首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
A series of new nickel complexes, namely [Tp*Ni(sub)]·EtOH (1), [Tp*Ni(ad)]·EtOH (2), [Tp*Ni(seb)(H2O)] (3), and [Tp*Ni(μ–suc)NiTp*(MeOH)2] (4) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate, H2sub = suberic acid, H2ad = adipic acid, H2seb = sebacic acid, H2suc = succinic acid), were synthesized in mixed solvents at room temperature. The complexes were characterized by physico-chemical and spectroscopic methods. In addition, X-ray crystal structure analysis indicates that the four complexes share a common scorpionate (Tp*) Ni core with different aliphatic dicarboxylic acid ligands, and the nickel atom is in a distorted octahedral environment with the N3O3 donor set. Surface voltage spectroscopy indicates that these complexes exhibit surface photovoltage responses in the range of 300–800 nm, which can be assigned to LMCT and d → d * electronic transitions. In addition, quantum chemistry calculations on the complexes were performed and are discussed.  相似文献   

2.
Three complexes with the formula [Co(Ip)(CuL)(H2O)2] · H2O (I), [Co(Ip)(NiL)(H2O)2] · H2O (II), [Co(CuL)2(Hbtc)(H2O)] (III), (H2Ip = m-isophthalic acid; H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; H3Btc = 1,3,5-benzenetricarboxylic acid) were synthesized and structurally characterized by elemental analysis, IR and UV spectroscopy. Single-crystal X-ray analyses reveal that the complexes I and II contain neutral heterometallic binuclear CoM (for I and II, M = Cu, Ni, respectively) moieties, and complex III contains discrete neutral trinuclear CoCu2 moieties. The structures of IIII consist of two-dimensional supramolecular architecture formed by strong O-H…O intermolecular hydrogen bonds. Furthermore, the magnetic properties of complex I were investigated and discussed in detail.  相似文献   

3.
Four coordination polymers associated with bent bis(imidazole) 1,3-bis(imidazol-l-yl-methyl)benzene (mbix) and isophthalic acid (H2ip) or 5-methylisophthalic acid (H2mip) ligands, formulated as {[Cd(mbix)(mip)]·H2O} n (1), {[Co(mbix)(mip)]·0.4H2O} n (2) [Ni(mbix)(mip)H2O] n (3) and [Ni(mbix)(ip)] n (4), were synthesized under hydrothermal conditions and characterized by physico-chemical and spectroscopic methods. Complexes 1 and 2 are isomorphous and exhibit a 1D loop-like chain. Complex 3 features a 2D (4,4) layer, which further extends into an unusual 2D (3,5)-connected 3,5L2 double-layered supramolecular network via classical O–H···O hydrogen bonding interactions. Complex 4 is a 3D network, which shows a rare binodal (3,5)-connected 3,5T1 framework. Moreover, the luminescence and catalytic properties of the complexes for the degradation of methyl orange by sodium persulfate in a Fenton-like process are reported.  相似文献   

4.
Two new 2D metal-organic complexes, namely [Cu(3-dpyb)(1,2,4-HBTC)(H2O)]·H2O (1) and [Cu3(3-dpyb)3(SIP)2(H2O)8]·6H2O (2) [3-dpyb?=?N,N??-bis(3-pyridinecarboxamide)-1,4-butane, 1,2,4-H3BTC?=?1,2,4-benzenetricarboxylic acid, H3SIP?=?5-sulfoisophthalic acid], have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction analyses. Single crystal X-ray analyses reveal that the two Cu(II) complexes show different 2D coordination networks, the 4-connected (44·62) topology for complex 1 and the (4·62)2(42·62·82) topology for complex 2. In the 2D layers of complexes 1 and 2, the 3-dpyb ligands adopt a typical ?? 2-bridging mode (via ligation of two pyridyl nitrogen atoms), while 1,2,4-HBTC and SIP serve as a linear spacer and a ??V??-like linker, respectively, to connect the adjacent Cu(II) centers. The adjacent 2D layers are extended to 3D supramolecular networks via hydrogen-bonding interactions. The fluorescence properties of both complexes and electrochemical properties of complex 2 have also been investigated. The complex 2 bulk-modified carbon paste electrode (2-CPE) displayed a one-electron redox wave in potential range of 600?C200?mV in 1?M H2SO4 aqueous solution, and 2-CPE showed good electrocatalytic activity toward the reduction of nitrite.  相似文献   

