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1.
Two pyridine-2,5-dicarboxylic acid (pydcH2) complexes of nickel(II) with 2,2′-bipyridine and 1,10-phenanthroline were synthesized and characterized by elemental, spectroscopic, thermal analysis, magnetic measurements and single crystal X-ray diffraction techniques. Both [Ni(pydc)(bipy)2]·7H2O and [Ni(pydc)(phen)2]·6.5H2O crystallize in the monoclinic system and P21/c space group. The Ni(II) ions are coordinated by two bidentate bipy or phen ligands and one pydc dianion in a distorted octahedral geometry. The pydc ligand is coordinated through the pyridine nitrogen atom and oxygen atom of carboxyl group as a bidentate ligand. Both carboxylate groups of pydc are deprotonated but only the 2-carboxylate is coordinated to the metal. Thermal decompositions of the complexes have been studied over the range 30–600 °C on heating in a static air atmosphere.  相似文献   

2.
Three novel heterobinuclear complexes have been prepared and identified as [Cu(oxap)Ni(L)2](ClO4)2·ξH2O, where oxap denotes theN,N′-bis(2-aminopropyl)oxamido dianion and L denotes 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen) or 5-nitro-1,10-phenanthroline (NO2-phen). The crystal structure of [Cu(oxap)Ni(phen)2]-(ClO4)2·2H2O has been determined. Crystal data: triclinic, space group , a=12.079 (6), b=12.409 (4), c=17.261 (8) ?, α=70.91 (2), β=86.72 (4), γ=89.19 (3)o. At room temperature, Z=2. The CuII is in a square planar environment and the NiII is in an octahedral environment. The Cu−Ni distance is 5.292 ?. The temperature dependences of the magnetic susceptibilities of [Cu(oxap)Ni(phen)2]-(ClO4)2·2H2O and [Cu(oxap)Ni(bipy)2](ClO4)2 have been studied in the 4.2–300 K range, giving the exchange integral J=−92.4 cm−1 for bipy and J=−94.3 cm−1 for phen. These results are commensurate with antiferromagnetic interactions between the adjacent metal ions.  相似文献   

3.
Two coordination complexes, namely [Co(phen)(H2O)L]·H2O and [Ni2(phen)2(H2O)2L2]·4H2O (phen = 1,10-phenanthroline, H2L = 1,3-adamantanedicarboxylic acid) have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. [Co(phen)(H2O)L]·H2O consists of 1D chains of the complex plus lattice H2O molecules. Interchain hydrogen bonds and π–π stacking interactions assemble the 1D chains into 2D layers. [Ni2(phen)2(H2O)2L2]·4H2O is a binuclear complex which is assembled into a 3D supramolecular structure by strong hydrogen bonds and π–π stacking interactions. Both complexes were characterized by physico-chemical and spectroscopic methods.  相似文献   

4.
Two hexa-coordinate copper(II) complexes formulated as [Cu(phen)(4-dmampy)2(ClO4)2] and [Cu(bpy)(3-ampy)2(ClO4)2] · 0.5CH3OH · 0.5H2O (phen = 1,10–phenanthroline bpy = 2,2′-bipyridine, 3-ampy = 3-aminopyridine, 4-dmampy = 4-dimethylaminopyridine), and one low-spin ferrous complex formulated as [Fe(dmbpy)3](ClO4)2 · H2O (dmbpy = 4,4′-dimethyl-2,2′-bipyridine), were synthesized by in situ ligand substitution at room temperature, and characterized by X-ray single-crystal diffraction. This is the first structural report where either 4-dmampy and phen molecules, or 3-ampy and bpy molecules, are located simultaneously around one metal center.  相似文献   

5.
A series of Cu(II) carboxylate complexes (carboxylate?=?2-fluorobenzoic acid (2-HFBA) or 4-fluorobenzoic acid (4-HFBA)) containing either one chelating 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and thermal analyses. In [Cu(bipy)(H2O)(2-FBA)2] (1), [Cu(bipy)(H2O)(4-FBA)2] (3), and [Cu(phen)(H2O)(2-FBA)2] (4), Cu is five-coordinate in a square pyramidal geometry and four-coordinate in [Cu(phen)(2-FBA)2] (2). The four complexes are extended into 1-D chains through hydrogen-bonding and π?···?π interactions in 1 and 4, only hydrogen-bonding in 2, and π?···?π interactions in 3. These contacts lead to aggregation and supramolecular self-assembly.  相似文献   

