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1.
《结构化学》2020,39(6):1057-1062
The syntheses, crystal structures and catalytic activities of two copper complexes are reported. Reaction of CuC l, 3-(pyridin-2-yl)imidazo[1,5-a]pyridine and pyridine-4-formaldehyde under solvothermal conditions gave [Cu_4(L1)_2Cl_2][CuCl_2]_2(1, L1 = 1,1?-(pyridin-4-ylmethylene)bis(3-(pyridin-2-yl)imidazo[1,5-a]pyridine). The ligand L1 was generated in situ from the reaction of 3-(pyridin-2-yl)imidazo[1,5-a]pyridine and pyridine-4-formaldhyde. The tetranuclear [Cu_4(L1)_2Cl_2]~(2+) moiety displays McClellan Saddle-like configuration. Reaction of Cu(BF_4)_2×6H_2O with 1,1?-(pyridin-4-ylmethylene)bis(3-(pyridin-2-yl)imidazo[1,5-a]pyridine(L2) in glass tube generated [Cu(L2)(H_2O)_2]_2[BF_4]_2(SiF_6)×2H_2O(2). The structures of 1 and 2 were characterized by Xray single-crystal diffraction analysis. The catalytic activities of 1 and 2 toward ketalization reactions were studied. They both exhibited high activities for the ketalization of aliphatic ketones by ethylene glycol.  相似文献   

2.
Two new dicopper(Ⅱ) complexes with two carboxyl bridgings in one molecule[Cu(dm-phen)(HCOO)]_2(NO_3)_2 3H_2O(1). [Cu(ds-phen)(CH_3COO)]_2 (NO_3)_2 3H_2O(2). one dicopper(Ⅱ) complex with one carboxyl bridging and one hydroxo bridging in one molecule [Cu_2(OH)(C_2H_5COO)(ds-phen)_2]. (NO_3)_2 H_2O(3) and one cononuclear Cu(Ⅱ) complex [Cu(de-phen)(CF_3COO)](NO_3).H_2O(4)(dm-phen= 2,9-dimethyl-1,10-phenanthrolin)were prepared and characterized. The effective magnetic moment, u elf, was measured and their magnetic properties were discussed. The coordination modes of carboxyl moieties in all the title complexes were proposed.  相似文献   

3.
A new 8-hydroxyquinoline derivative(5)was synthesized and characterized by ESI-MS,~1H NMR spectroscopy,elemental analysis and IR spectroscopy.The photophysical properties of compounds 5,6 and 7 were also deteminedby UV-vis and FL spectroscopy.The vibrational frequency of ligand 5 predicted by using B3LYP method is in goodagreement with experimentally determined values.The compositions of the corresponding copper(Ⅱ)and zinc(Ⅱ)complexes were confirmed to be Cu(C_(29)H_(21)N_2O)_2·H_2O(6)and Zn(C_(29)H_(21)N_2O)_2·H_2O(7)by elementary analysis,thermogravimetry analysis and IR spectroscopy.  相似文献   

4.
Two new hydrostable two-dimensional(2 D) uranyl coordination complexes [(UO_2)_5(μ_3-O)_2(nbca)_2].7 H_2O(1) and [(UO_2)_3(nbca)_2(H_2O)_3]·2 H_2O(2)(H_3 nbca=5-nitro-1,2,3-benzenetricarboxylic acid) were hydrothermal synthesized.Single-crystal structural refinements reveal that both of the two complexes were formed by the packing of 2D uranyl coordination sheets via the hydrogen bonds.The nbca ligand coordinating to the uranyl polyhedron centers constructed the 2D sheets.There are UO_8 hexagonal bipyramids and UO_7 pentagonal bipyramids in 1 while only U07 pentagonal bipyramids in 2.Photocatalytic degradation of rhodamine B(RhB) in aqueous solution was studied.Complex 2 possesses better performance than 1 with 96.2 % of the RhB was degraded in only 60 min.Mechanism studies reveal that the dissolved oxygens are essential to the RhB degradation.The photocurrent density of 2 is more stable than that of 1,which indicating the stronger ability to separate photoexcited electrons and hole pairs of 2.  相似文献   