5.
Two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes: [Mn((R,R)-Salphen)Fe(Tp)(CN)3]n (1) and [Mn((S,S)-Salphen)Te(Tp)(CN)3]n (2) (Salphen = N,N’-1,2-diphenylethylenebis (salicylideneiminato) dianion, Tp = tris(pyrazolyl) hydroborate), [Mn((R,R)-Salphen)Fe(Tp*)(CN)3·2H2O]n (3) and [Mn((S,S)-Salphen)Fe(Tp*)(CN)3·2H2O]n (4) (Tp* = hydridotris (3,5-dimethylpyrazol-1-yl) borate), have been successfully synthesized by the reactions of MnIII schiff-base complexes with the tricyanometalate building block, [(LTp)Fe(CN)3]- (LTp = Tp or Tp*). All complexes are made up of neutral cyano-bridged zigzag double chains with (-Fe-C≡N-Mn-N≡C-)n as the repeating unit. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes. Magnetic studies demonstrate that ferromagnetic interactions are operative in these complexes. The ferromagnetic couplings become weak in the chains with the bending of the Mn-N≡C angles.  相似文献   

6.
Two new polymeric networks, [Co(pbbm)(nip)] · H2O (1) and [Ni(pbbm)(nip) · (H2O)] (2) (pbbm = 1,1-(1,3-propanediyl)bis-1H-benzimidazole, H2nip = 5-nitroisophthalic acid) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is an interesting one-dimensional (1D) tube-like chain utilizing [Co2(pbbm)2] metallocycle as subunit. Complex 2 is also an interesting 1D tube-like chain based on [Ni2(pbbm)2] loop subunit. In the title complexes, the ??-?? stacking and H-bonding interactions extend the 1D tube into 3D supramolecular framework, respectively. The structural differences between the title complexes indicate the importance of metal ions for the creation of molecular architectures. Furthermore, the luminescent properties of 1 and 2 were investigated.  相似文献   

7.
Two new V(IV) complexes, [VO(Naph?Ctrp)(phen)]·CH3OH (1) and [VO(o-Van?Ctrp)(phen)]·CH3OH·H2O (2) (Naph?CTrp?=?Schiff base derived from 2-hydroxy-1-naphthaldehyde and l-tryptophan, o-Van?Ctrp?=?Schiff base derived from o-vanillin and l-tryptophan, phen?=?1,10-phenanthroline), have been synthesized and characterized by physicochemical methods. The V(IV) atoms in both complexes are six-coordinated in a distorted octahedral environment. In the crystals of complex 1, the C?CH···?? and ?ШC?? stacking interactions form a 1D chain structure, whereas for complex 2, hydrogen bonds connect the molecular units into a 2D plane structure. The DNA binding properties and cleavage efficiencies of the complexes have been investigated by spectroscopic methods, viscosity measurements and agarose gel electrophoresis. The results suggest that both complexes can bind to CT-DNA in an intercalative mode and can also cleave pBR322 DNA.  相似文献   

