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1.
Hydrothermal reaction of Co(II) salt with 1,4-di(1-imidazolyl)benzene (L1) and 4,4’-oxydiphthalic acid (H4OA) yields a new complex [Co3(HOA)2(L1)4(H2O)4] (I). [Ni(L2)2SO4] · 0.5H2O (II) can be obtained via the hydrothermal reaction of NiSO4 · 6H2O with 1,3-di(1H-imidazol-4-yl)benzene (L2). Complexes I and II have been characterized by single-crystal and powder X-ray diffraction (CIF files CCDC nos. 1019291 (I) and 1019292 (II)), IR, elemental, and thermogravimetric analyses. Complex I exhibits the uninodal six-connected 3D pcu framework structure of I with (412 · 63) topology; Complex II consists of the uninodal four-connected 2D sql (44 · 62) networks. In addition, magnetic property of I was investigated.  相似文献   

2.
Two heterometallic cluster compounds and one monometallic cluster compound, namely [Ni9Co6(PMIDA)6(BTC)2(H2O)12]·6H2O (1), [Co13Zn2(PMIDA)6(H2O)18]·6NO3·15H2O (2), and [Fe15(PMIDA)6(BTC)2(H2O)22]·38H2O (3), have been obtained under hydrothermal conditions using N-(phosphonomethyl)imino-diacetic acid (H4PMIDA) and 1,3,5-benzenetricarboxylate acid (H3BTC) as ligands, and structurally characterized by X-ray crystallography. Compound 1 exhibits a 3D open framework constructed from [Ni9Co6(PMIDA)6(H2O)12]6+ heteronuclear clusters and BTC3? ligands. Compounds 2 and 3 are both zero-dimensional polynuclear clusters, further extended into 3D supramolecular structures via hydrogen-bonding interactions. However, there are some differences in their crystal structures; compound 2 features an isolated spherical heteronuclear cation cluster based on PMIDA4? ligands, such that the NO3 ? anions only balance the charge, whereas compound 3 is characterized as a neutral monometallic cluster incorporating two different types of organic acid ligands, namely PMIDA4? and BTC3?, and the two BTC3? ligands exhibit regular distribution in each cluster. The luminescence properties of all three compounds have been investigated at room temperature.  相似文献   

3.
Reactions of the rigid–flexible N-heterocycle 1,3-bis(5-(pyridine-2-yl)-1,2,4-triazole-3-yl) propane (H2L) with MCl2 (M = Fe, Co, Cu or Zn) gave coordination complexes, {[Fe 2 III Cl4(H2L)2]·2Cl}·EtOH·H2O (1), {[Co3Cl5(HL)]·H2O} n (2), {[Co4Cl4(H2L)2(H2O)4]·[CoCl4]2}·H2O (3), [Cu2Cl3(HL)(H2O)]6·5H2O (4), [Cu 2 II CuICl4(HL)] n (5), {[Zn2Cl2(L)H2O]·H2O} n (6) and [Zn4Cl6(HL)2] (7), which have been characterized by single-crystal X-ray diffraction. Structural analysis reveals that the pyridine triazole ligand attains versatile coordination modes in these complexes. Complexes 1, 3, 4 and 7 consist of 0D clusters with binuclear or tetranuclear units; complex 2 presents a 2D network accompanied by HL? and chloride bridges; complexes 5 and 6 show 1D chains with [Cu3] and [Zn2] subunits. In addition, the electrospray ionization mass spectrometry properties of selected complexes were investigated, revealing the stabilities and structural states of these complexes in solution. These results indicate that H2L is an excellent multiconnection linker for the construction of diverse coordination complexes.  相似文献   