5.
《结构化学》2020,39(6):1103-1111
Two novel macrocyclic Schiff base complexes [LnL(PhCOO)(CH_3OH)](ClO_4)_2·(CH_3OH)_2(Ln =Ho, 1; Ln = Er, 2), in which L denotes the macrocyclic ligand, were synthesized via condensation of 2,6-diformyl-4-methyl-phenol and 1,3-diamino-2-propanol by employing benzoate as the second ligand. Their crystal structures were determined by X-ray diffraction, which showed that both complexes belong to a monoclinic system with space group P2_(1/c). The coordination polyhedron displayed a distorted bicapped trigonal prism with the coordination number of eight. Both complexes efficiently cleaved supercoiled DNA to its nicked circular form. The UV-vis absorption results and ethidium bromide(EB) fluorescence spectra indicated that the complexes bind to CT-DNA in an intercalative mode, with K_(sq) values to be 11830 and 10560, respectively.  相似文献   

6.
A series of novel heteronuclear Ln(Ⅲ)-Cu(Ⅱ) complexes with noncyclic polyether-amino acid Schiff base were synthesized. The general formula is [LnCu_2(H_2TALY)(NO_3)_5](NO_3)_2' nH_2O(Ln=La, Nd, Sm, Gd, n= 4; Ln=Yb, Y, n=3), where H_2TALY = tetraglycol aldehyde bis-lysine Schiff base. It is the first time to report the synthetic method for this new Cu(Ⅱ) complexes and Ln(Ⅲ)-Cu(Ⅱ) heteronuclear complexes. The complexes were characterized by elemental analysis, IR spectra, TG-DTA, magnetic susceptibility, and especially by a 500 MHz NMR spectrometer for 2D-COSY NMR. Coordination mechanism and structures of complexes have been suggested as well. Of particular interest is the potential that the novel complexes obtained may be used as a catalyst, which prompted us to investigate them. It shows 100% conversion with the viscosity-average molecular weight 120 000 for the polymerization of methyl methacrylate (MMA) without addition of any cocatalyst. Furthermore, the complexes with such aliphatic Schiff bas  相似文献   

7.
The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3(CO)_(12) with R-C≡C-R'(R = Fc(Ferrocenyl); R′ = Ph(Phenyl), Fc, H). The hexacarbonyldiiron cluster with ferracyclopentadiene ring(μ_2, η~4-C_4Ph_4)Fe_2(CO)_6(1) and one tetraphenyl substituted cyclopentadienone(Ph_4C_4CO)(2) were simultaneously obtained by the reaction of Fe_3(CO)_(12) with alkyne(Ph-C≡C-Ph). Only one ferrole cluster(μ_2, η~4-C_4Fc_2H_2)Fe_2(CO)_6(3) was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex(η~4-C_4Fc_4CO)Fe(CO)_3(4) and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3(CO)_2](5) were obtained by using Fc-C≡C-Fc as alkyne. A new complex(η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one)-tricarbonyl iron(η~4-C_4Ph_2Fc_2CO)Fe(CO)_3(6) was synthesized by the reaction of Fe_3(CO)_(12) with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.  相似文献   

8.
Two metal-organic frameworks(MOFs) of formulae [Co_7(L)_3(4,4?-BPy)_2(OH)_2(H_2O)_6]·-4 H_2O(1) and [Cd_2(L)(2,2?-BPy)2]n(2, H_4L = 5-(3,5-dicarboxybenzyloxy)-isophthalic acid,2,2?-BPy = 2,2?-bipyridine, 4,4?-BPy = 4,4?-bipyridine) were synthesized under solvothermal conditions. The structures of 1 and 2 were characterized by X-ray single-crystal diffraction analysis.In complex 1, six cobalt atoms were connected by oxygen atoms to form a defect dicubane structure. The defect dicubane structures were further linked by Co(4,4?-BPy) units to generate a3-D network structure. Compound 2 displays a 2-D chain structure. The photoluminescent property of complex 2 is investigated. The results show the exclusive luminescence emission bands being originated from intraligand π-π* transitions.  相似文献   

9.
Two silver(I)-sulfonate complexes,[Ag(NO_3)(4,4'-bipy)][Ag(HL)(4,4'-bipy)]·2H_2O(1) and[Ag(H_2O)(4,4'-bipy)][AgL(4,4'-bipy)]·2H_2O(2),have been synthesized by in situ reaction(H_2L = 2-formylbenzenesulfonic acid,4,4-bipy = 4,4-bipyridine).1 displays two parallel 1D chains expending to a 3D supramolecule by n—n interactions and O-H…O hydrogen bonds,in which the[Ag(NO_3)]or[Ag(HL)]units are joined by bridging 4,4'-bipy molecules,respectively.The interactions between the complexes and DNA were studied by means of fluorescence spectra and surface-enhanced Raman scattering(SERS) spectra.The special configuration and intercalation effects between 1 and DNA are stronger than that between 2 and DNA.  相似文献   