8.
Acid?Cbase equilibria of the aqua adducts of Ru(II) arene complexes, general formulae [(??6-p-cymene)Ru (L1?3)Cl2] where L1?=?3-acetylpyridine (1), L2?=?4-acetylpyridine (2) and L3?=?2-amino-5-chloropyridine (3), then [(??6-p-cymene)Ru(HL4)Cl2] with HL4?=?isonicotinic acid (4); [(??6-p-cymene)Ru(HL5?8)Cl] where H2L5?=?2,3-pyridine dicarboxylic acid (5), H2L6?=?2,4-pyridine dicarboxylic acid (6), H2L7?=?2,5-pyridine dicarboxylic acid (7) and H2L8?=?2,6-pyridine dicarboxylic acid (8) have been studied. pK a values were determined by potentiometry at 25?°C and constant ionic strength of 0.1?M NaNO3. The assumed equilibria were confirmed by UV and 1H-NMR spectroscopy.  相似文献   

9.
Two new Co(II) complexes, [Co2(H2O)(Bipy)2(Bript)2] n (I) and [Co(H2O)(Phen)(Bript)] · H2O (II), where H2Bript = 4-bromoisophthalic acid, Bipy = 2,2??-bipyridine, and Phen = 1,10-phenanthroline, have been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Complex I has binuclear units in which two Co2+ ions are bridged by two carboxylate groups and a coordinaiod-water molecule, and the binuclear units are connected by Bript to generate a 1D helical chain. These 1D helical chains are further linked by ????? stacking interactions to form a 3D supramolecular network, while complex II has a 2D layer motif. In I and II, there exists extensive hydrogen bonding interactions. The thermal behavior of the two corresponding complexes have briefly been investigated.  相似文献   

10.
The title compounds, (dmpH)[Cr(chelH)2]·3H2O, 1, (dmpH)[Co(chelH2)(chelH)]·3H2O, 2, (dmpH)[Ni(chelH2)(chelH)]·2H2O, 3 and [Cu(chelH)(dmp)]·3H2O, 4 (dmp is 2,9-dimethyl-1,10-phenanthroline and chelH3 is chelidamic acid or 4-hydroxypyridine-2,6-dicarboxylic acid) were obtained by one-pot reaction of 2,9-dimethyl-1,10-phenanthroline and 4-hydroxypyridine-2,6-dicarboxylic acid with corresponding salts in aqueous solution. The compounds were identified by IR, MS, elemental analysis and single crystal X-ray crystallography; also they were studied in the solution phase. The compounds 1, 2 and 3 are similar in coordination sphere around the metal ions, with some differences between protonation sites of chelidamate ion and the charge of complex, but compound 4 is essentially different. The compounds 1, 2 and 3 are six coordinated, but 4 is five coordinated. There are various O–H···O, O–H···N and N–H···O hydrogen bonds found in the structures. In a solution study, the protonation constants of dmp and chel, the equilibrium constants of the chel–dmp proton-transfer system and the stoichiometry and stability of complexation of this system with Cr(III), Co(II), Ni(II) and Cu(II) ions in an aqueous solution were investigated by potentiometric pH titration method. The stoichiometry of the most complexes species in solution was found to be very similar to the crystalline cited metal ion complexes.  相似文献   

11.
The first MnIII complexes with Schiff bases and tricyanomethanide-anion were synthesized: [Mn(salen)C(CN)3(H2O)] (1), [Mn(5-Brsalen)C(CN)3(H2O)] (2), [Mn(salpn)C(CN)3(H2O)] (3), [Mn(3-MeOsalen)C(CN)3(H2O)] (4), [Mn(5-Brsalen)(MeOH)(H2O)][C(CN)3] (5), and [Mn(3-MeOsalpn)(H2O)2][C(CN)3] (6), where SalenH2 is N,N′-bis(salicylidene)ethylenediamine, 5-BrsalenH2 is N,N′-bis(5-bromosalicylidene)ethylenediamine, SalpnH2 is N,N′-bis-(salicylidene)-1,3-diaminopropane, 3-MeOsalenH2 is N,N′-bis(3-methoxysalicylidene)-ethylenediamine, 3-MeOsalpnH2N,N′-bis(3-methoxysalicylidene)-1,3-diaminopropane. The tricyanomethanide anion in complexes 14 acts as a the terminal ligand, whereas in complexes 5 and 6 tricyanomethanide is not coordinated by MnIII and acts as an out-of-sphere counterion. The structures of complexes 14 are characterized by the formation of dimers due to hydrogen bonds between the water molecules and oxygen atoms of the Schiff bases. The Mn...Mn distances inside the dimers are 4.69–5.41 Å. Complex 6 has a zigzag chain structure consisting of the [Mn(3-MeOsalpn)(H2O)2]+ cations bound by double bridging aqua ligands. The study of the magnetic properties of complexes 1, 3, 4, and 6 showed the existence of antiferromagnetic interactions between the MnIII ions through the system of hydrogen bonds.  相似文献   

