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1.
A series of transition metal (Zn, Cu, Mn) complexes with chelidamic acid (2,6-dicarboxy-4-hydroxypyridine, H3CAM) and 4,4′-bipyridine (bipy), [Zn2(bipy)Cl2] n (1), {[Zn2(HCAM)(H2CAM)2]?·?(bipy)?·?3.5H2O} n (2), [Mn3(HCAM)3(H2O)7]?·?(bipy)?·?3H2O (3), [Mn2(HCAM)2(bipy)?·?(H2O)2]?·?4H2O (4), [Cu2(HCAM)2(bipy)?·?(H2O)2]?·?4H2O (5), and Cu2(HCAM)2(bipy)?·?(H2O)2 (6), have been synthesized by hydrothermal or solution methods and characterized by single-crystal X-ray diffraction. The structural analyses reveal that 1 exhibits a zigzag chain of Zn(II), Cl?, and 4,4′-bipyridine. In 2, a 1-D polymeric [Zn2(HCAM)(H2CAM)2] n chain and a discrete 4,4′-bipyridine assemble into a 2-D supramolecular network via H-bonds. Complex 3 consists of asymmetric units of Mn3(HCAM)3(H2O)7 that are linked by hydrogen bonds to form a 2-D H-bonded network. Complexes 46 are isomorphous and possess discrete structures. The photoluminescent properties of 16 at room temperature were studied.  相似文献   

2.
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   

3.
Self-assemblies of the 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and Cu(OH)2 in the presence of dicarboxylate ligands yielded four new complexes, [Cu4(bpca)4(L1)2(H2O)2]·5H2O (1), [Cu2(bpca)2(L2)(H2O)2]·2H2O (2), [Cu2(bpca)2(L3)(H2O)2]·H2O (3), and [Cu2(bpca)2(L4)(H2O)2]·3H2O (4) (bpca = bis(2-pyridylcarbonyl)amide anion, H2L1 = phthalic acid, H2L2 = succinic acid, H2L3 = maleic acid, H2L4 = acetylenedicarboxylic acid). Their structures were determined by single-crystal X-ray diffraction analyzes and further characterized by IR spectra and thermogravimetric analyzes. The five-coordinate Cu ions in 1 are bridged by phthalate to form 1-D chains, which are assembled into 3-D frameworks by extensive hydrogen bonds. Compounds 2–4 possess similar structures, built up of [Cu2(bpca)2(L)(H2O)2] (L = L2 for 2, L3 for 3, L4 for 4) and lattice molecules. The 3-D frameworks of 2–4 are completed by hydrogen bond interactions.  相似文献   

4.
Four metal(II) complexes with benzene-1,2,3-triyltris(oxy)triacetic acid (H3L), {[Co1.5(L)(H2O)6]·6H2O}n (1), {[Co1.5(L)(4,4′-bipy)1.5(H2O)4]·4H2O}n (2), {[Co(HL)(2,2′-bipy)(H2O)2]·1.5H2O}n (3), and {[Cu(HL)(phen)(H2O)2]·H2O}n (4) (4,4′-bipy = 4,4′-bipyridine; 2,2′-bipy = 2,2′-bipyridine; phen = phenanthroline), were prepared and structurally characterized. Complex 2 displays a 1-D structure, while 1, 3, and 4 reveal 0-D structures, which further extend to 3-D supramolecular networks by hydrogen bonding interactions, of which 1 and 4 contain double-helical chains, 2 includes meso-helices, and 3 comprises single-helices. Furthermore, the thermal stabilities and antibacterial activities of the complexes were studied.  相似文献   

5.
Three complexes [Zn2(IPA)2(phen)4](HIPA)2(NO3)2·H2O (1), {[Zn(IPA)2(bipy)]·3H2O}n (2), and {[Mn(IPA)2(bipy)(H2O)]·2H2O}n (3) (HIPA = indole-3-propionic acid, phen = 1,10-phenanthroline, bipy = 4,4′-bipyridine) were synthesized and characterized by physico-chemical and spectroscopic methods. Complex 1 displays a zero-dimensional structure, whilst 2 and 3 show one-dimensional chains, which are linked into supramolecular networks through hydrogen bonding interactions and/or π···π stacking interactions. The luminescence properties of complexes 1 and 2 were investigated.  相似文献   

