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1.
The self-assembly of a V-shaped ligand 3,3′,4,4′-diphenylsulfonetetracarboxylate (dstc) and metal salts in the presence of a series of N-donor ligands yielded four new complexes, namely, [Cu4(H2dstc)4(phen)4]·12H2O (1), {[Cu2(dstc)(bpe)(H2O)2]·4H2O}n (2), [Cu3(dstc)(bipy)(μ2-OH)2(H2O)2]n (3), {[Cd5(dstc)2(bipy)2(μ3-OH)2(H2O)4]·4H2O}n (4) (phen = 1,10-phenanthroline; bpe = 1,2-bis(4-pyridyl)ethene; bipy = 4,4′-bipyridine). All the complexes were structurally determined by single-crystal X-ray diffraction and characterized by elemental analyses, IR spectra, X-ray powder diffraction and TG analyses. Complex 1 is a discrete tetranuclear unit, which further assembles into a 3D supramolecular framework by intermolecular hydrogen bonding interactions. Complex 2 is composed of 2D 44 grid-like layers based on dinuclear copper units. Complex 3 features a rare 3D (6,8)-connected topological net consisting of trimetallic clusters. 12-connected pentanuclear cadmium clusters are observed in complex 4 and the resulting structure shows an uncommon (4,12)-connected topology. The structural differences among 1-4 demonstrate that the nature of the N-donor assistant ligands and metal ions can play critical roles in the formation and structures of the resulting complexes. Magnetic studies showed antiferromagnetic interactions for 1 and 3. In addition, the luminescent property of 4 was also studied. 相似文献
2.
C Valan AmburoseTheivanayagam C Deivaraj Ghee Xiong LaiJeyagowry T Sampanthar Jagadese J Vittal 《Inorganica chimica acta》2002,332(1):160-166
We have utilized the possibility of altering the ratio of reactants to result in tetrahedral anions, [M(SC{O}Me)nCl4−n]2− (n=3, 4) and [Cd2Cl2(SC{O}Me)4]2−. Complexes of the formula [Ph4P]2[M(SC{O}Me)4] (M=Zn(II) (1), Cd(II) (2) or Hg(II) (3)) were synthesized by the reaction of thioacetate ligand with the metal salts and Ph4PCl in 4:1:2 molar ratio in suitable solvents. The geometry of Zn(II) in 1 is nearly tetrahedral and the distortion in tetrahedron increases in the order of 1<2<3 as observed from the SMS angles in the crystal structures. The tendency of monoanionic complexes [Ph4P][M(SC{O}Me)3] to react with 1 mole equivalent of Ph4PCl resulted in complexes of the type [Ph4P]2[M(SC{O}Me)3Cl] (M=Cd(II) (4) or Hg(II) (5)). In the structures of 4 and 5, three sulfur atoms and one chloride atom occupy the corners of the tetrahedron around the metal centers. However, in a 4:2:2 or 2:1:2 molar reaction of Me{O}CS− with CdCl2 and Ph4PCl in aqueous medium resulted in a chloro bridged dimer, [Ph4P]2[Cd2(μ-Cl)2(SC{O}Me)4] (6) as determined by X-ray crystallography. 相似文献
3.
Hydrothermal reaction of a d10 configuration divalent metal precursor with flexible-arm aromatic ortho-dicarboxylates and a bis(pyridyl)piperazine-type neutral co-ligand has generated four coordination polymers, some with rare topologies. {[Cd(hmph)(4-bpmp)1.5]·4H2O}n (1, hmph = homophthalate, 4-bpmp = bis(4-pyridylmethyl)piperazine) manifests a new 3-fold interpenetrated uninodal 5-connected 3-D net with a very simple 4466 topology, different from the usual sqp 5-connected topology. [Cd2(hmph)2(4-bpfp)]n (2, 4-bpfp = bis(4-pyridylformyl)piperazine) displays a rare 4,5-connected binodal tcs net with (4462)(4466) topology. [Zn2(1,2-phda)2(4-bpmp)(H2O)2]n (3, 1,2-phda = 1,2-phenylenediacetate) possesses an uncommon 3,4-connected binodal 2-D layer with (426)(42638) (V2O5 prototype) topology. [Zn2(hmph)2(4-bpfp)]n (4) has a decorated (4,4) grid topology with embedded [Zn2(OCO)4] paddlewheel clusters. All materials exhibit ligand-centered fluorescent behavior. Thermal degradation behavior of the 3-D network materials is reported. 相似文献
4.