12.
The aim of this study was to explore the influence of the position and angles of carboxyl groups of polycarboxylates on constructing coordination polymers. Three Co(II) metal–organic coordination polymers based on a tri-pyridyl-bis-amide ligand, namely [Co(L)(1,2-BDC)(H2O)2]·2H2O (1), [Co(L)(1,4-BDC)(H2O)2]·2H2O (2) and [Co(L)2(BTEC)0.5]·H2O (3) (L = N,N′-bis(pyridine-3-yl)pyridine-2,6-dicarboxamide, 1,2-H2BDC = 1,2-benzenedicarboxylic acid, 1,4-H2BDC = 1,4-benzenedicarboxylic acid, H4BTEC = 1,2,4,5-benzenetetracarboxylic acid), have been obtained by tuning the auxiliary polycarboxylate ligands. Structural analyses reveal that complexes 13 display diverse structures. Complex 1 displays a meso-helical chain linked by L ligands, which is further extended into a three-dimensional supramolecular framework through hydrogen-bonding interactions. The 1,2-BDC with a chelating coordination mode only acts as the hydrogen bond acceptor. In complex 2, the 1,4-BDC anions connect adjacent Co(II) atoms to form a linear chain, which is connected by hydrogen-bonding interactions to construct a 3D supramolecular network. Complex 3 exhibits a chain, which is composed of left-/right-handed Co-L helical chains and Co-BTEC linear chain. The 1D chains are ultimately extended into a two-dimensional supramolecular network by hydrogen-bonding interactions. Moreover, the thermal stability and the fluorescent properties of the title complexes and the electrochemical behaviors of a bulk-modified carbon paste electrode with complex 2 have been investigated at room temperature.  相似文献   

13.
Cu(nor)2·H2O (1), Zn(nor)2·4H2O (2), Ni(nor)2·2H2O (3), [Cu(nor)(phen)]NO3·4H2O (4), [Zn(nor)(phen)]NO3·2H2O (5), and [Ni(nor)(phen)]NO3·3H2O (6) were synthesized and their action on Tetrahymena growth was studied by microcalorimetry. The growth constant (k), inhibitory ratio (I), and half-inhibiting concentration (IC50) were calculated, which showed that the complexes had a strong inhibitory effect on Tetrahymena. All these complexes can inhibit the growth of Tetrahymena more strongly than norfloxacin. The norfloxacin?Cmetal complexes exhibited better inhibitory activity than nor?Cphen?Cmetal complexes. The power?Ctime curves of Tetrahymena growth in the presence of norfloxacin were also measured. It was found that all complexes showed higher inhibitory activity than norfloxacin. And the inhibitory mechanism was discussed preliminarily. The diverse inhibition may be due to the ability of the complexes to penetrate into cells and the effect of these complexes on the nucleic acid. Microcalorimetry has been used extensively in many biological and chemical investigations as a universal, non-destructive, continuously running, and highly sensitive tool.  相似文献   

