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1.
A 1-D copper(II) coordination polymer and two mononuclear copper(II) complexes of 4-formylbenzoate, [Cu(L)2(H2O)2] n (1), [Cu(L)2(D,L-cam)] (2), and [Cu(L)(bpy)2]?·?(ClO4)(H2O) (3) (HL?=?4-formylbenzoic acid, D,L-cam?=?D,L-camphoric diamine, bpy?=?2,2′-bipyridine), have been obtained from cleavage of C=N double bonds of a bis-Schiff-base compound. 4-Formylbenzoate exhibits bidentate chelating and bidentate μ 2-bridging modes by terminal carboxylic and aldehydic groups in 1-D coordination polymer 1. In contrast, it shows bidentate chelating in 2 and monodentate and bidentate bonding in 3 by its terminal carboxylic group where the aldehydic group does not coordinate. Offset π–π stacking interactions and two types of 8-membered hydrogen-bonding rings are found between neighboring molecules of the copper(II) complexes.  相似文献   

2.
Three new mononuclear copper(II) complexes, [CuL(2-fca)(CH3OH)]ClO4?·?CH3OH (1), [CuL(m-nba)(CH3OH)]ClO4 (2), and [CuL(pic)(ClO4)]?·?CH3OH (3), were synthesized and structurally characterized, where L is 2,6-bis(benzimidazol-2-yl)pyridine, while 2-fca, m-nba, and pic are the anions of 2-furoic acid, m-nitrobenzoic acid, and picolinic acid, respectively. All of them were characterized by elemental analysis, infrared, UV-Vis, and X-ray crystallography. In 1 and 2, the Cu(II) resides within a distorted square-pyramidal N3O2 coordination sphere with three nitrogens of L, one carboxylate oxygen, and one methanol. In 3, Cu(II) is coordinated with three nitrogens of L, one nitrogen and one oxygen of picolinate, and one oxygen of perchlorate in a distorted octahedral geometry. Two molecules of 1, 2, and 3 are interacted by intermolecular hydrogen-bonding interactions and strong π–π stacking interactions to form a dinuclear structural unit. The dinuclear units are further connected by H-bonds via perchlorate or lattice methanol to form a 1-D chain for 1 and 2-D network structures for 2 and 3. Hydrogen-bonding and π–π stacking interactions are important for the stabilization of the final supramolecular structures of the three complexes.  相似文献   

3.
Four new substituted amino acid ligands, N-(3-hydroxybenzyl)-glycine acid (HL1), N-(3-hydroxybenzyl)-alanine acid (HL2), N-(3-hydroxybenzyl)-phenylalanine acid (HL3), and N-(3-hydroxybenzyl)-leucine acid (HL4), were synthesized and characterized on the basis of 1H NMR, IR, ESI-MS, and elemental analyses. The crystal structures of their copper(II) complexes [Cu(L1)2]·2H2O (1), [Cu(L2)2(H2O)] (2), [Cu(L3)2(CH3OH)] (3), and [Cu(L4)2(H2O)]·H2O (4) were determined by X-ray diffraction analysis. The ligands coordinate with copper(II) through secondary amine and carboxylate in all complexes. In 2, 3, and 4, additional water or methanol coordinates, completing a distorted tetragonal pyramidal coordination geometry around copper. Fluorescence titration spectra, electronic absorption titration spectra, and EB displacement indicate that all the complexes bind to CT-DNA. Intrinsic binding constants of the copper(II) complexes with CT-DNA are 1.32?×?106?M?1, 4.32?×?105?M?1, 5.00?×?105?M?1, and 5.70?×?104?M?1 for 1, 2, 3, and 4, respectively. Antioxidant activities of the compounds have been investigated by spectrophotometric measurements. The results show that the Cu(II) complexes have similar superoxide dismutase activity to that of native Cu, Zn-SOD.  相似文献   

4.
Two new coordination polymers, [Zn(bix)0.5(glu)]n (1) and {[Co(bix)(glu)]·4H2O}n (2), were synthesized (bix = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, glu = glutarate). In 1, each Zn(II) is connected by four glu ligands and extend to form a [Zn(glu)]n 2-D network. Adjacent [Zn(glu)]n 2-D networks are bridged by bix ligands to construct a 6-connected 3-D network based on the Zn2 unit. 2 shows an undulated 2-D (4,4) network. The interesting structural feature of 2 is that there are 1-D water chains. The O–H···O hydrogen bond interactions link the 2-D coordination networks and construct the 3-D supramolecular architecture in 2. The glu ligands are bis-(bidentate) bridges in 1 and bis-(monodentate) bridges in 2. The luminescence of 1 and thermal stability of 1 and 2 were investigated.  相似文献   

5.