6.
The reactions of the rhenium chalcocyanide cluster salts K4[Re4Q4(CN)12]·6H2O (Q = S or Se) with Cu2+ cations coordinated by the bidentate ligand 2,2′-bipyridyl (bipy) produced two new cluster compounds, [Cu(NH3)(bipy)2]2[Re4S4(CN)12]·bipy·3.25H2O (1) and [{Cu(bipy)2}2Re4Se4(CN)12]·bipy·8.5H2O (2). The structures of these complexes were solved by X-ray diffraction. Compound 1 is ionic. Compound 2 is molecular. In the structures of both compounds, there are staking interactions between the {Cu(bipy)2}2+ cationic moieties and the solvate 2,2′-bipyridyl molecules. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1875–1878, November, 2006.  相似文献   

7.
Reduced molybdophosphate-based supramolecular compounds, such as (4,4′-H2bipy)[Co(H2O)2]2[Co(H2PO4)2(HPO4)4(PO4)2(MoO2)12(OH)6] · 17H2O (1), [Co(2,2′-bipy)2(H2O)]4[Co(H2O)2][Co(HPO4)6(PO4)2(MoO2)12(OH)6] · 2H2O (2), and [Co(2,2′-bipy)2(H2O)]4[Co(H2PO4)(H2O)2]2[Co(HPO4)6(PO4)2(MoO2)12(OH)6] · 8H2O (3) (4,4′-bipy=4,4′-bipyridine, 2,2′-bipy=2,2′-bipyridine), have been synthesized under hydrothermal conditions and characterized. Compound 1 exhibits a three-dimensional supramolecular twofold interpenetrating architecture built up of one-dimensional [P4Mo6]-based infinite covalent chains and free 4,4′-bipy molecules. Compound 2 also shows a three-dimensional supramolecular network constructed from one-dimensional covalent [P4Mo6]-based chains. Unlike compounds 1 and 2, compound 3 exhibits an interesting three-dimensional ‘honeycomb-like’ supramolecular network constructed by the stacking of [Co(2,2′-bipy)2(H2O)] units with one-dimensional channels, in which the [P4Mo6]-based polyoxometalate chains are located. The magnetic properties of compounds 2 and 3 are reported. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

8.
Four novel organic–inorganic hybrid compounds [Cu5 I(4,4′-bpy)3(2,2′-bpy)4][BW12O40] · H2O (1), [Ni0.5(2,2′-bpy)1.25][Ni(2,2′-bpy)3][Ni(2,2′-bpy)2(H2O)(SiW11VIWVO40)] · 0.5H2O (2), [H2bpy]2[Zn(2,2′-bpy)3]2[Si2W18O62] · 1.5H2O (3) and [CuII(2,2′-bpy)2]2[SiW12O40] · 2H2O (4) (2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, electrochemical measurements and single-crystal X-ray diffraction. Compound (1) is a novel [BW12O40]5− polyoxoanion bisupported by copper(I) coordination cations with mixed 2,2′-bpy and 4,4′-bpy ligands. Compound (2) is constructed from the [SiW11VIWVO40]5− polyoxoanions supported by [Ni(2,2′–bpy)2]2+. Compound (3) is composed of a novel [Si2W18O62]8− cluster and [Zn(2,2′–bpy)3]2+ complexes, which held together into a three-dimensional (3D) supramolecular network through hydrogen-bonding interactions. Compound (4) shows a 2D layer framework constructed from a bisupporting Keggin polyoxoanion cluster and [Cu(2,2′–bpy)2]2+ coordination polymer fragments, resulting in 3D networks via supramolecular interactions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