6.
Two 3D open-framework nickel diphosphonates, [Ni3(H2zdn)2(bpe)2]·4H2O (1) and [Ni3(H2zdn)2(bpy)2]·bpy·4H2O (2) (H5zdn = zoledronic acid, bpe = trans-4,4-vinylenedipyridine, bpy = 4,4′-dipyridyl), have been prepared and structurally characterized. In complex 1, the metal centers are linked by zoledronate ligands to generate a 2D layer, containing 14- and 24-membered rings. These 2D layers are further pillared by the bpe ligands into a 3D network structure with cylindrical channels. Magnetic susceptibility measurements reveal ferrimagnetism at T c = 3.8 and 4.4 K for complexes 1 and 2, respectively.  相似文献   

7.
Six transition metal coordination compounds with H2mand and different N-donor ligands, [Co(Hmand)2(2,2′-bipy)]·H2O (1), [Ni(Hmand)2(2,2′-bipy)]·H2O (2), [Ni(Hmand)2(bpe)] (3), [Zn(Hmand)2(2,4′-bipy)(H2O)]·2H2O (4), [Zn(Hmand)(bpe)(H2O)]n[(ClO4)]n·nH2O (5), and [Zn(Hmand)(4,4′-bipy)(H2O)]n[(ClO4)]n (6), were synthesized under different conditions (H2mand = (S)-(+)-mandelic acid, bpe = 1,2-di(4-pyridyl)ethane, 4,4′-bipy = 4,4′-bipyridine, 2,4′-bipy = 2,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine). Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, infrared spectra, thermogravimetric analysis, powder X-ray diffraction, and circular dichroism. Compounds 1 and 2 are isostructural (0-D structures), which are extended to supramolecular 1-D chains by hydrogen bonding. Compound 3 exhibits 1-D straight chain structures, which are further linked via hydrogen bond interactions to generate a 3-D supramolecular architecture. Compound 4 displays a discrete molecular unit. Neighboring units are further linked by hydrogen bonds and ππ interactions to form a 3-D supramolecular architecture. Compound 5 displays a 2-D undulated network, further extended into a 3-D supramolecular architecture through hydrogen bond interactions. Compound 6 possesses a 2-D sheet structure. Auxiliary ligands and counteranions play an important role in the formation of final frameworks, and the hydrogen-bonding interactions and ππ stacking interactions contributed to the formation of the diverse supramolecular architectures. Compounds 1, 2, 4, 5, and 6 crystallize in chiral space groups, with the circular dichroism spectra exhibiting positive cotton effects. Furthermore, the luminescent properties of 46 have been examined in the solid state at room temperature, and the different crystal structures influence emission spectra significantly.  相似文献   

8.
The two complexes of composition Cu2(OAc)4(phen)(H2O)2 ( 1 ) andCu2(OAc)4(phen)2(H2O) ( 2 ) have been synthesized and characterized by chemical analysis and IR and electronic spectroscopies. Compound 2 has the structure of a dimer with a phenanthroline molecule and two monodentate acetate groups coordinated to each copper atom and a water molecule as the only bridging ligand between them. Each copper atom has a distorted square‐planar pyramidal coordination, determined by two oxygen atoms at 1.94(3) and 1.959(3) Å, two nitrogen atoms at 2.023(4) Å and the oxygen atom of the bridging water molecule at 2.289(2) Å. The distance between the two copper atoms is of 4.29 Å and the angle Cu(1)‐O(3)‐Cu(1A) 139.2(2)°. The water molecule is involved in two intramolecular hydrogen bonds with non coordinated oxygen atoms. The distance between the molecules of phenanthroline is 3.75 Å. Magnetic and EPR results for Cu2(OAc)4(phen)(H2O)2 ( 1 ), Cu2(OAc)4(phen)2(H2O) ( 2 ), Cu2(OAc)4(bipy) ( 3 ) and Cu2(OAc)4(bipy)2(H2O)2 ( 4 ) have been analysed and compared. For 1 and 3 an antiferromagnetic dimer unit [Cu2(μ‐OAc)4] with 2J = ?325 and ?292 cm?1, respectively, and other two copper atoms without significant magnetic interaction are present. Triplet signals are detected in the EPR spectra. In 2 and 4 there is no practically magnetic exchange and the orthorhombic signals are observed in the EPR spectra.  相似文献   