The novel transition metal saccharinato complexes of N-(2-hydroxyethyl)-ethylendiamine (HydEt-en) have been synthesized and characterized by elemental analyses, magnetic moments, UV-Vis and IR spectra. Coordination behaviour of HydEt-en has been studied. The Mn(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) form mononuclear complexes, while the Fe(II) and Co(II) complexes are dimeric. The crystal structures of the [Cu(sac)2(HydEt-en)2] and [Cd(sac)2(HydEt-en)2] complexes, where sac is the deprotonated form of saccharin, were determined by x-ray diffraction. The metal ions are octahedrally coordinated by these ligands. The amine ligand acts as a bidentate N-donor ligand and its ethanol group is not involved in coordination. The sac ions coordinate through the deprotonated N as a monodentate ligand. The NH and OH groups of the amine ligand are involved in intra- and intermolecular hydrogen bonding with the carbonyl and sulphonyl oxygens of the sac ions to form a three-dimensional infinite network.  相似文献   

6.
A bidentate iminophenol (HL = 2-((4-methoxyphenylimino)methyl)-4,6-di-tert-butylphenol derived from condensation of 4-methoxyaniline and 3,5-di-tert-butyl-2-hydroxybenzaldehyde) was mixed with divalent metal salts to form the corresponding mononuclear metal complexes [MII(L)2] (M = Co (1), Cu (2), and Zn (3)). The complexes are characterized by different spectroscopic and analytical tools. X-ray crystal structures of the complexes revealed homoleptic mononuclear complexes with MN2O2 coordination. The cobalt(II) (1) and zinc(II) (3) complexes display a pseudo-tetrahedral coordination geometry, whereas the copper(II) complex (2) exhibits a distorted square-planar coordination. The zinc(II) complex (3) emits at 460 nm with a twofold enhancement of emission with respect to the free iminophenol.  相似文献   

7.
The complex [Cu(HGLYO)2(bipy)] ( I ) and two new copper(II) coordination polymers with the formulas {[Cu(GLYO)1‐x(ox)x(bipy)]·2.5H2O}n [GLYO = glycolato dianion, ox = oxalato dianion, bipy = 2, 2′‐bipyridine, x = 0.56 (in II ) or 0.71 (in III )] were synthesized using copper(II) glycolate as starting material and were characterized by IR, UV‐Vis and EPR spectrometry, by magnetic measurements ( II and III ), and by single‐crystal X‐ray diffractometry. Both II and III crystallized as one‐dimensional polymers composed of Cu2O2‐centred dimers with a Cu‐Cu distance of 3.282(1)Å (mean of II and III ) that are linked by Cu2(OCO)2 rings with a Cu‐Cu distance of 5.237(1)Å (mean of II and III ), both dianions acting as (μ‐1, 1, 2, 3) three‐way bridges connecting the two copper atoms of one dimer with one copper atom of a neighbouring dimer. Each copper atom is coordinated tetragonally in a CuN2O4 chromophore. In the mononuclear complex I the copper atom has a tetragonally distorted octahedral environment.  相似文献   

8.
Three polycarboxylate coordination polymers containing 2-(2-pyridyl)benzimidazole as co-ligand, [Cu(Bdc)(2-PyBIm)] n (1), [Cu(HBtc)(2-PyBIm)] n (2) and [Cd2(HBtc)2(2-PyBIm)2] n ·; nH2O (3) (H2Bdc?=?1,4-benzenedicarboxylic acid; H3Btc?=?1,3,5-benzenetricarboxylic acid), have been synthesized and characterized by elemental analyses, IR spectra, TG-DSC and X-ray structural analyses. Complex 1 is a one-dimensional zigzag chain in which the Cu(II) is cis six-coordinated by two chelating carboxyl groups and a 2-PyBIm ligand. Complex 2 is a two-dimensional (4, 4) network in which H3Btc is partially deprotonated. Complex 3 has a three-dimensional framework in which one Cd(II) is six-coordinate and the other is seven-coordinate. All 2-PyBIm groups are neutral, chelating, bidentate ligands in 13. These complexes are quite thermally stable. The luminescence of 3 has also been investigated.  相似文献   

