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1.
The self-assembly reaction of 1,4-bis(1,2,4-triazol-1-yl)butane (btb) and Ni(II) salts gives three coordination polymers {[Ni(btb)2(NCS)2]?·?H2O} n (1), [Ni(btb)2(NCO)2] n (2), and [Ni(btb)2Cl2] n (3). Compound 1 is comprised of a twofold interpenetrating 4-connected 65?·?8-CdSO4 3-D coordination network. Compounds 2 and 3 are neutral 2-D (4,4) networks with the ABAB?···?and ABCABC?···?stacking modes, respectively. The thermal stabilities of 13 were investigated.  相似文献   

2.
The reaction of three positional isomer ligands of bis(1,2,4-triazol-1-ylmethyl)benzene and Co(NCS)2 gives three coordination polymers [Co(obtz)2(NCS)2] n (1), [Co(mbtz)2(NCS)2] n (2), and {[Co(bbtz)2(NCS)2]?·?2DMF} n (3). Polymers 1 and 2 are comprised of similar 1-D double chains. In 1, each chain forms π–π stacking interactions with four adjacent chains (two above and two below) to extend to a 3-D supramolecular network. Polymer 3 is a neutral 2-D (4,4) network. The dangling NCS? inserts into the window of adjacent layers in a mutual relationship and result in a 2-D?→?3-D polythreaded network in 3. The thermal stability and the diffuse reflectance UV-Vis spectroscopy of 1, 2, and 3 were measured.  相似文献   

3.
Three new Zn(II) complexes, [Zn(ox)(imb)] (1), [Zn2(mal)2(imb)2] (2), and [Zn(suc)(imb)]·H2O (3) (imb = 2-(1H-imidazolyl-1-methyl)-1H-benzimidazole, H2ox = oxalic acid, H2mal = malonic acid, H2suc = succinic acid), have been synthesized and structurally characterized. Complex 1 is a 3-D framework with a 4-connected diamond topology with the topological notation of 66. Complex 2 exhibits 2-D layers with (6,3) networks. Complex 3 displays a 3-D framework constructed through unusual 2-D → 3-D parallel interpenetration of corrugated 2-D (6,3) networks. IR spectra, PXRD patterns, thermogravimetric curves, and photoluminescence spectra are addressed.  相似文献   

4.
Ten new complexes, [Cu2(L1)(NO3)2]·2H2O (1), [Cu4(L1)2]·4ClO4·H2O (2), [Cu2(L1)(H2O)2]·(adipate) (3), [Cu6(L1)2(m-bdc)4]·2DMF·5H2O (4), [Cu2(L1)(Hbtc)]·5H2O (5), [Cu2(L1)(H2O)2]·(ntc)·3H2O (6), [Co2(L2)]·[Co(MeOH)4(H2O)2] (7), [Co3(L2)(EtOH)(H2O)] (8), [Ni6(L2)2(H2O)4]·H2O (9) and [Zn4(L2)(OAc)2]·0.5H2O (10), have been synthesized. 1 displays a [Cu2(L1)(NO3)2] monomolecular structure. 2 shows a supramolecular chain including [Cu2L1]2+. In 3, two Cu(II) ions are connected by L1 to form a [Cu2(L1)(H2O)2]2+ cation. In 4, the m-bdc anions bridge Cu(II) ions and L1 anions to form a layer. Both 5 and 6 display 3-D supramolecular structures. 7 consists of both [Co2L2]2? and [Co(MeOH)4(H2O)2]2+ units. 8 and 9 show infinite chain structures. In 10, Zn(II) dimers are linked by L2 to generate a 3-D framework. The magnetic properties for 4 and 8 and the luminescent property for 10 have been studied.  相似文献   