Four novel topological nets of lanthanide metal-organic frameworks: [Sm2(op)3(H2O)]n (1), {Ln2(op)2(ox)(H2O)4] · H2O}n (Ln = La, 2; Sm, 3), {[La2(mp)2(ox)(H2O)4] · 2H2O}n (4), [La2(op)2(mp)(H2O)4]n (5) (op = o-phthalate, mp = m-phthalate, and ox = oxalate), have been hydrothermally synthesized and characterized. Compound 1 exhibits novel (3,4,5,6)-connected five-nodal two-dimensional net, compound 2 and 3 show the (3,4)-connected V2O5 topologies, compound 4 has the (4,5)-connected topological net, and compound 5 shows the (4,5)-connected four-nodal three-dimensional network. Photoluminescent analyses of 1 and 3 show strong blue emission in the solid state at room temperature. 相似文献
5.
Gregory A. Farnum 《Inorganica chimica acta》2011,376(1):590-597
Hydrothermal reaction of cadmium salts with homophthalic acid (H2hmph) and 1,3-bis(4-pyridyl)propane (dpp) afforded coordination polymers whose topologies are determined by the absence or presence of any unligated counteranions. [Cd(hmph)(dpp)]n (1) has a zig-zag (4,4) layer topology with simple AAA stacking. {[Cd6(hmph)4(dpp)11(H2O)4] (ClO4)4·4H2O}n (2) has a complicated, unprecedented tetranodal self-penetrated cationic three-dimensional net built from the linkage of 5-fold interpenetrated 3-connected 4.142cds-a topology [Cd6(H2O)4(dpp)11]n12n+ subnets by bridging and exotridentate hmph ligands. Luminescent properties of these materials are also discussed. 相似文献
6.
Two novel coordination polymers with interesting supramolecular architecture, [Zn2(OH)(BTC)(bix)] (1) and [Cd2(CDC)2(bix)2] (2) (H3BTC = 1,3,5-benzenetricarboxylic acid, H2CDC = trans-1,4-cyclohexanedicarboxylic acid and bix = 1,2-bis(imidazol-1-ylmethyl)benzene) have been obtained via hydrothermal reaction and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 features a 3D network with one of the scarce (3,8)-connected (43)2(46.618.84) topology based on the rare CdI2-type layer constructed from secondary building units (SBUs) of zinc clusters. While 2 exhibits a scarcely reported eight-connected 36.416.56 net with dinuclear cadmium clusters as secondary building units. The luminescent properties of 1 and 2 along with the bix ligand in the solid state were investigated. 相似文献
7.
Xiao-Li Chen Qing-Ran Wu Feng Fu Yuan-Yuan Hui Gang-Lin Xue 《Inorganica chimica acta》2010,363(2):360-3894
Three novel d10 metal coordination polymers, {[Cd(H2odpa)(phen)2]·H2O}n (1), [Cd2(odpa)(phen)(H2O)2]n (2), {[Zn4(odpa)2(phen)2(H2O)2]·H2O}n (3), (H4odpa = 4,4′-oxydiphthalic acid, phen = 1,10-phenanthroline) were obtained with different metal/ligand ratios through hydrothermal method and characterized. Compound 1 forms a one dimensional zigzag chain, in which two phen ligands chelate to one cadmium atom. Compound 2 shows a three dimensional network structure comprised of new tetranuclear cadmium clusters as the nodes and (odpa)4− anions as the linkers, exhibits an unusual topological structure. Compound 3 is an unprecedented three dimensional polymer based on octanuclear zinc clusters cross-linked by (odpa)4− anions. In 1-3, central CdII/ZnII ions and (odpa)4− ligand display completely different coordination modes and conformations. In addition, the thermal stabilities and photoluminescence properties of 1-3 were also studied. 相似文献
8.