9.
Two temperature-dependent Cu(II) compounds, [Cu(mpdaH)2(H2O)4] · 4H2O (1) and [Cu(mpdaH)2] n (2) (H2mpda = 2,6-dimethylpyridine-3,5-dicarboxylic acid), have been synthesized under hydrothermal conditions and characterized by X-ray single crystal diffraction, elemental analysis, thermogravimetric analyses, and IR spectra. The structure at room temperature confirms that 1 is mononuclear with the octahedral coordination geometry. However, on warming to 120°C the same reaction gives 2, in which copper(II) has square planar coordination and is further bridged by mpdaH? ligands to form extended 2-D layers with parallelogram-like (4,4) topology. Furthermore, in both complexes, through π–π stacking and hydrogen bonding interactions, 3-D supramolecular networks are assembled.  相似文献   

10.
Three new copper(II) complexes with isonicotinic acid N-oxide (HL) and 1,10-phenanthroline (phen) as ligands, [Cu(L)(phen)(H2O)]2(NO3)2···2H2O (1), [Cu(L)(phen)(H2O)]2(ClO4)2···2H2O (2), and [Cu(L)(phen)Br]2- [Cu(L)(phen)(H2O)]2Br2···6H2O (3) have been synthesized and structurally characterized. The structures of all three complexes feature a Cu2 dimer formed by two Cu(II) ions interconnected by two bridging ligands. Each copper(II) ion has a distorted square pyramidal coordination geometry with elongated axial coordination by an aqua ligand or halogen anion. The isonicotinic acid N-oxide anion is bidentate, being coordinated to two Cu(II) ions through its N-O oxygen and one of its carboxylate oxygen atoms. Magnetic susceptibility measurements show a Curie–Weiss paramagnetic behavior characteristic of one unpaired electron for a copper(II) ion for all three complexes.  相似文献   

11.
Reactions of copper salts, zoledronic acid, and 2,2′-bipyridine/1,10-phenanthroline in aqueous ethanolic solutions afforded four phosphonate oxygen-bridged copper complexes, Cu(bipy)(H4zdn)(HSO4) (1), [Cu2(bipy)2(H2zdn)(H2O)(Cl)]·4H2O (2), [Cu2(phen)2(H2zdn)(H2O)(Cl)]·2.5H2O (3), and [Cu3(bipy)3(H4zdn)(H2zdn)(SO4)]·5H2O (4) (H5zdn = zoledronic acid, bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline). The copper centers of 14 have square pyramidal coordination geometries. The Cu(II) ions are coordinated to bipy/phen, zoledronate, and HSO4?/Cl? forming mononuclear units for 1, dinuclear for 2 and 3, and trinuclear for 4. These building units are further extended into 3-D supramolecular networks via multiple hydrogen bond interactions. Temperature-dependent magnetic properties of 2 and 4 suggest weak antiferromagnetic coupling (J = ?4.53(8) cm?1 for 2, J = ?1.69(4) cm?1 for 4). The antitumor activity of 2 was evaluated against the human lung cancer cell line and indicates effective time- and dose-dependent cytotoxic effects.  相似文献   

12.
Four copper(II) complexes and one copper(I) complex with pyridine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (HLpz) and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide (HLpz?) were synthesized and characterized. The X-ray crystal structures of [Cu2(Lpz)2(4,4?-bipy)(OTf)2] (1, OTf?=?trifluoromethanesulfonate, 4,4?-bipy?=?4,4?-bipyridine) and [Cu(Lpz)(py)2]OTf·H2O (2, py?=?pyridine) revealed binuclear and mononuclear molecular species, respectively, while [Cu(Lpz)(μ2-1,1-N3)]n (3), [Cu(Lpz?)(μ2-1,3-N3)]n (4), and [Cu(HLpz)Cl]n (5) are coordination polymer 1-D chains in the solid state.  相似文献   

13.
A new 3-D copper(II) complex, formulated as [Cu2(btec)(en)2] n (1) [H4btec = benzene-1,2,4,5-tetracarboxylate, and en = ethylenediamine], was hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single crystal X-ray diffraction. The structural analysis of 1 reveals that copper(II) connect by μ6-bridging btec to form a 3-D coordination polymer, in which four carboxylates of btec show monodentate and bidentate coordination. Complex 1 was used as solid bulkmodifier to fabricate renewable carbon paste electrode (1-CPE) by direct mixing method. The cyclic voltammogram of 1-CPE displayed one-electron quasi-reversible redox waves in potential range 300 to ?300 mV due to Cu(II)/Cu(I). Moreover, 1-CPE showed electrocatalytic activity toward the reduction of nitrite.  相似文献   