5.
Seven new transition metal complexes formulated as [M2(1,4-tpbd)(diimine)2(H2O)2]4+ [M = Zn, Co, Ni, Cd; 1,4-tpbd = N,N,N′,N′-tetrakis(2-pyridylmethyl)benzene-1,4-diamine; diimine is a N,N-donor heterocyclic base like 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 4,5-diazafluoren-9-one (dafo)] have been synthesized and structurally characterized by X-ray crystallography: [Zn2(1,4-tpbd)(phen)2(H2O)2]4+ (1), [Zn2(1,4-tpbd)(bpy)2(H2O)2]4+ (2), [Co2(1,4-tpbd)(phen)2(H2O)2]4+ (3), [Ni2(1,4-tpbd)(phen)2(H2O)2]4+ (4), [Ni2(1,4-tpbd)(bpy)2(H2O)2]4+ (5), [Ni2(1,4-tpbd)(dafo)2(H2O)2]4+ (6) and [Cd2(1,4-tpbd)(phen)2(H2O)2]4+ (7). Single crystal diffraction reveals that the metals in the complexes are all in a distorted octahedral geometry. The interactions of the seven complexes with calf thymus DNA (CT-DNA) have been investigated by UV absorption, fluorescence, circular dichroism spectroscopy and viscosity measurements. The apparent binding constants (Kapp) are calculated to be 5.2?×?105 M?1 for 1, 1.05?×?105 M?1 for 2, 5.76?×?105 M?1 for 3, 4.57?×?105 M?1 for 4, 1.29?×?105 M?1 for 5, 1.7?×?105 M?1 for 6, 2.53?×?105 M?1 for 7, the binding propensity to the calf thymus DNA in the order: 3 (Co-phen) > 1 (Zn-phen) > 4 (Ni-phen) > 7 (Cd-phen) > 6 (Ni-dafo) > 5 (Ni-bpy) > 2 (Zn-bpy). Furthermore, these complexes display efficient oxidative cleavage of supercoiled DNA; the Zn(II)/H2O2 and Cd(II)/H2O2 systems efficiently cleave DNA attributed to the peroxide ion coordinated to the Zn(II) and Cd(II), which enhanced their nucleophilicity, this is rare.  相似文献   

6.
Four new fpa-metal complexes, [Co(fpa)2(H2O)2] (1), [Cu(fpa)2(H2O)] (2), [Zn2(fpa)4(bpp)2] n (3), and {[Zn(bpy)(H2O)4]?·?2(fpa)} n (4), have been synthesized and fully characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, and thermogravimetric analysis (TGA), (Hfpa?=?2,2-difluoro-2-(pyridine-2-yl)acetate, bpp?=?1,3-bis(4-pyridyl)propane, bpy?=?4,4′-bipyridine). X-ray diffraction analyses reveal that 1 and 2 with 0-D structures are both extended into 3-D supramolecular networks through hydrogen bonds and π···π interactions. Complex 3 with chiral centers possesses a 1-D structure constructed by two kinds of bpp molecules and four kinds of fpa? molecules with different conformations, with bbp and fpa? bridging and capped ligands, respectively. In 4, bpy links [Zn(H2O)4]2+ into a 1-D polymeric cationic chain and uncoordinated fpa? compensates the framework charge. The results of TGA reveal that fpa? decomposes through two processes. Both 3 and 4 show strong fluorescence in the solid state at room temperature.  相似文献   

7.
Three new polynuclear compounds based on a dicarboxylic acid ligand are reported. In particular, two Cu(II) coordination compounds, [Cu2(H2O)6(Hbzlidp)2](CF3SO3)2·2H2O (1) and [Cu(NO3)(Hbzlidp)] (2) (bzlidp2? = N-benzyliminodipropionate anion), and a Ni(II) dinuclear compound, [Ni2(H2O)4(bzlidp)2] (3), were synthesized and characterized by IR spectroscopy, elemental analysis and single crystal X-ray diffraction. Different structures were obtained depending on the reaction conditions. The structural analyses reveal that 1 was formed by dinuclear [Cu2(H2O)6(Hbzlidp)2]2+ units built by two copper(II) ions joined through two Hbzlidp? ligands, while 2 was formed by pairs of Cu(II) centers bridged by four syn,syn carboxylate groups to generate “paddle wheel” units. The dinuclear copper units are arranged in a rhombus type grid, in a 2-D layer structure. In both cases, the N was protonated and not coordinated to the metal center. Compound 3 was formed by [Ni2(H2O)4(bzlidp)2] neutral dinuclear units, with octahedral Ni(II) centers. Solution studies of the ligand–M(II) systems (M(II) = Mn, Co, Ni, Cu, Zn, Cd, and Pb) were also carried out.  相似文献   