4.
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   

5.
Two coordination polymers, namely {[Co2L(dpe)2]·0.42H2O} (1), and {[Zn4L2(dpe)4]·4H2O} (2), were solvothermally prepared from a flexible tetrapodal ligand tetrakis[(3-carboxyphenyl)oxamethyl]methane acid (H4L) and a secondary bidentate linker (E)-1,2-di(pyridin-4-yl)ethane (dpe). Single-crystal X-ray diffraction analysis revealed that these compounds possess similar three-dimensional structures, in which the frameworks are constructed from dinuclear SBUs (secondary building units) [M2(COOR)4N4] (M?=?Co or Zn) and tetrahedral L4? linkers. The overall structures of both compounds can be described as (4, 6)-connected binodal networks, with a Schläfli symbol of {42537}{4255647282} according to the topological analysis. Compound 2 exhibits strong photoluminescence at room temperature, with a peak at 422 nm (excitation at 370 nm), most probably from an intraligand and/or ligand-to-ligand charge transfer (LLCT). The emission of compound 2 was quenched efficiently by Fe3+ ion, suggesting that 2 could be used as a fluorescence sensor for Fe3+.  相似文献   

6.
Three new complexes based on 1-tetrazole-4-imidazole-benzene (Tibz), namely, [Cd(Tibz)2(H2O)2] n (I), [Mn(Tibz)2(H2O)4] · 2H2O (II) and [Co(Tibz)2(H2O)4] · 2H2O (III) have been synthesized through hydrothermal method and structurally characterized by element analyses, IR spectroscopy and single-crystal X-ray diffraction analyses (CIF files CCDC nos. 1443867 (I), 1443868 (II), 1443869 (III)). Single-crystal X-ray diffraction reveals that complex I is a 1D double-chain architecture, II and III are both mononuclear complexes. The results of single-crystal X-ray diffraction analyses indicate that the hydrogen bond and π··· π stacking exist in the complexes, which make great contribution to the stabilities of complexes IIII. The fluorescent properties of these complexes have also been studied in the solid state at room temperature.  相似文献   

7.
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   

8.
Four novel coordination polymers, [Zn(HL1)2(phen)2]·2CH3OH·2H2O (1), [ZnCl(HL1)(4,4′-bipy)0.5] n (2), [Cd(HL1)(L2)0.5(2,2′-bipy)2]·3H2O (3), [Zn(L3)0.5(N3)1.5(phen)] n (4) (H2L1 = 9-(1H-tetrazole-5-yl)-10-carboxyl anthracene, H2L2 = 9,10-di-(1H-tetrazole-5-yl) anthracene, HL3 = 9-(1H-tetrazole-5-yl)-10-cyan anthracene, 1,10-phen = 1,10-phenanthroline, 4,4′-bipy = 4,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine), have been constructed by in situ ligands synthesis system. The formation of tetrazole-based ligands H2L1, H2L2 and H2L3 involves the in situ Sharpless [2 + 3] cycloaddition reaction between 9,10-dicyanoanthracene (DCA) and NaN3 in the presence of Zn2+/Cd2+ ions as Lewis-acid catalysts under hydro/solvothermal conditions. At the same time, there is also another in situ carboxyl ligand synthesis reaction by hydrolysis from nitrile in compounds 1 and 2. The four compounds have been characterized by elemental analysis, IR and single-crystal X-ray diffraction analysis. Compound 1 exhibits a butterfly-shaped mononuclear structure. Compound 2 represents a 2D framework constructed by six-membered {Zn6} rings as secondary building units (SBUs). Compound 3 presents a dinuclear {Cd2} structure with two butterflies “flying side by side” fashion. While compound 4 displays a 1D chain structure based on a dinuclear {Zn2} SBUs. Moreover, the luminescence properties of 1–4 have been also investigated.  相似文献   