9.
The electrochemical oxidation of anodic cobalt, nickel, and zinc in acetonitrile containing both 2-pyrrole-[N-(o-hydroxyphenyl)methylimines] (H2L) and a bidentate ligand (1, 10-phenanthroline(phen) or 2,2′-bipyridine(bipy)) yielded compounds of general formula M(HL)2 · phen and M(HL)2 · bipy (M = Co, Ni, Zn). The crystal structure of 2,2′-bipyridine bis{2-[(2-pyrrole)methylimino]5-methylphenolato}nickel(II) was determined by X-ray diffraction. This compound crystallizes in the orthorhombic space group Pccn with a = 19.430(2), b = 28.488(2), c = 17.567(1) Å. The nickel atom has a distorted octahedral geometry, and the pyrrole nitrogen is not coordinated. The IR, 1H-NMR and UV-visible spectra of the complexes are discussed and related to the structure.  相似文献   

10.
Summary The electrochemical oxidation of anodic metal (nickel or cobalt) in MeCN solutions of 1-hydroxy-2-pyridinethione (HPT) gives [Ni(PT)2], [Co(PT)2] or [Co(PT)3]. When 1,10-phenanthroline (phen) or 2,2-bipyridine (bipy) are added to the electrolytic phase the product is a complex, [Ni(PT)2L] or [Co(PT)2L] (L = bipy or phen). The i.r., u.v. and 1H- and 13C-n.m.r. spectra of the complexes are discussed.This paper was presented at the 5th Inorganic Chemistry Meeting of the Royal Spanish Chemical Society, Tossa de Mar, Girona, Spain, September 1991.  相似文献   

11.
Two new supramolecular metal–organic complexes have been synthesized under hydrothermal conditions. Complex 1 exhibits a three-dimensional supramolecular network, constructed from [Co2(H3BPTC)2(phen)2] (H4BPTC = 3,3′4,4′-benzophenone tetracarboxylate acid, phen = 1,10-phenanthroline) discrete units. Complex 2 similarly exhibits discrete [Cu2(DPA)2(bipy)2(H2O)2] (DPA = 1,1′-biphenyl-2,2′-dicarboxylate acid, bipy = 2,2′-bipyridine) units, which are linked to form a three-dimensional supramolecular network through π–π interactions. It is interesting that during the synthesis of complex 1, the H4BPTC ligands undergo partial decomposition to give 1,2,4-benzenetricarboxylate (H3BTC) ligands, which react with Co to form [Co3(BTC)2]n (3). Complex 3 shows a three-dimensional covalent network. The magnetic properties of complexes 1 and 2 have been studied.  相似文献   

12.
Potentiometric (PT) and conductometric (CT) titration methods have been used to determine the stoichiometry and formation constants in water for a series of ternary complexes of Co(II) and Ni(II) involving the oxydiacetate anion (ODA) and 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) ligands, namely [Co(ODA)(phen)(H2O)], [Co(ODA)(bpy)(H2O)], [Ni(ODA)(phen)(H2O)] and [Ni(ODA)(bpy)(H2O)]. The ternary complex formation process was found to take place in a stepwise manner in which the oxydiacetate ligand acts as a primary ligand and the phen or bipy ligands act as auxiliary ones. The stability of the ternary complexes formed is discussed in the relation to the corresponding binary ones. Furthermore, the kinetics of the substitution reactions of the aqua ligands in the coordination sphere of the Ni-ODA and Co-ODA complexes to phen or bipy were studied by the stopped-flow method. The kinetic measurements were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (4–7 mM). The influence of experimental conditions and the kind of the auxiliary ligands (phen/bipy) on the substitution rate was discussed.   相似文献   

13.
The ligand N-(2-propionic acid)-salicyloyl hydrazone(H3L, 1) and its new transition metal(II) complexes [NiHL(bipy)H2O] (2), [CdHL(bipy)(H2O)2]2·2H2O (3) and [NiHL(phen)H2O]·H2O (4) (HL is a dianion, bipy?=?2,2′-bipyridine and phen?=?1,10-phenanthroline) were synthesized and characterized on the basis of elemental analyses, IR, 1H NMR, molar conductivity and thermal analysis. Single crystal X-ray diffraction showed that 1 is in keto form and connected by hydrogen bonds to form a two-dimensional supermolecular compound. Complexes 2 and 4 have the same structure with distorted meridional octahedral geometry with 1 as a tridentate ligand with keto-form coordination by azomethine, carboxyl O and acyl O. In 3, ligand 1 bridges two Cd(II) atoms by μ 2-O of carboxyl. H-bonding is an important weak interaction for constructing supermolecular frameworks. There are π–π interactions between bipy or phen rings in 3 or 4, respectively.  相似文献   