14.
Tuning reaction temperatures as well as the variation in starting copper salts and solvents led to the formation of a new series of Cu(II) coordination compounds with 2,3-bis(2-pyridyl)pyrazine (dpp): a mononuclear [Cu(acac)(dpp)(NO3)] (1) complex, two dinuclear [Cu2(acac)2(dpp)(NO3)(H2O)]NO3 (2) and [Cu2(Hdpp)2(ox)(Cl)2(H2O)2]Cl2·6(H2O) (4) complexes, and four coordination polymers {[Cu4(dpp)2(ox)(Cl)6]}n (3), {[Cu4(dpp)2(ox)(NO3)6(H2O)2]∙1.2(H2O)}n (5), {[Cu(dpp)(NO3)](NO3)·(H2O)}n (6) and {[Cu(dpp)(SO4)(H2O)2]}n (7), where acac = acetylacetonate, ox2− = oxalate. Remarkably, the treatment of Cu(II) chloride dihydrate with dpp in methanol solution led to an unusual in situ condensation of dpp with acac to produce [Cu2(acdpp)2(Cl)4]·2(MeOH) (8). The structure of 1 consists of neutral, mononuclear [Cu(acac)(dpp)(NO3)] units with acac and dpp acting as bidentate ligands. In 2, the dpp ligand coordinates in a bis-chelating mode to two Cu(II) ions and bridges them into a dimeric entity, whereas an oxalate linker joins [Cu(Hdpp)(Cl)2(H2O)]+ units into a dimer in 4. Compounds 3, 5, 6 and 7 are 1D chain coordination polymers, which incorporate two symmetry independent metal centers and different bridging ligands: Hdpp+ as a protonated cationic or dpp as a neutral chelating ligand and oxalate, Cl anions or sulfate di-anions as bridging ligands. Magnetic studies were performed on samples 1 and 2, and the analysis reveals a very weak magnetic exchange coupling mediated via the dpp ligand.  相似文献   

15.
One nonlinear and one linear trinuclear copper(II) complex [Cu3(dien)2(pdc)2CH3OH]2?·?6CH3OH (1) and [Cu3(pdc)2(CH3OH)6(H2O)4] (2) were prepared and characterized structurally, where dien is diethylenetriamine and pdc3? the trianion of 3,5-pyrazoledicarboxylic acid. Both complexes consist of 3,5-pyrazoledicarboxylato-bridged trinuclear copper(II) centers. In 1, copper(II) ions are five-coordinate in distorted square pyramids with bond angles 164.78° for Cu(1)–Cu(2)–Cu(3) and 164.51° for Cu(4)–Cu(5)–Cu(6). In 2, the three copper(II) ions are six-coordinate with elongated octahedral geometry. The trinuclear units of 1 and 2 interact through hydrogen bonds to form 3-D and 2-D supramolecular networks, respectively. Variable temperature magnetic susceptibility measurements show that 1 and 2 are antiferromagnetically coupled with J values of ?11.2 and ?13.3?cm?1.  相似文献   

16.
Three new transition metal tricyanomethanide complexes [Cu(dpyam)(tcm)2] ( 1 ), [Cu(dpyam)(tcm)(OAc)] ( 2 ) and Zn(dpyam)2(tcm)2 ( 3 ) were synthesized and characterized by single crystal X‐ray diffraction analysis. In 1 each copper(II) atom is coordinated to three tcm anions and one dpyam molecule to form a square pyramide geometry. In 2 the coordination geometry around the central metal is also square pyramidal, and each copper atom is surrounded by two tcm anions, one dpyam ligand and one OAc. Both 1 and 2 display a µ1,5‐tcm bridged infinite chain structure. In 3 each zinc(II) atom is coordinated by two tcm anions and two dpyam molecules to form a distorted octahedral geometry. Different from the former two complexes, 3 shows a mononuclear structure. Magnetic susceptibility measurement in the range 2–300 K indicates that there are weak antiferromagnetic couplings between adjacent copper(II) ions in 1 (J=?0.03 cm?1) and 2 (J=?0.11 cm?1) respectively.  相似文献   