14.
Four copper(II) complexes containing Schiff base and reduced Schiff base ligands derived from pyridine-2-aldehyde and amino acid containing carboxylate and sulfonate functional groups (N-(2-pyridylmethylene)-amino acid and N-(2-pyridylmethyl)-amino acid, (amino acids = ??-alanine and aminoethanesulfonic acid) namely, [Cu(Pbals)(H2O)2]ClO4·H2O 1, [Cu(Pbal)(ClO4)(H2O)] 2, [Cu2(Paes)2(ClO4)2]·2H2O 3, and [Cu(Pae)(H2O)]·ClO4·H2O 4 have been synthesized and characterized. The structural features of carboxylate and sulfonate donor groups have been elucidated. These copper(II) complexes demonstrate different coordination behaviour of the carboxylate and sulfonate groups. Carboxylate groups in complexes 1 and 2 bridge the metal centers and facilitate the formation of 1D helical coordination polymeric structures. In compound 3, the sulfonate groups bridge the metal centers to form a discrete dinuclear complex. In 4, the sulfonate groups link the neighbouring metal centers to form a 1D coordination polymeric structure.  相似文献   

15.
The development of resistance and unwanted harmful interaction with other biomolecules instead of DNA are the major drawbacks for application of platinum (Pt) complexes in cancer chemotherapy. To conquer these problems, much works have been done so far to discover innovative Pt complexes. The objective of the current study was to evaluate the anti cancer activities of a series of four and five-coordinated Pt(II) complexes, having deprotonated 2-phenyl pyridine (abbreviated as C^N), biphosphine moieties, i.e., dppm?=?bis(diphenylphosphino) methane (Ph2PCH2PPh2) and dppa?=?bis(diphenylphosphino)amine (Ph2PNHPPh2), as the non-leaving carrier groups. The growth inhibitory effect of the Pt complexes [Pt(C^N)(dppm)]PF6: C 1 , [Pt(C^N)(dppa)]PF6: C 2 , and [Pt(C^N)I(dppa)]: C 3 , toward the cancer cell lines was measured using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay. In addition, the florescence quenching experiments of the interaction between human serum albumin (HSA) and the Pt complexes were performed in order to obtain the binding parameters and to evaluate the denaturing properties of these complexes upon binding to the general carrier protein of blood stream. The structure?Cactivity relationship studies reveal that four-coordinated Pt complexes C 1 and C 2 with both significant hydrophobic and charge characteristics, not only exhibit strong antiproliferation activity toward the cancer cell lines, but also they display lower denaturing effect against carrier protein HSA. On the other hand, five-coordinated C 3 complex with the unusual intermolecular NH??Pt hydrogen binding and the intrinsic ability for oligomerization, exhibits poor anticancer activity and strong denaturing property. The current study reveals that the balance between charge and hydrophobicity of the Pt complexes, also their hydrogen binding abilities and coordination mode are important for their anticancer activities. Moreover, this study may suggest C 1 and C 2 as the potential template structures for synthesis of new generation of four-coordinated Pt complexes with strong anticancer activities and weak denaturing effects against proteins.  相似文献   

16.
Two new bis(5,6-dimethybenzimidazole)-based CoII complexes, Co(pydca)(L)2·2H2O (1) and [Co(bdc)(L)] n (2) (L = 1,3-bis(5,6-dimethylbenzimidazol-1-yl)-2-propanol, H2pydca = pyridine-2,6-dicarboxylic acid, H2bdc = 1,4-benzenedicarboxylic acid) were synthesized and characterized by physicochemical, spectroscopic methods and single-crystal diffraction. The cobalt(II) centers display different environments with distorted square-pyramidal geometry in 1 and a perfect tetrahedral geometry in 2. Complex 1 is a mononuclear structure, which is further assembled into a 3D supramolecular network via strong hydrogen bonding as well as ππ interactions; while complex 2 possesses a 2D corrugated (4,4) network that is further formed into a (3,4,4)-connected network with (62.84)(63)2(64.82)2-3,4,4T25 topology due to classical hydrogen bonds. The fluorescence and catalytic performances of the two complexes for the degradation of methyl orange by sodium persulfate have been investigated.  相似文献   