Hydrothermal synthesis has afforded divalent cadmium coordination polymers containing isophthalate (ip) or 5-methylisophthalate (mip) dicarboxylate ligands and bis(4-pyridylformyl)piperazine (4-bpfp) or bis(4-pyridylmethyl)homopiperazine (4-bpmh) tethers. {[Cd2(ip)2(H2O)2(4-bpfp)]·7H2O}n (1) displays a (4,4) grid topology based on {Cd2O2} dimeric clusters, along with “infinite” water molecule tapes with rare T4(0)A(1) classification. {[Cd(mip)(H2O)(4-bpfp)]·3H2O}n (2) also exhibits (4,4) grid layers but with 2D + 2D → 3D mutual inclined interpenetration instead of parallel stacking. [Cd4(ip)4(4-bpmh)2]n (3) has tetrameric {Cd4(ip)4} cluster units linked by ip and 4-bpmh ligands into a unique self-penetrated 3,5,5,5-connected tetranodal net with (4.82)(436285)(446482)(4.5648) topology. {[Cd2(mip)2(H2O)2(4-bpmh)]·2H2O}n (4) possesses a structure similar to that of 1, without the aggregated water molecule tapes. All four materials emit visible light upon ultraviolet excitation, ascribed to ligand-based electronic transitions. 相似文献
9.
Karyn M. Blake 《Inorganica chimica acta》2011,373(1):201-210
Divalent cobalt coordination polymers containing both ortho-phenylenediacetate (ophda) and rigid dipyridyl ligands 4,4′-bipyridine (bpy) or 1,2-bis(4-pyridyl)ethylene (dpee) display different topologies depending on carboxylate binding mode, tether length, and inclusion of charged species. [Co(ophda)(H2O)(dpee)]n (1) displays a common (4,4) grid layer motif. Use of the shorter bpy tether afforded {[Co2(ophda)2(bpy)3(H2O)2][Co(bpy)2(H2O)4](NO3)2·2bpy·7H2O}n (2) or [Co(ophda)(bpy)]n (3) depending on cobalt precursor. Compound 2 manifests 5-connected [Co2(ophda)2(bpy)3(H2O)2]n pillared bilayer slabs with rare 4862 SnS topology and entrained [Co(bpy)2(H2O)4]2+ complex cations. The 3-D coordination polymer 3 has an uncommon 4,6-connected binodal (4462)(446108) fsc topology, and shows ferromagnetic coupling (J = +1.5(2) cm−1) along 1-D spiro-fused [Co(OCO)2]n chain submotifs. 相似文献
10.
Reaction of CdCl2 with N-alkylaminopyrazole ligands 1-[(2-ethylamino)ethyl]-3,5-dimethylpyrazole (deae), 1-[(2-(tert-butylamino)ethyl)]-3,5-dimethylpyrazole (deat), bis-[(3,5-dimethylpyrazolyl)methyl]ethylamine (bdmae), and bis-[(3,5-dimethylpyrazolyl)ethyl]ethylamine (ddae) in absolute ethanol yields [CdCl2(NN′)] (NN′ = deae (1), deat (2)), [CdCl2(bdmae)] (3), and [CdCl(ddae)]2[CdCl4] (4). The Cd(II) complexes have been characterised by elemental analyses, conductivity measurements, IR, 1H, 13C{1H} and 113Cd NMR spectroscopies, and X-ray diffraction methods. 1H and 113Cd NMR experiments at variable temperature for 3 and 4 show that dynamic processes are taking place in solution. We report the measurements of 113Cd NMR chemical shift data for complexes 1-4 in solution. X-ray crystal structures for complexes 2 and 3 have been determined. The Cd(II) is coordinated to the deat ligand, in 2, by one nitrogen atom of the pyrazolyl group and one nitrogen atom of the amine. It finishes a tetrahedral geometry with two chlorine atoms. The bdmae ligand is linked to Cd(II), in 3, by two nitrogens atoms of the pyrazolyl groups and one amine nitrogen, along with two chlorine atoms, in a distorted trigonal bipyramidal geometry. 相似文献
11.