9.
In this paper, self-assembly reactions of copper(II) ions, methoxybenzoate isomers and 2,2′-bipyridine yield two copper-oxygen polynuclear complexes: [Cu2(bpy)2(2-C8H7O3)3]·(2-C8H7O3)·14H2O 1, [Cu4(bpy)4(H2O)(OH)4]·4(3-C8H7O3)·17H2O 2, and a simple mononuclear complex [Cu(bpy)(H2O)(4-C8H7O3)2] 3. (bpy = 2,2′-bipyridine, C8H7O3 = methoxybenzoate ion). Single crystal X-ray diffraction analyses reval that compound 1 is a dinuclear copper(II) complex which bridged by three carboxylate groups, and 2 presents a discrete step-like tetra-nuclear copper Cu4O4 core. Compound 3 shows a square pyramidal mononuclear geometry. The magnetic susceptibility of complex 1 measured from 2 to 300 K, revealed an antiferromagnetic interaction between the Cu(II) ions. Furthermore, the results about IR spectra and thermal analyses were discussed.  相似文献   

10.
Two copper(II) coordination polymers, {[Cu2(btre)(hsuc)Cl(H2O)]·1.5H2O}n (1) and {[Cu2(btre)(hsuc)Br(H2O)]·1.5H2O}n (2) (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H3hsuc = 2-hydroxysuccinic acid), were synthesized by the hydrothermal method via in situ hydroxylation reaction with fumarate (fum), btre and CuCl2/CuBr2, and characterized by elemental analyses, IR, TG and X-ray diffraction. 1 and 2 are isostructural and show a 4-connected 2-D network based on [Cu2O] dimers. 1 and 2 show good photocatalytic activity for the degradation of organic dyes methylene blue and methyl orange under UV light irradiation.  相似文献   

11.
Eight new platinum(II)/palladium(II) complexes with 4-toluenesulfonyl-L-amino acid dianion and diimine/diamine ligands, [Pd(en)(Tsile)]·H2O (1), [Pd(bipy)(Tsile)] (2), [Pd(bipy)(Tsthr)]·0.5H2O (3), [Pd(phen)(Tsile)]·0.5H2O (4), [Pd(phen)(Tsthr)]·H2O (5), [Pd(bqu)(Tsthr)]·1.5H2O (6), [Pt(en)(Tsser)] (7), and [Pt(en)(Tsphe)]·H2O (8), have been synthesized and characterized by elemental analyses, 1H NMR and mass spectrometry. The crystal structure of 7 has been determined by X-ray diffraction. Cytotoxicities were tested by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide and sulforhodamine B assays. The complexes exert cytotoxicity against HL-60, Bel-7402, BGC-823, and KB cell lines with 4 having the best cytotoxicity against HL-60, Bel-7402, and BGC-823 cell lines; the compounds are less cytotoxic than cisplatin.  相似文献   

12.
Three mono-, bi- and tetranuclear copper(I) complexes, [Cu(phen)(triphos-O)]BF4 (1) (phen = 1,10-phenanthroline, triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane), [Cu2(bipy)(triphos)2](BF4)2 (2) (bipy = 4,4′-bipyridine), and [Cu4(MeOC^N^N)4(triphos)2(bipy)](BF4)4 (3) (MeOC^N^N = 6-(4-methoxyphenyl)-2,2′-bipyridine), have been synthesized and characterized by NMR spectroscopy, electrospray ionization, and matrix-assisted laser desorption ionization time-of-flight mass spectrometries, elemental analysis, and X-ray crystal analysis. The crystal structure investigation revealed the copper ions of the complexes have pseudo-tetrahedral coordination geometry. The electronic absorption spectra of 1, 2, and 3 contain low-energy bands at 350–500 and 400–650 nm, which are assigned to d(Cu) → π*(phen or bipy) and a mixture of d(Cu) → π*(MeOC^N^N) and d(Cu) → π*(bipy) transitions, respectively. Complex 2 displays a strong, long-lived solid-state emission with a maximum at 555 nm and lifetime of 13.6 μs at room temperature. Photoinduced electron-transfer properties of 2 and 3 involving nanosecond time-resolved absorption spectroscopy and electron spin resonance techniques were studied.  相似文献   