9.
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   

10.
Using an octadentate ligand, namely tetrakis[(3,5-dicarboxyphenoxy)methyl] methane (H8L), four coordination polymers, [Ni3L(OH)2(H2O)2][NH2(CH3)2]4·5H2O (1), [Co4L(H2O)4]·9H2O (2), [Zn4L(H2O)4]·DMF·11H2O (3) and [Li4(H4L)(H2O)4] (4) (DMF = N,N-dimethylformamide), have been solvothermally synthesized and structurally characterized by X-ray crystallography. Complex 1 is an anionic three-dimensional open framework built from tricluster {Ni3(COOR)8} and square planar L ligands to give a uninodal 6-connected pcu network. Complexes 2 and 3 are isostructural, possessing a non-interpenetrated three-dimensional network with rare (4,8)-connected scu topology. Complex 4 consists of 4-connecting {Li2(COOR)4} clusters which form a 2D Shubnikov tetragonal plane net with sql topology. Complexes 1–3 all have large solvent accessible voids, but only complex 3 possesses permanent porosity as confirmed by N2, H2, CO2 and CH4 gas adsorption measurements. In addition, complex 3 shows strong photoluminescent emissions at room temperature with a peak at 365 nm, owing to a ligand-centered excited state. The emission intensities of 3 varied upon contact with different solvents or analytes.  相似文献   

11.
Six new complexes [Mn8(μ4-O)4(phpz)8(MeOH)4]·(MeOH)(H2O) (1) [Co2(HphpzH)(Hphpz)2(phpz)2]·4(MeOH) (2), Ni(Hphpz)2 (3), [Ni(Hphpz)2]·H2O (4), [Zn4(pzpy)4Cl4] (5) and [Cu2(pzpy)2(HCO2)2(H2O)2] (6) have been synthesized by hydrothermal reactions of MCl2·4H2O (M = Mn, Co, Ni, Zn or Cu) with 5-(2-hydroxyphenyl)-3-pyrazole (HphpzH) or 2-(1H-pyrazol-3-yl)pyridine (Hpzpy). The complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Complex 1 is an octanuclear Mn(III) cluster, complexes 2 and 6 are binuclear Co(III) and Cu(II), respectively, complexes 3 and 4 are isomorphous mononuclear species, while complex 5 is a tetranuclear Zn(II) cluster. The magnetic behavior of complex 1 was investigated. Magnetic susceptibility measurements revealed antiferromagnetic exchange interactions between the metal centers in the clusters. The luminescence properties of the complexes were investigated at room temperature in the solid state.  相似文献   

12.
Three Ag(I) coordination polymers [Ag(L1)]·(H3bptc)·H2O (1), [Ag2(L2)(oba)]·H2O (2), and [Ag2(L2)2]·(H2bptc) (3) [L1 = 1,4-bis(3,5-dimethylpyrazole)butane, L2 = 1,4-bis(2-methylbenzimidazole)butane, H4bptc = 3,3′,4,4′-biphenyltetracarboxylic acid, H2oba = 4,4′-oxybis(benzoic acid)] constructed from N-containing ligands with different flexibilities and organic carboxylates as co-ligands have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis. All three complexes display 1D chain structures, which are further extended into 2D supramolecular networks via non-classical C–H···O hydrogen bonding interactions. The fluorescence and catalytic properties of the complexes 13 have been investigated in detail. Complexes 2 and 3 reveal promising catalytic activities for the degradation of methyl orange in a Fenton-like process.  相似文献   

13.
Four new complexes, [Cu2(Bpca)2(L1)(H2O)2] · 3H2O (I), [Cu2(Bpca)2(L2)(H2O)2] (II), [Cu2(Bpca)2(L3)] · 2H2O (III), [Cu2(Bpca)2(L1)(H2O)] · 2H2O (IV) (Bpca = bis(2-pyridylcarbonyl)amido, H2L1 = glutaric acid, H2L2 = adipic acid, H2L3 = suberic acid, H2L4 = azelaic acid) have been synthesized and characterized by single-crystal X-ray diffraction methods (CIF files CCDC nos. 1432836 (I), 1432835 (II), 817411 (III), and 817412 (IV)), elemental analyses, IR spectra. Structural analyses reveal that compounds I, II, and IV have similar structures [Cu(Bpca)]+ units bridged by dicarboxylate forming dinuclear units, whereas the dinuclear of compound III are edge-shared through two carboxylate oxygen atoms of different suberate anions. Hydrogen bonds are response for the supramolecular assembly of compounds I to IV. The temperature-dependent magnetic property of III was also investigated in the temperature range of 2 to 300 K, and the magnetic behaviour suggests weak antiferromagnetic coupling exchange.  相似文献   

