectroscopy, thermogravimetric and XRPD analysis. Complex 1 displays a 1D tube‐like chain, which is packed into a 3D supramolecular network by π–π stacking interactions. Complex 2 features an infinite 1D linear chain. Complex 3 contains a 1D wave‐like chain, which is extended into a 3D supramolecular network through O–H ··· O hydrogen bonding interactions. Moreover, these coordination polymers exhibit catalytic properties for degradation of methyl orange in Fenton‐like processes. 相似文献
Two MnII coordination polymers based on the flexible bis(benzimidazole) and dicarboxylic acids, namely, [Mn(L1)(bpdc)(H2O)0.5]n ( 1 ) and [Mn(L2)(Htbi)2]n ( 2 ) [L1 = 1,4‐bis(5,6‐dimethylbenzimidazol‐1‐ylmethyl)benzene, H2bpdc = 4,4′‐biphenyldicarboxylic acid, L2 = 1,4‐bis(5,6‐dimethylbenzimidazole)butane, H2tbi = 5‐tert‐butyl isophthalic acid] were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, as well as single‐crystal X‐ray diffraction. Both of the complexes crystallize in the triclinic P$\bar{1}$ space group and present distorted octahedral configurations. Complex 1 possesses a 2D binodal (3,5)‐connected 3,5L2 network with the point symbol of (42.67.8)(42.6), whereas 2 features a 2D uninodal 3‐connected hcb topology and the Schläfli symbol is (63). Complexes 1 and 2 ultimately are extended into 3D supramolecular framework via π–π stacking and O–H ··· O hydrogen bonding interaction, respectively. Moreover, both of the complexes manifest excellent catalytic activities for the degradation of Congo red. 相似文献
The cobalt(II) coordination polymers{[Co(L1)(nda)] · 2H2O}n ( 1 ) and [Co(L2)2(nda)]n ( 2 ), [L1 = 1,2‐bis(2‐methylbenzimidazol‐1‐ylmethyl)benzene, L2 = 1,4‐bis(5,6‐dimethylbenzimidazol‐1‐ylmethyl)benzene, H2nda = 2,6‐naphthalenedicarboxylic acid] were hydrothermally synthesized by self‐assembly of cobalt chloride with H2nda and different semi‐rigid bis(benzimidazole) derivatives and characterized by IR spectroscopy, elemental analysis, and X‐ray single‐crystal diffraction. Complex 1 displays a 2D layer with (4,4) topology, complex 2 exhibits a 1D infinite chain structure, both complexes were further packed into 3D and 2D supramolecular architectures by weak hydrogen bonding. The catalytic activities of the complexes for degradation of Congo red in a Fenton‐like process are presented. In addition, the electrochemical and electrocatalytical behavior of CPEs modified with both cobalt complexes (Co‐CPE) were investigated in detail. 相似文献
To determine the influence of the size of the aromatic chelate ligands on the frameworks of metal tretracarboxylate polymers, two new coordination polymers [Cd(btc)0.5 (2,2′‐bpy)] ( 1 ) and [Cd(btc)0.5(phen)]·H2O ( 2 ) (H4btc = biphenyl‐3,3′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized under similar hydrothermal conditions. In complex 1 , the dimeric Cd2 units are linked by bridging btc4? ligand to form a 2D layered network, whereas complex 2 possesses a 3D metal‐organic framework consisting of the dimeric Cd2 units. The differences of two metal‐organic frameworks demonstrate that the size of the rigid aromatic chelate ligands have an important effect on the structures of their complexes. Additionally, the two complexes show strong fluorescence in the solid state at room temperature. 相似文献
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
Four new cobalt, manganese, and copper bis(phosphonates), [Co2{Cl2C(PO3)2}(H2O)7 · 4H2O] ( 1 ), [Co{Cl2C(PO2O(C(O)C6H5))2(H2O)5} · 2H2O{Cl2C(PO2O(C(O)C6H5))2}{Co(H2O)6}] ( 2 ), [Mn{[Cl2C(PO2O(C(O)C6H5))2](H2O)3}] ( 3 ), and [Cu{(CH2C5H5N)C(OH)(PO3H)2}2 · 4H2O] ( 4 ), were prepared by gel, liquid, and evaporation crystallisation methods. Compounds 1 – 4 were characterised by X‐ray single‐crystal diffraction, elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The effects of metal and various substituted groups in bis(phosphonate) ligands on the structure formation of bis(phosphonates) were studied. In the structure of 1 , the clodronic acid ligand ( L1 ) is in bischelating bonding mode, and the dinuclear units of 1 are surrounded by two‐dimensional water cluster patterns. The hydrogen bond