Two new zinc-triazole-carboxylate frameworks constructed from secondary building units (SBUs), [Zn5(trz)4(btc)2(DMF)2(H2O)2]·2H2O·DMF (1) and [Zn4(trz)3(btc)2(CH3CN)(H2O)]·5H2O·(Bu4N) (2), [Htrz = 1,2,4-triazole, H3btc = 1,2,4-benzenetricarboxylate, Bu4N = tetrabutylammonium], have been synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction analyses, X-ray power diffraction, elemental analyses, infrared spectra and thermogravimetric analyses. Both compounds 1 and 2 exhibit 3D (3,8)-connected tfz-d nets with {43}2{46.618.84} topology symbol built from rod-shaped {[Zn5(trz)4]6+}n SBUs (1) and {[Zn4(trz)3]5+}n SBUs (2). In two compounds, rodlike units are connected by btc ligands via different modes. Additionally, solid state fluorescent emission spectra of two compounds show fluorescent properties at room temperature. 相似文献
12.
Five new complexes, [Co3(HL1)2(Py)8]·4CH3OH (1), [Ni3(HL1)2(Py)4]2·2DMF (2), [Co3(H2L2)2(Py)8]·2NO3 (3), [Ni2(HL2)(Py)6] (4) and [Cu4(HL2)2(Py)4]·4DMF (5) (H4L1 = N-propionyl-4-hydroxysalicylhydrazide, H44-hopshz; H5L2 = N-(3-carboxy-cis-2-propenoyl)-4-hydroxysalicylhydrazide, H54-hocpshz) have been obtained from two N,N′-diacylhydrazide ligands and characterized by elemental analysis, FT-IR, X-ray diffraction and antimicrobial activities. These di-, tri-, and tetrameric complexes are connected into three-dimensional supramolecular architectures with interesting topologies through O-H?O, C-H?O and C-H?π interactions. 1-3 are linear trimeric complexes with the ligands triply-deprotonated. Topological analysis indicates that they exhibit 2D (4,4), 3D (6,8)-connected (3349526)(3441257647) and 8-connected (42563) net, respectively. 4 and 5 possess dimeric and tetrameric structures, which are extended into 7-connected (33413536) and 4-connected (4,4) net, respectively. 相似文献
13.
Karyn M. Blake 《Inorganica chimica acta》2010,363(1):88-68
Hydrothermal synthesis has afforded divalent cadmium coordination polymers containing bis(pyridylmethyl)piperazine (bpmp) tethers and either phenylenediacetate (phda) or phenylenedipropionate (phdp) ligands. {[Cd(1,4-phda)(4-bpmp)]·1.5H2O}n (1) displays a (4,4)-grid layered structure based on 4-connected {Cd2O2} dimeric units. Extension of the pendant arms generated {[Cd(1,4-phdp)(H4-bpmp)](ClO4)·3.5H2O}n (2, phdp = phenylenedipropionate), which possesses a rare (3,6) 2D trigonal lattice based on 6-connected {Cd2O2} dimers. Changing the nitrogen donor atom disposition by using 3-bpmp as the nitrogen co-ligand yielded [Cd(1,4-phdp)(3-bpmp)(H2O)]n (3), which crystallizes in a 3-fold interpenetrated achiral diamondoid lattice. [Cd(1,3-phda)(4-bpmp)]n (4) adopts a very similar structure to that of 1. Complexes 1-4 undergo blue-violet luminescence upon exposure to ultraviolet radiation. 相似文献
14.
By regulating the pH values, two new zinc(II) coordination polymers, formulated as [Zn4(μ7-CTAI)(μ3-OH)(μ2-OH)3(H2O)2]n·2n(H2O) (1), [Zn2(μ7-CTAII)(H2O)3]n (2) have been prepared by a flexible ligand, cyclohexane-1,2,4,5-tetracarboxylic acid (H4CTA) under hydrothermal conditions. Complex 1 exhibits a two-dimensional binodal (3,6)-connected topological network containing rare octanuclear zinc(II) clusters as the secondary building units (SBU1). Complex 2 displays a three-dimensional binodal (4,8)-connected topological network containing unusual Zn4(COO)6 secondary building units (SBU2). And importantly, the conformation of H4CTA in 1 exhibits (a,e,e,a) fashion and transforms to thermodynamically more stable conformation (e,a,e,e) type in 2 by pH-controlled. In addition, both of the complexes show strong photoluminescence at room temperature, and may be good candidates for potential luminescence materials. 相似文献
15.