14.
New transition metal complexes of Co(II), Cu(II), Ni(II), and Fe(III) of the ligands 6,6′-(1E,1′E)-(4,5-dimethyl-1,2-phenylene)bis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)bis(7-hydroxy-5-methoxy-2-methyl-4H-chromen-4-one) H2L1 and 6,6’-(1E,1′E)-cyclohexane-1,2-diylbis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)bis(7-hydroxy-5-methoxy-2-methyl-4H-chromen-4-one) H2L2 have been prepared and characterized using physio-chemical and spectroscopic methods. The results obtained for the complexes indicated that the geometries of the metal centres are either square planar or octahedral. Cyclopropanation reactions of unactivated olefins by ethyldiazoacetate (EDA) in the presence of [L1Cu]·H2O, [L2Cu]·2H2O and [L2*Co]·2H2O as catalysts were examined. The results showed that only [L2*Co]·2H2O can act as a catalyst for the cyclopropanation reaction of unactivated olefins with very high selectivity (up to 99% based on EDA).  相似文献   

15.
This article describes the synthesis of a polypyridyl ligand, namely 2-(2, 5-dimethoxyphenyl)-1H-imidazo[4,5-f]1,10-phenanthroline (DMPIP) and its Ru(II) complexes, namely [Ru(bipy)2DMPIP]2+ (1), [Ru(dmb)2DMPIP]2+ (2) and [Ru(phen)2DMPIP]2+ (3) ((bipy = 2,2′-bipyridine, dmb = 4,4′-dimethyl-2,2′-bipyridine, phen = 1,10-phenanthroline). The complexes were characterized by elemental analysis, plus IR, 1H-NMR and 13C [1H]-NMR spectra. The interactions of the complexes with calf thymus DNA were investigated. The results indicate that the three complexes can intercalate into DNA. Under irradiation at 365 nm, all three complexes promote the photocleavage of plasmid pBR 322 DNA. Inhibitor studies suggest that singlet oxygen plays a significant role in the cleavage mechanism for the complexes.  相似文献   

16.
Three isomorphous coordination polymers of general formula {[M(H2bna)·(DMF)2·(H2O)2]·DMF}n (M = Co for 1, Mn for 2, Ni for 3, respectively, where H4bna = 2,2′-dihydroxy-[1,1′]-binaphthalene-3,3′-dicarboxylate) were synthesized under solvothermal conditions and characterized by FTIR, single crystal X-ray diffraction, thermogravimetric analysis, and X-ray power diffraction analysis. All three polymers crystallize in the same monoclinic space group P21/n. The complexes are assembled into 1D helical chains, and each adjacent helical chain of the same chirality is further connected to form a chiral layer by hydrogen bond interactions. The layers are packed in alternating left-(M) and right-handed (P) chirality arrays. Magnetic studies reveal the presence of antiferromagnetic coupling interactions in complexes 1 and 2.  相似文献   

17.
Two new neutral Keggin-polyoxometalate derivatives: [{Co(2,2′-bipy)2(H2O)}2]–[PMoVI7MoV5O40(VIVO)2] (1) and [{Ni(phen)2(H2O)}2](H3O) [PMoVI10MoV2O40] · 4H2O (2) have been synthesized under hydrothermal conditions and characterized by i.r., t.g. analysis, x.p.s. spectra and single-crystal X-ray diffraction. In the case of (1), the polyoxoanion cluster [PMo12O40]8− is capped by two vanadium atoms via four bridging oxo groups on two opposite {Mo4O4} pits of the Keggin polyoxoanion. Two {Co (2,2′-bipy)2(H2O)} fragments are supported on the two vanadium atoms through two terminal oxygen atoms from two vanadium atoms. In (2), two {Ni(phen)2(H2O)}2+ moieties are linked to the molybdophosphate cluster [PMo12O40] core to form a neutral bimetallic cluster. Furthermore, through the linkages of ππ stacking interactions and hydrogen bond contacts, extended three-dimensional supramolecular networks in the solid of (1) and (2) were formed.  相似文献   