13.
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   

14.
Three Zn(II) complexes, [Zn2(bpp)2(FNA)2]·H2O (1), [Zn(bpp)(FNA)]·H2O (2), and Zn2(bpp)2(FNA)2 (3) (bpp = 1,3-bi(4-pyridyl)propane, H2FNA = 4-nitrobenzene-1,2-dicarboxylic acid), were synthesized and characterized by single-crystal and powder X-ray diffraction methods, IR spectroscopy, TG analyses, elemental analyses, and fluorescent analysis. In 1, the Zn(II) ions are linked by FNA anions and bpp into 2-D layers. The Zn(II) ions in 2 are bridged by FNA anions into chiral chains, which are interlinked by bpp into 3-D metal–organic framework with (65·8) CdS topology. Complex 3 features 1-D zigzag chains, which are interconnected by bpp ligands to give a 3-D framework with (6·74·8)(64·7·8) topology. Complexes 2 and 3 exhibit significant ferroelectric behavior (for 2 remnant polarization Pr = 0.050 μC cm?2, coercive field Ec = 1.13 kV cm?1, saturation of the spontaneous polarization Ps = 0.239 μC cm?2; for 3 Pr = 0.192 μC cm?2, Ec = 4.64 kV cm?1, Ps = 0.298 μC cm?2).  相似文献   

15.
A dicyanoamide-bridged polymeric copper(I/II) complex, [CuII(sal)(bipy)CuI(dca)2]n, was prepared by reaction of 5-methylchlorosalicylaldehyde (Hsal), 2,2′-bipyridine (bipy), sodium dicyanoamide (Nadca), and copper perchlorate in methanol. The complex was characterized by elemental analyses, infrared and electronic spectroscopy, and single-crystal X-ray determination. CuII has a square pyramidal coordination, and CuI has triangular coordination. The complex showed high urease inhibitory activity with IC50 value of 0.16 ± 0.23 μM.  相似文献   

16.
范赛荣  朱龙观 《中国化学》2005,23(10):1292-1296
Cobait(Ⅱ) nitrate reacted with 1,10-phenanthroline (phen) and 5-sulfosaiicylic acid (H3ssal) to yield the cobait(Ⅰ) complex [Co(phen)2(H2O)2](Hssal)o4H2O (1) and the reaction of 1 with copper acetate led to a novel complex [Co(phen)(H2O)4][Cu2(ssal)2(phen)2]·5H2O (2). These two complexes were cationanion species and the cationic motif [Co(phen)2(H2O)2]^2+of 1 could be converted to [Co(phen)(H2O)4]^2+ in the formation process of new anion [Cu2(phen)2(ssal)2]^2- of 2. In both complexes abundant hydrogen bonds construct different supramolecular architectures, thus the conversion reaction can provide a new path to create novel supramolecular network.  相似文献   