10.
La(Ⅲ), Y(Ⅲ) complexes with diglycol aldehyde bis-arginine (H_2DAAR) and tetraglycol aldehyde bislysine (H_2TALY) Schiff bases were synthesized. They were characterized and formulated as La(H_2DAAR) (NO_3)_3·6H_2O and Y (H_2TALY)(NO_3)_3·5H_2O separately by elemental analyses. The obtained complexes were investigated in detail by high resolution solid state (HRSS) ~(13)C NMR using cross polarization, magic angle spinning (CPMAS), and total suppression of sidebands (TOSS)techniques. The results are supported by the liquid state 2D-~1H-~(13)C COSY NMR spectra. Some new information about the splitting peaks of ~(13)C for—CH=N—group and alkene carbon bands, etc. in HRSS ~(13)C NMR spectra are given.  相似文献   

11.
《结构化学》2019,38(7)
Three novel complexes, namely {[La(tapipa)(4,4′-bibp)·(H_2O)_2]·H_2O}n(1), {[La-(tapipa)(H_2O)_4(OH)]·3 H_2O}n(2), [Co(tapipa)(1,4-bbib)]n(3)(tapipa = 5-(3-(tetrazo-5-yl)phenyl)isophthalic acid, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl, and 1,4-bbib = 1,4-bis(benzimidazo-1-ly)benzene) have been synthesized under solvothermal conditions and characterized by PXRD, IR,TGA, and so on. Complex 1 presents a 2 D layer structure, which is finally packed into a 3 D supramolecular structure by means of hydrogen bonds; complexes 2 and 3 exhibit 1 D chains and 2 D wavy-type structures, respectively, which are expanded into 3 D supramolecular structures through hydrogen bonds and π-π interactions. Furthermore, the luminescence properties of complex 1 and the variable-temperature magnetic susceptibilities of 3 were investigated. Complex 1 has highly selective sensing for Fe~(3+) and Cr_2O_7~(2-) ions.  相似文献   

12.
2-Oxo-butyric acid salicylacylhydrazone dibenzyltin(IV) complexes 1 {[o-OHC_6H_4(O)C=N-N=C(Et)COO](CH_3OH)[(C_6H_5CH_2)_2Sn]}_2 and 2 {[o-OH-C_6H_4(O)C=N-N=C(Et)-COO](CH_3OH)[(2,4-Cl_2C_6H_3CH_2)_2Sn]}_2 have been synthesized. The complexes were characterized by IR, ~1H, ~(13)C and ~(119)Sn NMR spectra, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex 1 belongs to triclinic system, space group P1 with a = 8.9121(6), b = 10.3875(7), c = 14.5658(10) ?, α = 89.534(5), β = 86.790(5), γ = 70.103(6)°, Z = 1, V = 1265.85(15) ?3, Dc = 1.488 Mg·m~(-3), m(Mo Kα) = 1.047 mm-1, F(000) = 576, R = 0.0466 and w R = 0.1054. The crystal of complex 2 belongs to monoclinic system, space group P21/n, a = 12.7165(10), b = 17.8466(14), c = 12.8538(10) ?, β = 95.1310(10)°, Z = 2, V = 2905.4(4) ?~3, Dc = 1.612 Mg·m~(-3), m(Mo Kα) = 1.286 mm-1, F(000) = 1408, R = 0.0369 and w R = 0.0958. In vitro antitumor activities of both complexes were evaluated by the 3-(4,5-dimethylthiazoly-2-yl)-2,5-diphenyltetrazolium bromide(MTT) assay against three human cancer cell lines(NCI-H460, HepG2, MCF7) and one human cell line(HL7702). Two complexes exhibited strong antitumor activity, and then they were expected after further chemical optimization of candidate compounds as anti-cancer drugs. The interaction between complexes and calf thymus DNA were studied by EB fluorescent probe. The interactions of the two complexes with calf thymus DNA were intercalation.  相似文献   

13.
Cyclic phosphoester monomer ethyl ethylene phosphate (EEP) modified poly(ethylenimine) (PEI),denoted as PEI-EEP,was developed for gene delivery.Three PEI-EEP polymers were synthesized and their structures were characterized by 1H and 31P NMR methods.All the PEI-EEP polymers could condense DNA efficiently at N/P ratios higher than 0.5/1.The physiochemical characteristics of PEI-EEP/DNA complexes were analyzed by particle size and zeta potential measurements.The particle sizes of complexes were around 160–250...  相似文献   