8.
Three coordination polymers, {[Co(C10H5N3O5)(H2O)2]·H2O}n (1), {[Mn3(C10H5N3O5)2Cl2(H2O)6]·2H2O}n (2), and {[Cu3(C10H4N3O5)2(H2O)3]·4H2O}n (3), based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide (H3DCImPyO), were synthesized under hydrothermal conditions. The polymers showed diverse coordination modes, being characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray structure analysis. In 1, the HDCImPyO2? generated a 1-D chain by adopting a μ2-kN, O : kN′, O′ coordination mode to bridge two Co(II) ions in two bis-N,O-chelating modes. In 2, the HDCImPyO2? adopted a μ3-kN, O : kO′, O′′ : O′′′ coordination mode to bridge two crystallographically independent Mn(II) ions, forming a 2-D hcb network with {63} topology. In 3, by adopting μ4-kN, O : kO′, O′′ : kN′′, O′′′ : O′′′′ coordination, DCImPyO3? bridged three crystallographically independent Cu(II) ions to form a 3-D framework having the stb topology.  相似文献   

9.
Reactions of fresh M(OH)2 (M = Zn2+, Cd2+) precipitate and (RS)-2-methylglutaric acid (H2MGL), 2,2′-bipyridine (bipy), or 1,10-phenanthroline (phen) in aqueous solution at 50°C afforded four new metal–organic complexes [Zn2(bipy)2(H2O)2(MGL)2] (1), [Zn2(phen)2(H2O)(MGL)2] (2), [Cd(bipy)(H2O)(MGL)] · 3H2O (3), and [Cd(phen)(H2O)(MGL)] · 2H2O (4), which were characterized by single crystal X-ray diffraction, IR spectra, TG/DTA analysis as well as fluorescence spectra. In 1, the [Zn(bipy)(H2O)]2+ moieties are linked by R- and S-2-methylglutarate anions to build up the centrosymmetric dinuclear [Zn2(bipy)2(H2O)2(MGL)2] molecules. In 2, the 1-D ribbon-like chains [Zn2(phen)2(H2O)(MGL)2] n can be visualized as from centrosymmetric dinuclear [Zn2(phen)2(H2O)2(MGL)2] units sharing common aqua ligands. Both 3 and 4 exhibit 1-D chains resulting from [Cd(bipy)(H2O)]2+ and [Cd(phen)(H2O)]2+, respectively, bridged alternately by R- and S-2-methylglutarate anions in bis-chelating fashion. The intermolecular and interchain π···π stacking interactions form supramolecular assemblies in 1 and 1-D chains in 24 into 2-D layers. The hydrogen bonded lattice H2O molecules are sandwiched between 2-D layers in 3 and 4. Fluorescence spectra of 14 exhibit LLCT π → π* transitions.  相似文献   

10.
Reactions of Zn(II) salts, 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and 2-mercaptobenzoic acid or 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H3PrIDC), result in two mixed-ligand coordination polymers (CPs), [Zn2(IPT)(DSDB)(OH)]n (H2DSDB = 2,2′-disulfanediyldibenzoic acid, 1) and [Zn2(IPT)(PrIDC)(H2O)]n (H3PrIDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, 2). Compound 1 possesses a 2-D structure built by 1-D [Zn(IPT)]n chains and DSDB2? connectors, in which the DSDB2? is generated via in situ reaction from 2-mercaptobenzoic acid. It displays a new intricate 4-nodal {3·4·6·7·8·9}{3·6·7·8·9·10}{3·8·9}{4·6·8} topology. Compound 2 displays a 3-D framework with new 3-connected topology with Schläfli symbol of (4·8·10) (8·122), in which the 1-D Zn-carboxylate chains were bridged by 3-connected IPT? ligands. The thermal stabilities and luminescence properties of 1 and 2 have also been studied. The compounds exhibit intense solid-state fluorescent emissions at room temperature.  相似文献   