17.
Two complexes, [Cu2(TFSA)(2,2′-bpy)4]?·?TFSA?·?8H2O (1) and {[Cu(4,4′-bpy)(H2O)2]?·?TFSA?·?6H2O} n (2) (H2TFSA?=?tetrafluorosuccinic acid, 2,2′-bpy?=?2,2′-bipyridine, and 4,4′-bpy?=?4,4′-bipyridine), have been synthesized and structurally characterized by X-ray structural analyses. Complex 1 is a binuclear molecule bridged by TFSA ligands; 2 is a 1-D chain bridged by 4,4′-bpy ligands. The asymmetric units of the two complexes are composed of cationic complexes [Cu2(TFSA)(2,2′-bpy)4]2+ (1) and [Cu(4,4′-bpy)(H2O)2]2+ (2), free TFSA anion, and independent crystallization water molecules. A unique 2-D hybrid water–TFSA anionic layer by linkage of {[(H2O)8(TFSA)]2?} n fragments consisting of 1-D T6(0)A2 water tape and TFSA anionic units by hydrogen bonds in 1 was observed. Unique 2-D hybrid water–TFSA anionic layer generated by the linkage of {[(H2O)6(TFSA)]2?} n fragments consisting of cyclic water tetramers with appended water molecules and TFSA anionic units, and 1-D metal–water tape [Cu–H2O?···?(H2O)6?···?H2O?] n in 2 were found. 3-D supramolecular networks of the two complexes consist of cationic complexes and water–TFSA anionic assemblies connected by hydrogen bonds.  相似文献   

18.
Four new anthraquinone-1,5-disulfonate (L)-based metal complexes with N,N-bidentate chelating coligands, {[Pb(phen)2(L)]?·?4H2O} n (1), {[Mn2(2,2′-bipy)2(H2O)6(L)]?·?L?·?6H2O} (2), [Co(phen)2(H2O)(L)] (3), and [Zn(phen)2(H2O)(L)] (4) (phen = 1,10-phenanthroline and 2,2′-bipy?=?2,2′-bipyridine), have been hydrothermally synthesized and were structurally characterized by single-crystal X-ray diffraction, elemental analyses, FT-IR spectra, thermogravimetric curves, and solid luminescence spectra. Structural analysis suggests that 1 is a polymeric 1D zigzag chain bridged by dianionic L. In contrast, the other three complexes have discrete centrosymmetric binuclear structure for 2 and isolated isomorphic mononuclear entities for 3 and 4, which are further assembled into 3D supramolecular networks by abundant hydrogen-bonding and/or π–π stacking interactions. Additionally, 2 and 4 exhibit favorable luminescent emissions, suggesting they are potential candidates for light emission materials.  相似文献   

19.
Two copper(II) complexes, [Cu2(μ-benzoato)(L1)2]NO3·2H2O (1) and [Cu2(μ-succinato)(L2)2(H2O)]ClO4 (2), have been synthesized, where L1 = N′-[(E)-phenyl(pyridin-2-yl)methylidene]benzoylhydrazone and L2 = N′-[(E)-pyridin-2-ylmethylidene]benzoylhydrazone. These complexes were characterized including by single-crystal X-ray diffraction studies. The copper is five-coordinate in 1 while in 2 one copper is five-coordinate and the other is six-coordinate. Electrochemical behavior of these complexes was measured by cyclic voltammetry. The conproportionation equilibrium constants (Kcon) for both complexes have been estimated. The superoxide dismutase (SOD) activities of 1 and 2 were measured by nitro blue tetrazolium assay. Complex 1 has better SOD activity than 2.  相似文献   

20.
Three dinuclear copper(II) complexes with the anti-inflammatory drug Fenoprofen [Hfen, 2-(3-phenoxyphenyl)propionic acid] and nitrogen donors of general formula [Cu2(fen)4(L)] n were prepared from [Cu2(fen)4(dmf)2]·2H2O (1) [dmf?=?N,N′-dimethylformamide; L?=?4,4′-bipyridine (2), pyrazine (3), and 2,5-dimethylpyrazine (4)]. The new complexes were characterized by chemical analysis, spectroscopic, and thermogravimetric techniques. Antioxidant properties of 1–4 were evaluated for superoxide-dismutase-mimic activity employing the XTT method. Complex 2 presented the highest antioxidant activity (IC50?=?0.260?µmol?L?1). Anti-inflammatory properties of 2 were evaluated employing carrageenan-induced paw edema in mice, revealing that the Fenoprofen–copper(II) complex containing 4,4′-bipyridine does not present enhanced anti-inflammatory activity compared to the uncomplexed parent drug Fenoprofen calcium salt.  相似文献   

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