14.
Two new complexes [Ag(bix)]n·n NAA·n H_2O(1) and [Cd(NAA)(phen)_2(H_2O)]2· 2CH_3COO-·H_2O(2)(bix = 1,4-bis(imidazol-1-ylmethyl)benzene,HNAA = α-naphthylacetic acid,phen = 1,10-phenanthroline) have been successfully synthesized under hydrothermal conditions.Their structures have been determined by elemental analyses,IR spectroscopy,TG and single-crystal X-ray diffraction analysis.The intermolecular hydrogen bonding or π-π stacking interactions extend the complexes into a 3D supramolecular structure.Moreover,the luminescent properties of complex 2 have been investigated in the solid state.  相似文献   

15.
The chemical preparation, crystal structure and infrared spectroscopic characterization of the triaqua(4-amino-6-methoxypyrimidine) cuprate(II) sulfate, [Cu(C_5H_7N_3)(H_2O)_3]SO_4, is reported. The compound crystallizes in the noncentrosymmetric orthorhombic space group P2_12_12_1 with lattice parameters a = 7.9025(3), b = 11.1189(4), c = 12.9720(4) , V = 1139.81(7) ~3 and Z = 4. The Cu(II) cation is fivecoordinated, in an early half-way between square pyramidal and trigonal bipyramidal fashion, by two nitrogen atoms of the 4-amino-6-methoxypyrimidine ligand and three water oxygen atoms. In the atomic arrangement, the organic ligands and the 5-connected Cu centers are linked with each other to give a 1-D corrugated hybrid chain running along the b-axis direction. The chains are interconnected by the SO_4~(2-) anions via O–H...O, O–H...S, C–H...O and N–H...O hydrogen bonds to form layers spreading parallel to the(011) plane. The vibrational absorption bands were identified by infrared spectroscopy. Quantitative measurements of the second harmonic generation(SHG) of a powdered sample at 1064 nm were performed and a relative efficiency of 5.2 times the KDP standard was observed. Magnetic properties were also defined to characterize the complex. Magnetic measurements revealed that this material had a onedimensional antiferromagnetic character. The magnetic parameters were g = 2.11 and 2J/k B = -36 K.  相似文献   

16.
A new carboxylic acid ligand, 2,4-bis-oxyacetate-benzoic acid(H3BOABA), was designed and introduced to construct novel metal-organic framework materials. [Zn Na(BOABA)(phen)(H2O)]·H2O(1), Zn Na(BOABA)(2), Mn3(BOABA)2(phen)2(3), [Mn2(BOABA)(OH)]·(H2O)2(4)(CCDC: 885138, 885137, 894225, 883094) were hydrothermally synthesized and characterized by elemental analysis, IR spectra and thermal gravimetric analyses. Crystal structures of the complexes were determined by single crystal X-ray diffraction method. Complex 1 is a one dimensional double edges non-interpenetrated framework decorated by the phen ligands on the surface. Complex 2 is an unique three dimensional open framework, consisting of Zn(II) and Na(I). Complex 3 is an unique double edges one dimensional MOF containing a [Mn3(BOABA)2(phen)2]n non-interpenetrated structure. Complex 4 is a two dimensional plane structure containing two Mn atoms in the same coordination environment. The interaction between four complexes and DNA were studied by Et Br fluorescence probe. Meanwhile, photoluminescence studies revealed that these four complexes display strong fluorescent emission bands in the solid state at room temperature.  相似文献   

17.
Two new d~(10 )metal-based metal-organic frameworks,{[Zn_3(btc)_2(bib)_2(H_2O)_2]·2H_2O}_n(1)and{[Cd_3(btc)_2(bib)_(1.5)(H_2O)_6]·6H_2O}_n(2)(btc=1,3,5-benzenetricarboxylate anion,bib=1,4-bis(1-imidazolyl)benzene)have been prepared under hydrothermal conditions by the reactions of d~(10 )metal oxides of ZnO and CdO with the aromatic polycarboxylic H_3btc and the N-heterocyclic bib.The two products were characterized by single-crystal X-ray diffraction analysis,elemental analysis,thermogravimetric analysis(TGA),and IR spectroscopy.Complexes 1 and 2 crystallize in monoclinic C2/c and triclinic P 1 space groups,respectively.1 shows a 3D framework,and the potential large voids of the 3D network lead to a 3-fold interpenetrating architecture.2 displays a 2D framework,and the adjacent 2D layers expand into a 3D supramulecular network via rich hydrogen bonds.Moreover,the luminescent properties of the two complexes are investigated in solid state.  相似文献   