17.
The 2-methylimidazole complexes of Co(II), Ni(II), Cu(II) and Zn(II) orotates, mer-[Co(HOr)(H2O)2(2-meim)2] (1), mer-[Ni(HOr)(H2O)2(2-meim)2] (2), [Cu(HOr)(H2O)2(2-meim)] (3) and [Zn(HOr)(H2O)2(2-meim)] (4), were synthesized and characterized by elemental analysis, spectral (UV–Vis and FT-IR) methods, thermal analysis (TG, DTG and DTA), magnetic susceptibility, antimicrobial activity studies and single crystal X-ray diffraction technique. The complexes 1 and 2 have distorted octahedral geometries with two monodentate 2-methylimidazole and one bidentate orotate and two aqua ligands. The complexes 3 and 4 have distorted square pyramidal and trigonal bipyramidal geometry, respectively, with one 2-methylimidazole, bidentate orotate and aqua ligands. The orotate coordinated to the metal(II) ions through deprotonated nitrogen atom of pyrimidine ring and oxygen atom of carboxylate group as a bidentate ligand. The antimicrobial activities of 1 and 4 were found to be more active gram (+) than gram (−) and 4 could be use for treatment Staphylococcus aureus.  相似文献   

18.
To investigate the potential cytotoxicity of copper(II)-based complexes, three coordination compounds with heterocyclic ligands, Cu(pbmbt)Cl2(CH3OH) (1), Cu2(ddbib)2(NO3)4·3CH3OH (2), and Cu3(ttmtmb)2Cl6·2.5H2O (3), which include mononuclear, dinuclear, and trinuclear structures, have been synthesized from reactions of corresponding copper(II) salts with 1-((2-pyrazinyl)-1H-benzoimidazol-1-yl)methyl)-1H-benzotriazole (pbmbt), 2-(2,3-dihydropyrazin-2-yl)-1-((4-((2-(2,3-dihydropyrazin-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phenyl)methyl)-1H-benzo[d]imidazole (ddbib), and 1,1′,1′′-((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)tris(2-methyl-1H-benzoimidazole) (ttmtmb), respectively. IC50 values revealed that 2 and 3 show strong cytotoxicity, whereas 1 is weakly cytotoxic after being tested against a panel of several human alimentary system carcinoma cell lines (SGC7901, EC109, SMMC7721, and HT29). The number of copper centers and different structures could make a tremendous difference on their cytotoxicity.  相似文献   

19.
Pseudohalide complexes of copper(II) with aliphatic bidentate amines, [Cu(N3)2(N,N-diEten)]2 1, [Cu(NCO)2(N,N-diEten)]2 2, [Cu(NCO)2(N,N-diMeen)]2 3, [Cu(N3)(NCS)(N,N'-diMeen)]2 4 and [Cu(N3)(NCO)(N,N-diMeen)]2 5 (N,N-diEten=N,N-diethylethylenediamine; N,N-diMeen=N,N- dimethyl-ethylenediamine and N,N'-diMeen = N,N'-dimethylethylenediamine), were prepared, characterized and their thermal behavior was investigated by TG curves. According to thermal analysis and X-ray diffraction patterns all compounds decomposed giving copper(II) oxide as final product. The mechanisms of decomposition were proposed and an order of thermal stability was established.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

20.
Three new copper coordination compounds derived from 2,2-bis(hydroxymethyl)propionic acid (dmpa) and hexamethylenetetramine (hmta) were obtained and their crystal structures were determined. The stoichiometry of the reagents applied in the syntheses reflects the metal to ligand molar ratio in the formed solid products. Due to the multiple coordination modes of the used ligands, wide structural diversity was achieved among synthesized compounds, i.e., mononuclear [Cu(dmp)2(hmta)2(H2O)] (1), dinuclear [Cu2(dmp)4(hmta)2] (2), and 1D coordination polymer [Cu2(dmp)4(hmta)]n (3). Their supramolecular structures are governed by O—H•••O and O—H•••N hydrogen bonds. The compounds were characterized in terms of absorption (UV-Vis and IR) and thermal properties. The relationships between structural features and properties were discussed in detail. Owing to discrepancies in the coordination mode of a dmp ligand, bidentate chelating in 1, and bidentate bridging in 2 and 3, there is a noticeable change in the position of the bands corresponding to the stretching vibrations of the carboxylate group in the IR spectra. The differences in the structures of the compounds are also reflected in the nature and position of the UV-Vis absorption maxima, which are located at lower wavelengths for 1.  相似文献   

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