network of compound 1 is extended to a three‐dimensional framework when the phosphonate oxygen atoms serve as hydrogen‐bond acceptors. In complex 2 , the CoO6 octahedron shares a corner of one PCO3 tetrahedron of the dibenzoyl derivative of clodronic acid ligand ( L2 ), and forms a two‐dimensional hydrogen bonding network, which consists of [Co(H2O)6}]2+ cations, lattice water molecules and L2 ligand molecules. Compound 3 , in turn, consists of dimeric building blocks built up of PCO3 tetrahedra of the ligand L2 , which connect the corner‐sharing MnO6 octahedra and form an overall 2D structure through hydrogen bonds of coordinated and crystal water molecules and phosphonate oxygen atoms. Complex 4 is among the first metal complexes of risedronic acid ( L3 ). In compound 4 , two L3 ligand molecules chelate tridentately the CuII atom at the center of symmetry, and the monomeric units of 4 are connected to a 3D structure through hydrogen bonding of coordinated and lattice water molecules to both protonated and deprotonated phosphonate oxygen atoms and protonated nitrogen atoms in the pyridine ring. 相似文献
A new 3d–4f heterometallic coordination framework, {[Eu(ox)(H2O)4] · [CuBr(2‐pzc)2] · 4H2O} ( 1 ) [ox = oxalate; 2‐pzc = pyrazine‐2‐carboxylate] was synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis, as well as single‐crystal X‐ray diffraction. Complex 1 represents one 3D supramolecular heterometallic coordination framework that is assembled from rare lanthanide‐ox anionic chains and CuBr(2‐pzc)2 cationic units through hydrogen bonds. 相似文献
Three metal coordination polymers {[Co(L)2(H2O)2]2+ · 2NO3–}n ( 1 ), {[Mn(L)2(H2O)2]2+ · 2Cl– · 3H2O}n ( 2 ), and [ZnL(ba)2]n ( 3 ) [L = 3,5‐bis(imidazole‐1‐yl)pyridine and Hba = benzoic acid] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X‐ray powder diffraction, and X‐ray single crystal diffraction. Complex 1 shows a one‐dimensional (1D) chain structure. Adjacent chains are connected by hydrogen bonding and nitrate groups to form a 3D network. Complex 2 features a 2D layer structure. A three‐dimensional network is constructed through the cluster consisting of two chloride ions and three water molecules. Complex 3 shows a 1D zigzag chain structure that further twists together to form a 3D network. The X‐ray powder diffraction patterns were compared with the simulated ones. Moreover, the luminescent properties of 1 – 3 were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the three complexes. 相似文献
A series of cadmium(II) coordination polymers constructed from 1, 3‐bis(pyridine‐3‐carbonyl)imidazolidin‐2‐thioxo (3‐bpit) and 1, 3‐bis(pyridine‐4‐carbonyl)imidazolidin‐2‐thioxo (4‐bpit), namely,{[Cd(SCN)2(3‐bpit)2] · 2(CH3OH)}n ( 1 ), {[Cd(NO3)2(3‐bpit)2] · 2(CH3OH)}n( 2 ), [CdI2(4‐bpit)]n ( 3 ), and [CdCl2(4‐bpit)4]n ( 4 ) were prepared and characterized by single‐crystal X‐ray diffraction. Complexes 1 and 2 display different types of infinite 1D helical chain structures, both of which contain 24‐membered metallocyclic rings. Complex 3 is composed of 1D zigzag chains, which further form a 3D supramolecular architecture by weak C–H ··· S and S ··· I interactions. Complex 4 also features a 3D supramolecular network assembled from 2D rhombus‐shaped layer through intermolecular hydrogen bonding. These structures indicate that the conformation of the ligand and the diverse anions take important roles in the formation of different frameworks. Thermogravimetric and fluorescent properties over complexes are also discussed. 相似文献
Hydrothermal synthesis has afforded a family of new coordination polymers incorporating 3,3′‐bipyridine (3,3′‐bpy), {[M(3,3′‐bpy)(H2O)4](SO4)·2H2O} (M = Co, Ni, Zn). The crystal structures revealed 1‐D undulating cationic ribbons of formulation {[M(3,3′‐bpy)(H2O)4]}n2n+ with both unligated charge‐balancing sulfate anions and water molecules of crystallization entrapped by hydrogen bonding. The 1‐D ribbons run along the (101) crystal direction and further aggregate via extensive hydrogen bonding patterns. Thermal decomposition data were consistent with stepwise loss of water molecules of crystallization and aquo ligands followed by decomposition due to ligand removal. 相似文献