17.
Tris[2-(N-ethyl)benzimidazylmethyl]amine (Etntb) and two of its complexes, [Zn(Etntb)(cinnamate)]NO3·2DMF (1) and [Ni(Etntb)(cinnamate)·(H2O)]NO3 (2) have been synthesized and characterized by physico-chemical and spectroscopic methods. Single-crystal X-ray diffraction revealed that the complexes have different structures. In complex 1, the coordination sphere around Zn(II) is distorted trigonal bipyramidal, whereas the coordination sphere around Ni(II) is distorted octahedral in complex 2. The DNA-binding properties of the free ligand and its complexes have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that the ligand and both complexes bind to DNA via an intercalative mode, and their binding affinity for DNA follows the order 1 > 2> ligand.  相似文献   

18.
The enantioselective interactions between chiral tetra-amidic receptors and nucleosides have been investigated by the ESI-IT-MS and ESI-FT-ICR-MS methodologies. Configurational effects on the CID fragmentation of diastereomeric [M H 2 ?H?A]?+ aggregates (A?=?2'-deoxycytidine dC, citarabine (ara-C) were found to be mostly offset by isotope effect in [S X 2 ?H?A]?+ (X?=?H, D) differently from the results obtained on the analogues (A?=?cytidine C and gemcitabine G). This result points the involvement of two different nucleoside/tetraamide isoforms. The structural differences of the [M H 2 ?H?A]?+ (A?=?C and G) complexes vs. the [M H 2 ?H?A]?+ (dC and ara-C) ones is fully confirmed by the kinetics of their uptake of the 2-aminobutane enantiomers, measured by FT-ICR mass spectrometry. Indeed, uptake of the 2-aminobutane enantiomers by [M H n ?H?A]?+ (n?=?1,2; A?=?dC and ara-C) complexes is reversible, while that by [M H n ?H?A]?+ (n?=?1,2; A?=?C and G) is not. The most encouraging result concerning the measured fragmentation and kinetic differences between C and ara-C, that are just epimers, indicates the possibility to subtly modulate the non-covalent drug/receptor interactions, through the electronic properties of the 2'-substituent on the nucleoside furanose ring, and furthermore on its three-dimensional position.  相似文献   

19.
The complexes [Fe(bpz*mpy)2](ClO4)2 (1a), [Cu(bpz*mpy)2](ClO4)2 (1b) and [Ag(bpz*mpy)(Ph3P)](ClO4) · H2O (2) (bpz*mpy = pyridin-2-yl-bis(3,5-dimethylpyrazol-1-yl)methane) have been synthesized and characterized by physicochemical and spectroscopic methods. X-ray crystallographic analysis reveals that the central FeII and CuII ions in complexes 1a and 1b are located on a twofold rotation axis and have a distorted octahedral coordination sphere, while the AgI center in complex 2 is tetrahedrally coordinated. The electrochemical properties of complex 1b have been investigated. Furthermore, a variable temperature magnetic susceptibility study of complex 1a has also been performed over the measured temperature range 2–300 K.  相似文献   

20.
The homonuclear water-soluble and air stable compounds (dmpH) (H5O2) au][M(pydc)2].0.5H2O (M = Ni(II) (1), Cu(II) (2), Zn(II) (3); pydcH2 = pyridine-2,6-dicarboxylic acid, dipicolinic acid, dmp = 2,9-dimethyl-1,10-phenanthroline) have been prepared by self-assembly synthesis in aqueous solution at room temperature, and characterized by IR, 1H NMR, 13C NMR, elemental analysis and X-ray diffraction single crystal analyses for 1, 2 and 3. The complexes 1–3 represent the isostructural features. Extensive hydrogen bonding interactions involving all aqua ligands, dipicolinate oxygens and lattice water molecules further stabilize the complex units by linking them to form three dimensional polymeric networks. The stoichiometry and stability of the all three complexes in aqueous solution were investigated by potentiometric pH titration.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号