Li-Zhen Cai Ming-Lai Fu Ming-Sheng Wang Wen-Tong Chen Jin-Shun Huang 《Inorganica chimica acta》2006,359(14):4483-4492
Assembly of isonicotinic acid ligand (HL) with metal halide, five new hybrid complexes [CdI2(C5H4NCOOH)(C5H4NHCOO)] · H2O (1), Nan[ZnCl2(C5H4NCOO)]n · 2nH2O (2), [CdX(C5H4NCOO)]n (X = Br (3), I (4)) and [Cd3Cl2(OH)2(C5H4NCOO)2]n (5) were obtained, which display a variety of structural motifs, ranging from zero-dimensional to complicated three-dimensional networks. Complex 1 possesses an isolated unit MX2 that is further connected into 3D networks through hydrogen bonding and π-π stacking interactions. Complex 2 is characterized by an infinite one-dimensional chain of zinc atoms bridged by L− ligands. While complexes 3 and 4 possess X-bridging ∞1[CdX2/2] inorganic chains connected by L− ligands to form a 2D hybrid network structure. In the case of 5, the cadmium(II) cation is bridged by μ3-Cl atom and μ3-OH− group to form a 2-D ∞2[Cd6/2Cl6/3(μ3-OH)2] inorganic layer which is further extended into 3-D framework by bridging L− ligand via Cd-N and Cd-O bonds. The optical properties of 1, 4, and 5 in the solid state are investigated at room temperature and time-dependent DFT (TDDFT) calculation using the B3LYP functional has been performed on 1. The result indicated that the emission band of 1 is attributed to an admixture of MLCT (metal-to-ligand charge-transfer) and LLCT (ligand-to-ligand charge-transfer). 相似文献
16.
Xiao-Feng Zheng 《Inorganica chimica acta》2011,365(1):419-429
Four coordination polymers based on AgI/3-sulfobenzoate/N-donor ligands, [Ag2Na2(3-sb)2(H2O)7]n (1), {[Ag2(3-sb)(apy)]·(H2O)}n (2), {[Ag2(4,4′-bipy)2(H2O)3]·[Ag2(4,4′-bipy)2(H2O)2]·2(3-sb)·4(H2O)}n (3) and {[Ag(3-sb)(bpe)(H2O)][Ag(bpe)(H2O)]·3(H2O)}n (4) where 3-sb is 3-sulfobenzoate, apy is 2-aminopyridine, bipy is 4,4′-bipyridine and bpe is 1,2-bis(4-pyridyl)ethylene, were prepared and characterized, and their fluorescence and electric conductivity properties were studied. Complex 1 is a 3D architecture in which 3-sb ligands exhibit μ4-κ1(O1,O2-Ag): κ1(O3,O5-Na) trans-trans coordination mode. The molecular structure of 2 is a 2D layer. Complexes 3 and 4 are cation-anion species and 1D polymers. In these complexes hydrogen bonds provide additional assembly forces, giving 3D hydrogen bonding networks for 1 and 3, and 2D layers for 2 and 4. Abundant weak interactions, such as Ag-Ag interactions in 1-3, Ag-π interactions in 1-4, π-π interactions in 1, 3-4, and C-H···π interactions in 3-4, also can be found. The weak interactions are strongly related to the fluorescence and electric conductivity properties, providing the way for understanding the relationship between structures and properties. 相似文献
17.