Two nickel(II) coordination polymers, formulated as {[Ni2(bix)2(tbta)2(H2O)4] · 0.25H2O}n ( 1 ) and [Ni2(bix)(aip)2(H2O)2]n ( 2 ) [bix = 1, 4‐bis(imidazol‐1‐ylmethyl)benzene, H2tbta = tetrabromoterephthalic acid, H2aip = 5‐aminoisophthalic acid] were synthesized under hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction methods, IR spectroscopy, TGA, and elemental analysis. Complex 1 exhibits a 2D (4, 4) layer with {44.62} topology. Complex 2 shows 2D (3, 4)‐connected 3 , 4L83 sheets, which are finally extended into an unusual (5, 6)‐connected 3D supramolecular network by classic hydrogen bond interactions. Fluorescence, UV/Vis diffuse reflection spectra, and catalytic properties of two complexes for the degradation of the methyl orange dye in a photo‐Fenton‐like process were investigated. 相似文献
The reaction of cadmium salts with various amounts of the tridentate NS2‐chelating ligands 1‐(2‐mercapto‐acetophenone)‐4‐triphenylmethylthiosemicarbazone (H2L1) and 1‐(5‐mercapto‐3‐methyl‐1‐phenylpyrazole‐4‐carboxaldehyde)‐4‐triphenyl‐methylthiosemicarbazone (H2L2) in the presence of bases like N‐methylimidazole (N–MeIm), pyridine (py) or triethylamine (Et3N) provided a series of novel mono‐, di‐, tri‐ and heptanuclear cadmium complexes. They are of the general formulas [CdL1(N–MeIm)]2 ( 1 ), [CdL1(py)]2 ( 2 ), [CdL2(N–MeIm)]2 ( 3 ), [CdL2(py)3] · 0.25 C6H14 · 0.5 py ( 4 ), [Et3NH]2[Cd3L ] · 7 MeOH ( 5 ), [Et3NH]2[Cd3L ] ( 6 ) and [Et3NH]2[Cd7L ] · 14 MeOH ( 7 ). The compounds were characterized by elemental analysis, IR‐ and 1H‐NMR‐spectroscopy. Single‐crystal X‐ray structure analyses are reported for the complexes 2 , 4 , 5 and 7 . While 2 has a dimeric structure where each cadmium ion is pentacoordinated in a N2S3‐environment, 4 consists of a monomeric cadmium center with distorted octahedral N4S2‐coordination. The complexes 5 and 7 exhibit new structural types for tri‐ and heptanuclear cadmium compounds. It is shown that sulfur bridging might proceed via arylthiolates, iminothiolates or even both functions of the ligand. Aggregation is influenced by various factors like solvents, counterions and ligand properties. 相似文献
The polymers [Cd(L)(H2O)] ( 1 ) and [Zn(L)(4, 4′‐bipy)(H2O)3] ( 2 ) (L = 2, 2‐dimethylsuccinated anion) were synthesized under hydrothermal conditions and characterized by IR spectrosopy, elemental analyses, and single‐crystal X‐ray diffraction analysis. The latter reveals that the polymer 1 exhibits a four‐connected dia‐topology net based on the novel tetranuclear CdII units, whereas polymer 2 displays a 4‐connnected CdSO4 topology net. Moreover, the photoluminescent properties of 1 and 2 were investigated. 相似文献
Keeping their cool : Fabrication of a 2D weblike nanonetwork of gold was successfully demonstrated through a two‐step procedure including complexation of gold precursors to a weblike supramolecular assembly of surfactant followed by in situ reduction of the precursors to gold. Molecular assemblies stabilized by hydrogen bonding provided a sound template, leading to the highly integrated structure of gold through room‐temperature (cold) nanostructure fusion.
The present paper aims at exploring the candidate hybrid structures of the Cr/trimesic acid system by assembling pre‐defined hybrid building‐blocks in direct space. Two possible hybrid building‐blocks were identified where the connection of the 1, 4 BDC molecules to an inorganic metal‐containing trimer forms a large supertetrahedron (ST) or alternatively a large supercube (SC). From existing topologies derived from the space filling packing of corner‐sharing cubes and tetrahedra, two candidates hybrid crystal structures were constructed. Lattice energy minimizations were performed on each candidate structure, as a preliminary step towards the estimation of their relative stabilities. This work further illustrates the computational design of very open hybrid frameworks using the concept of pre‐defined building blocks and their assembly in 3D space. 相似文献
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