11.
Four new compounds, [Mn(HL)(phen)2(H2O)] (1), [Ni(HL)(phen)2(H2O)] (2), [Zn(HL)(4,4′-bipy)1.5(H2O)] n ?·?2nH2O (3) and [Zn2(HL)2(H2O)6] (4), have been synthesized from an asymmetric semi-rigid V-shaped multicarboxylate 4-(4-carboxy-phenoxy)-phthalic acid (H3L) with 1,10-phenanthroline (phen), or 4,4′-bipyridine (4,4′-bipy) as auxiliary ligands. Single-crystal X-ray diffraction analysis reveals that 1, 2 and 4 have 0-D structures with 3-D supramolecular frameworks formed by intermolecular hydrogen bonds. Compound 3 shows a 1-D infinite ribbon bridged by 4,4′-bipy, which further forms a 3-D supramolecular architecture by π–π stacking interactions and hydrogen bonds. Thermal stabilities of 14 and luminescence properties of 3 and 4 have also been investigated.  相似文献   

12.
Two new complexes, [Zn(phen)2(H2O)2]2L·H2O (1) and [Cu(phen)(L)(H2O)2]L·3H2O (2), where HL?= 4-aminobenzenesulfonic acid and phen = o-phenanthroline, have been synthesized and their crystal structures determined by X-ray diffraction. In the complexes the Cu(II) and Zn(II) atoms revealed two different coordination environments. Complex 1 consists of a cation [Zn(phen)2(H2O)2]2+, in which Zn(II) is six-coordinated by four nitrogen atoms from two o-phenanthroline molecules and by two water molecules. Complex 2 has two crystallographically unique Cu(II) ions, where Cu(II) ion is five-coordinate with two nitrogen atoms of o-phenanthroline, two water molecules and one sulfonate oxygen atom. The electrochemical behavior and FT-IR of the two compounds have also been studied in detail.  相似文献   

13.
Three complexes constructed with 2,2′-biphenyldicarboxylic acid, multidentate nitrogen donors, and metal salts, {[Cd(2,2′-dpdc)(tppp)(H2O)]2?·?2H2O} n (1), {[Pb(2,2′-dpdc)(pyphen)]2} n (2), and {[Pb(2,2′-dpdc)(dppz)]} n (3) (H2dpdc = 2,2′-diphenyldicarboxylic acid; tppp = 4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)phenol; pyphen?=?pyrazino[2,3-f]-[1,10]phenanthroline; and dppz = dipyrido[3,2-a:2′,3′-c]phenazine), are synthesized under hydrothermal conditions. These complexes are characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and photoluminescence. In 1, two 2,2′-dpdc ions bridge two Cd(II) ions to form an isolated cluster with Cd?···?Cd distance of 5.023(4)?Å. These clusters are further linked by intermolecular hydrogen bonds, yielding a 2-D supramolecular structure. Complex 2 contains two crystallographically independent Pb(II) ions in the asymmetric unit. Pb1 ions are bridged by 2,2′-dpdc anions to form a chain along the x-axis. Two Pb2 ions are coordinated by two 2,2′-dpdc anions and two pyphen ligands to form a cluster. These clusters are linked by π–π interactions to yield a 1-D supramolecular chain along the y-axis. In 3, neighboring Pb(II) atoms are bridged by 2,2′-dpdc anions to form a 1-D chain structure. Further, the chains are linked into a 3-D supramolecular network through aromatic π–π interactions.  相似文献   