18.
A new organic-inorganic hybrid sandwich-type polyoxotungstate [Cu(dien)-(H_2O)_2]_2[{Cu(dien)(H_2O)}_3{Cu_(4.5)W_(0.5)(B-α-Sb W_9O_(33))_2}](OH)4·7H_2O(1, dien = diethylenetriamine) has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, TG analysis, and single-crystal X-ray diffraction analysis. Crystal data for 1: monoclinic, C2/c, a = 31.527(3), b = 13.9309(13), c = 24.297(2) ?, β = 1108.269(2)o, V = 10133.2(17) ?3, Dc = 4.024 g/cm3 and Z = 4. X-ray crystallographic study shows that the molecular structure of 1contains an infrequent penta-nuclearity {Cu4.5W0.5} cluster sandwiched polyanion [{Cu4.5W0.5(B-α-Sb W9O33)2}]6-, on which three [Cu(dien)(H_2O)]~(2+) complexes decorated as pendants. Interestingly, two [Cu(dien)(H_2O)]2+ pendants linked the two neighboring sandwich-type polyanions via double Cu-μ_2-O-W bridges, resulting in a 1-D chain. The magnetic measurements show compound 1exhibits obvious antiferromagnetic interactions.  相似文献   

19.
KHALIL M. M. H.  MASHALY M. M.   《中国化学》2008,26(9):1669-1677
A new series of binary mononuclear complexes were prepared from the reaction of the hydrazone ligand, 2-carboxyphenylhydrazo-benzoylacetone (H2L), with the metal ions, Cd(II), Cu(II), Ni(II), Co(II), Th(IV) and UO2(VI). The binary Cu(II) complex of H2L was reacted with the ligands 1,10-phenanthroline or 2-aminopyridine to form mixed-ligand complexes. The binary complexes of Cu(II) and Ni(II) are suggested to have octahedral configurations. The Cd(II) and Co(II) complexes are suggested to have tetrahedral and/or square-planar geometries, respectively. The Th(IV) and UO2(VI) complexes are suggested to have octahedral and dodecahedral geometries, respectively. The mixed-ligand complexes have octahedral configurations. The structures of all complexes and the corresponding thermal products were elucidated by elemental analyses, conductance, IR and electronic absorption spectra, magnetic moments, 1H NMR and TG-DSC measurements as well as by mass spectroscopy. The ligand and some of the metal complexes were found to activate the enzyme pectinlyase.  相似文献   

20.
A series of eight N-mono-substituted aryl acylguanidines L~(1~8) were synthesized from the reactions of their parent acylthioureas and respective primary amines, including five R~1C(O)N=C(NHR~2)_2 with balanced arms(denoted as R~1–R~2–R~2: Ph–Ar'–Ar', L~1(1); Ph–Ar'–Ar', L~2(2); 1-Naph–Ar'–Ar', L~3(3); 1-Naph–Ar'–Ar', L~4(4); 2-Naph–Ar'–Ar', L`5(5); Ar' = 2,6-Me_2C_6H_3, Ar' = 2,6-iPr_2C_6H_3) and three R~1C(O)N=C(NHR~2)NHR~3 with unbalanced arms(denoted as R~1–R~2–R~3: Ph–Ar'–Ph, L~6(6); Ph–Ar' –Ph, L~7(7); Ph–Ar' –Ar', L~8(8)). Treatment of L~(1~5)(1~5) with copper acetate in a molar ratio of 2:1 in dichloromethane led to the formation of homoleptic Cu(Ⅱ) complexes trans-L_2~(n')Cu(9~13), in which the Cu(Ⅱ) center was stabilized by deprotonated ligands Ln'(n = 1~5) in the O,N-bidentate mode. When similar reactions of L~6(Ph–Ar'–Ph)(6) and L~7(Ph–Ar'–Ph)(7) that contain unbalanced arms were investigated, the Cu(Ⅱ) products trans-L_2~(6')Cu(14) and trans-L_2~(7')Cu(15) were formed by deprotonating the bulky amine groups in Ln(-NHAr' for L~6 and-NHAr' for L~7) rather than the-NHPh group. In sharp contrast, trans-L_2~(8')Cu(16) was obtained from two-arm unbalanced L~8(Ph–Ar'–Ar')(8) not by deprotonating the more bulky-NHAr' group but the relatively less bulky-NHAr' group. In a further exploration, the reaction of 1:1 mixed ligands Ln and Lm with copper acetate was found to give only homoleptic Cu(Ⅱ) complex L_2~(n')Cu instead of the heteroleptic one L~(n')CuL~(m'). The in vitro antibacterial activity of L~n was evaluated against S. aureus, E. coli and C. albicans by determining the minimum inhibitory concentrations(MICs) using Kirby-Bauer test.  相似文献   

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