18.
Under similar hydrothermal synthetic conditions, the reactions of Fe(NO3)3/FeCl2, CuCl2, NiCl2, and CdCl2 with phenanthroline (phen) and 3,3′,4,4′-biphenyltetracarboxylic acid (H4BPTC) afforded complexes [Fe(phen)3](H3BPTC)2 (1), [Cu(phen)(BPTC)0.5 · H2O] · H2O (2), [Ni3(phen)3(BPTC)1.5(H2O)5] · 4H2O (3) and [Cd(phen)(BPTC)0.5] · H2O (4). The short Fe–N distance in the monomeric Fe(phen)3(H3 BPTC)2 (1) shows that the Fe(II) is in a low-spin state. H3 BPTC4− acts as a counter-ion in this complex. In [Cu(phen)(BPTC)0.5 · H2O] · H2O (2), the central Cu(II) is five-coordinated in a square-pyramidal geometry. The ligand BPTC4− is centrosymmetric and the four deprotonated carboxylic groups of BPTC4− are coordinated to four different copper ions to form a 1D ladder complex indicating a comparatively strong coordination. In [Ni3(phen)3(BPTC)1.5(H2O)5] · 4H2O (3), all nickel(II) atoms are in an octahedral coordination environment. There are two different BPTC4− ligands; one is centrosymmetric and the other is asymmetric. Metal ions are linked through fully deprotonated BPTC4− ligands to form a 2D metal-organic sheet. [Cd(phen)(BPTC)0.5] · H2O (4) has a 3D metal-organic framework. TG, IR, and fluorescence data for the complexes are presented.  相似文献   

19.
The Re(NO)2+ moiety as [Re(NO)(NCS)3H2O] or [Re(NO)(NCS)2(L-L)H2O]· [L-L = phen (1,10-phenanthroline) or bipy (2,2′-bipyridine)] undergoes proton-induced oxidation reaction with HX (X = Cl, Br) to produce a Re(NO)3+ moiety. The spectral and physico-chemical data suggest that the anionic complex is 5 coordinate and the neutral one is 6 coordinate with axial NO group and two NCS ligands intrans-equatorial positions. The complex, [Re(NO)(NCS)2(phen)Br]·H2O shows complicated magnetic behaviour which is discussed in the paper. The ESR spectrum of this compound shows typical rhenium hyperfines and <g>-tensor anisotropy compatible with the loss of axial symmetry. However, the spectrum of [Re(NO)(NCS)2Br2] quite reasonably shows axial symmetry, other features being grossly comparable to the L-L compounds. The anionic species and the neutral L-L complex show irreversible one-electron oxidation waves at different voltages. This may correspond to a conversion of Re(NO)3+ to Re(NO)4+ in both the cases. Interestingly enough, only the neutral complexes exhibit an irreversible reduction wave due probably to a conversion of Re(NO)3+ to Re(NO)2+.  相似文献   

20.
Three Co(II) and Ni(II) complexes, namely [Co(bpdc)(H2O)2] (1), [Ni(bpdc)(H2O)2] (2), and [Co2(bpdc)2(prz)0.5(H2O)3]·0.5H2O (3) (H2bpdc = 2,2′-bipyridine-6,6′-dicarboxylic acid and prz = piperazine), have been synthesized from H2bpdc and the corresponding metal salts under hydrothermal conditions. The complexes were characterized by physico-chemical and spectroscopic methods, as well as by X-ray crystallography. Compounds 1 and 2 both consist of neutral mononuclear molecules, of [Co(bpdc)(H2O)2] and [Ni(bpdc)(H2O)2], respectively. Compound 3 consists of a mononuclear molecule of [Co(bpdc)(H2O)2] and a binuclear molecule of [Co2(bpdc)2prz (H2O)2]. The discrete neutral complexes 13 further extend their structures into three-dimensional supramolecular architectures by intermolecular O–H⋯O and C–H⋯O hydrogen bonds as well as π–π stacking interactions. Magnetic susceptibility measurements show that complex 3 exhibits weak ferromagnetic interactions between the two Co(II) ions bridged by the prz ligand, with C = 5.41 cm3 mol−1 K and θ = +27.6 K, respectively.  相似文献   

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