14.
Three structurally diverse PbII coordination complexes, [Pb3O(OH)(4-sphth)]2(H2O) (1), [Pb(3,5-Hdhb)]H2O (2), and [Pb3(4-nphth)2(OH)2] (3) (4-H3sphth, 4-sulfophthalic acid; 3,5-H2dhb, 3,5-dihydroxybenzoic acid; 4-H2nphth, 4-nitrophthalic acid), were synthesized under hydrothermal conditions. X-ray diffraction analyses reveal that 1 is constructed from [Pb4O4] cubanes, based on which ladder-shaped structure is built via 4-H3sphth bridge. This is the first Pb4O4-containing polymer. The Pb2O2 units in 2 are bridged by two parallel 3,5-HDHB ligands along the a-axis and two other parallel 3,5-HDHB ligands along the b-axis, forming a 3-D framework. For 3, the crystal structure is built up of a layer motif consisting of corner-sharing pyramidal Pb3O units, which are linked through Pb corners to form a hexagonal unit. Each PbO6 polyhedron is connected to three polyhedra (Pb3O) via sharing an edge (two μ 3-oxygen atoms) and two faces (three μ 3-oxygen atoms), thus yielding an infinite 2-D Pb–O–Pb (3,6-net) honeycomb layer. The luminescence of 13 demonstrates that they may be good candidates for luminescent materials.  相似文献   

15.
A new inorganic–organic hybrid based on polyoxometalate, [Cu2(daphen)2(H2O)4(PW11WVO40)]?·?6H2O (1) (daphen?=?5,6-diamino-1,10-phenanthroline), was synthesized hydrothermally and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy, and thermal analysis. Single-crystal X-ray diffraction analysis reveals that in 1 the Keggin anion [PW12O40]4? is tetradentate, linking four Cu(II)-daphen fragments with its four terminal oxygen atoms in a plane; Cu2+ is coordinated by two terminal oxygen atoms of two [PW12O40]4? anions, two water molecules, and two nitrogen atoms of the phen ring of a daphen, forming a polymeric layer. The 3-D architecture of the compound is further formed via hydrogen bonds between these layers. The daphen is bidentate chelating and does not participate in formation of hydrogen bonds. Redox of 1 was examined.  相似文献   

16.
Three new lead(II)-based coordination polymers, [Pb(5-OH-BDC)] n ?·?nH2O (1) (5-OH-BDC?=?5-hydroxyisophthalate), [Pb2(5-CH3-BDC)2] n (2), and [Pb2(5-CH3-BDC)2(phen)2] n ?·?2nH2O (3) (5-CH3-BDC?=?5-methylisophthalate, phen?=?1,10-phenanthroline), have been hydrothermally synthesized, structurally determined by single-crystal X-ray diffraction, and characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Both 1 and 2 exhibit 2-D double-layer network structures, while 3 possesses 1-D chain structure bridged by 5-CH3-BDC. The coordination sphere of Pb(II) in 1 is holodirected, whereas in 2 and 3 the spheres feature hemidirected structures. Fluorescence properties of 13 have been investigated in the crystalline state at room temperature.  相似文献   

17.
Four complexes, [Ag4(bipy)2(Himdc)2(H2O)2] n (1), [Ag(H2imdc)] n (2), [K(H3imdc)(H2imdc)(H2O)2] n (3), and [Cu(Himc)2] (4) (H3imdc?=?1H-imidazole-4,5-dicarboxylic acid, H2imc?=?1H-imidazole-2-carboxylic acid, and bipy?=?4,4′-bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis and elemental analysis. The obtained complexes exhibit different coordination structures; 1 contains a 2-D supramolecular layer based on two chains arraying uniformly in an ABAB manner. Compound 2 displays sawtooth-shaped 1-D chains extending to 2-D layers via hydrogen bond interactions. Compound 3 possesses a 3-D framework structure based on a 1-D chain via hydrogen bonding interactions. Compound 4 has a 3-D framework structure bearing a pcu-type topology. In addition, the photoluminescence for 1 has been investigated.  相似文献   