Lei Gou Zhong-Xi Han Qing-Ran Wu Zhen-Hua Yang Fei Wang Gang-Lin Xue 《Inorganica chimica acta》2010,363(11):2590-2599
Five structurally diverse complexes, [Cd2(pyip)2(suc)2]n·1.5nH2O (1), [Zn(pyip)(glu)]n (2), [Cd(pyip)(glu)]n (3), [Zn(pyip)2(adip)2]n·2.5nH2O (4), [Cd3(pyip)2(adip)3]n (5) (pyip = 2-(pyridin-3-yl)-1H-imidazo[4,5-f][1,10]phenan-throline, H2suc = succinic acid, H2glu = glutaric acid, H2adip = adipic acid), have been hydrothermally synthesized. Complexes 1 and 4 are ribbon-like chains, in which pyip ligands attach to the both sides of the chain in pairs. Complex 2 is a one dimensional (1D) wave-like chain, while the pyip ligands attach to only one side of the chain. Complexes 3 and 5 are both two dimensional (2D) networks, in which the dicarboxylate ligands connect the dinuclear or trinuclear CdII units into layers with (4, 4) topological network. The structural differences among these complexes show that the organic acids have important influences on the final structures. 相似文献
18.
Lei Li 《Inorganica chimica acta》2010,363(4):748-55
Three Cd (II)-M (II) hetero-nuclear coordination polymers, [FeCd2(Hcit)2(H2O)2]n (1), [CoCd2(BTC)2(H2O)4]n (2) and [Cd3(Hcit)2(H2O)2]n (3) (H4cit = citric acid, H3BTC = 1,3,5-benzenetricarboxyl acid), were synthesized through hydrothermal method. They were characterized through elemental analysis, IR spectra, UV-Vis absorption spectra, X-ray powder diffraction, single-crystal X-ray diffraction and surface photovoltage spectra (SPS). Structural analysis indicates that 1 and 3 possess 2D structures, which are further connected to 3D structures by hydrogen bonds. 2 is a 3D Cd-Co coordination polymer bridged by BTC3− groups. The SPS show that 1 and 2 present positive photovoltage response in 300-550 nm, but the photovoltage response of 3 appears in 300-400 nm. It is indicated that the limits of SPS response bands of polymers 1 and 2 are wider than those of 3 because of introduction of the other transition metal ions. There is a good corresponding relationship between SPS and UV-Vis absorption spectra. 相似文献
19.
Two new zinc(II)-triazole-aliphatic dicarboxylate coordination polymers, [Zn(trz)(Hsuc)]n (1), [Zn2(trz)2(tar)]n (2), have been hydrothermally synthesized by reaction of Zn salt, Htrz with H2suc and H2tar, respectively (Htrz = 1,2,4-triazole, H2suc = succinic acid, H2tar = tartaric acid).Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by X-ray powder diffraction, elemental analyses, IR spectra and TG analyses. Compound 1 displays a 2D layer structure containing {[Zn4(trz)4]4+}n layers decorated by the suc ligand. Compound 2 is in a 3D structure formed by the interconnection of 2D {[Zn4(trz)4]4+}n layers with tar ligand, resulting a 3,4-connected topological network. Due to the different coordination mode and conformation of aliphatic carboxylate ligand, the similar 2D {[Zn4(trz)4]4+}n layers stack in the -AAA- fashion in 1, while the {[Zn4(trz)4]4+}n layers hold together in the -ABAB- stacking sequence in 2. Additionally, the two compounds show strong fluorescence in the solid state at room temperature. 相似文献
20.
Slow diffusion conditions have afforded a pair of cobalt isothiocyanate coordination polymers incorporating the flexible and hydrogen-bonding capable organodiimines N,N′-bis(3-pyridylmethyl)piperazine (3-bpmp) and N,N′-bis(4-pyridylmethyl)piperazine (4-bpmp), which were characterized by single-crystal X-ray diffraction and spectral and elemental analysis. While both [Co(NCS)2(3-bpmp)2]n (1) and {[Co(NCS)2(H2O)2(4-bpmp)] · 2H2O}n (2) possess one-dimensional (1-D) coordination polymer units, the donor disposition within the organodiimine promotes significant structural disparities. Compound 1 displays a 1-D double-chain motif, where each cobalt ion is bridged by two exobidentate 3-bpmp ligands. In contrast, compound 2 manifests a single chain pattern, with only one tethering 4-bpmp ligand joining adjacent cobalt ions. Extensive hydrogen-bonding patterns within the structure of 2 results in an intriguing supramolecular 2-D (3,4)-connected layer with (4.62)2(42.62.82) topology. Thermal properties of these materials are also discussed. 相似文献