18.
Five N-heterocyclic carboxylate-based coordination complexes, [Co(L1)2(H2O)2]·2H2O (1), [Cd(L1)2(H2O)2]·2H2O (2), [Co(L2)(H2O)3] (3), [Ni(L2)(H2O)3] (4), and [Cu2(L2)2(H2O)2] (5), have been synthesized and characterized by elemental analysis, IR spectroscopy, Powder X-ray diffraction, thermogravimetric analyses, and single-crystal X-ray crystallography, where HL1 is 2-((5-amino-1H-1,2,4-triazol-3-yl)thio)acetic acid and H2L2 is 2-((5-amino-1-(carboxymethyl)-1H-1,2,4-triazol-3-yl)thio)acetic acid. In these complexes, the hydrogen bonds (H-bonds) play an important role in their packing structures. Complex 1 has nine H-bonds showing a 3-D sqc38 topology. Complex 2 has 17 H-bonds exhibiting a 3-D hxl network. Complexes 3 and 4 are isomorphic, both of which possess ten H-bonds to present a 3-D btc topology. Complex 5 with eight H-bonds forms a 2-D sq1 structure. In addition, complex 3 catalyzes the decolorization of methyl orange. Meanwhile, 1, 3, and 5 show certain anticancer activities to inhibit the growth of HepG2 cells.  相似文献   

19.
Ruthenium(II) Phthalocyaninates(2–): Synthesis and Properties of (Acido)(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc2?]? (X = Cl, Br, I, NCO, NCS, N3) (nBu4N)[Ru(OH)2Pc2?] is reduced in acetone with carbonmonoxid to blue-violet [Ru(H2O)(CO)Pc2?], which yields in tetrahydrofurane with excess (nBu4N)X acido(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc2?]? (X = Cl, Br, I, NCO, NCS, N3) isolated as red-violet, diamagnetic (nBu4N) complex salt. The UV-Vis spectra are dominated by the typical π-π* transitions of the Pc2? ligand at approximately 15100 (B), 28300 (Q1) und 33500 cm?1 (Q2), only fairly dependent of the axial ligands. v(C? O) is observed at 1927 (X = I), 1930 (Cl, Br), 1936 (N3, NCO) 1948 cm?1 (NCS), v(C? N) at 2208 cm?1 (NCO), 2093 cm?1 (NCS) and v(N? N) at 2030 cm?1 only in the MIR spectrum. v(Ru? C) coincides in the FIR spectrum with a deformation vibration of the Pc ligand, but is detected in the resonance Raman(RR) spectrum at 516 (X = Cl), 512 (Br), 510 (N3), 504 (I), 499 (NCO), 498 cm?1 (NCS). v(Ru? X) is observed in the FIR spectrum at 257 (X = Cl), 191 (Br), 166 (I), 349 (N3), 336 (NCO) and 224 cm?1 (NCS). Only v(Ru? I) is RR-enhanced.  相似文献   

20.
Three 2-D layered coordination polymers with (4,4) topology, {[Cu(trzp)2(H2O)]·1.18H2O} n (1), {[Co(trzp)2(H2O)2]·2H2O} n (2), and {[Cd(trzp)2(H2O)]·2H2O} n (3), have been synthesized with the flexible, bifunctional ligand 1H-1,2,4-triazole-1-propionate (trzp?) as a two-connected bridge. In addition, a complicated 3-D MOF [Ag3(trzp)2(NO3)] n (4) has been obtained with the help of Ag?Ag interactions and trzp? as a four-connected linker. Htrzp and 14 have been characterized by single-crystal X-ray diffraction, elemental analysis, and infrared spectroscopy. The structural analysis showed that Htrzp has a gauche conformation in the solid state. However, both gauche and trans conformers of trzp? are observed in the crystals of 1; only one conformer of trzp? exists in the other three compounds (trans conformation in 2 and 3, and gauche conformation in 4). The thermal behaviors of 14 have been examined by thermal gravimetric analysis under nitrogen, which revealed that metal cyanide salts M(CN) n (M?=?Cu(II), Co(II), Cd(II), and Ag(I), n?=?1 or 2) may be an intermediate pyrolytic decomposition product of the corresponding compounds.  相似文献   

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