14.
The incorporation of LnIII ions into the 12-metallacrown-4 topology affords the formation of four mixed 3d-4f pentanuclear complexes of compositions [NH(C2H5)3]{[Ln(OAc)4] [12-MC Mn III (N)shi-4]}·xH2O (Ln = Sm (1), Gd (2), Tb (3), Dy (4); x = 0.5 for 1 and 3, x = 0.25 for 2, x = 0 for 4; H3shi = salicylhydroxamic acid). Compounds 14 were obtained from the reactions of H3shi with Mn(CH3COO)2·4H2O and Ln(NO3)3·6H2O, in the presence of N(C2H5)3. They all contain a crown-like [Mn4Ln(μ-NO)4]11+ core with four MnIII atoms being at the rim of the crown and an LnIII ion occupying the dome of the crown. The peripheral ligation about the core is provided by four η11:µ acetate groups. The identity of the LnIII ions slightly affects the 12-metallacrown-4 frameworks, as demonstrated by the gradual decrease of the distances between the LnIII ions and the centres of the Mn4 planes (1.85 Å for 1, 1.81 Å for 2, 1.80 Å for 3, and 1.77 Å for 4). Variable-temperature dc magnetic susceptibility studies were carried out on polycrystalline samples of 14. Antiferromagnetic interactions are determined for complexes 14.  相似文献   

15.
Two new coordination polymers [Co(H2O)2(bpy)2]·2(Adi) (1) and [Co4(OH)2(Adi)6(bpe)2] (2) (HAdi = 4-amino-3,5-diiodobenzoic acid, bpy = 4,4′-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene) have been synthesized by methods of hydrothermal reactions and their crystal structures determined. In 1, the mononuclear Co atoms are linked by bpy ligands forming cationic two-dimensional square grids, which are connected by the intercalated Adi guest molecules through significant hydrogen-bonding interactions to give a three-dimensional supramolecular porous network with one-dimensional channels. 2 has a one-dimensional chain structure based on rhombic tetranuclear CoII clusters, connected by bpe ligands. Through special I···I interactions, adjacent chains are extended into a three-dimensional supramolecular structure. The structure versatility indicates that the amino and iodo groups of Adi ligands play a crucial role in modulating the coordination polymers. A discussion of the crystal structures, thermal stabilities, as well as the noncovalent interactions of Adi molecules is provided. IR, elemental analysis and XRPD confirmed the phase purity of the bulk materials. Magnetic properties of 2 in the 300–2 K have been discussed, which reveal the occurrence of antiferromagnetic interactions between CoII ions.  相似文献   

16.
The coordination reactions of 3d metal salts with malonic acid N,N′-bis(salicyloyl) bishydrazide (H6mbshz) afforded three complexes, namely [Cu2(H2bshz)(Py)4Cl2]·Py (1) (Py = pyridine), [Fe2(bshz)(Py)2] (2) and the known complex [Ni4(aehba)2(DMF)2(H2O)2]·2DMF (3), where bshz = N,N′-bis(salicyloyl)hydrazine anion and aehba4? = azo-enolic-2-hydroxybenzamide anion. The X-ray crystal structures of all three complexes have been obtained. Complexes 1 and 2 are composed of N–N-bridged binuclear units, while complex 3 displays a planar tetranuclear structure in which four Ni(II) centers are linked together by N–N and N=N bonds. The bshz anions in 1 and 2 and aehba4? anions in 3 were all generated in situ from H6mbshz. A mechanism for these reactions is proposed, involving tandem C–N cleavage and C–N/N–N coupling processes via free radical intermediates. Magnetic investigations revealed dominant antiferromagnetic interactions between the metallic centers of each complex.  相似文献   

17.
Three coordination polymers, namely {[Ni(L1)(nip)(H2O)]·2H2O} n (1), [Co(L2)(tbip)] n (2), and {[Co2(L3)2(bptc)]·3H2O} n (3) (L1 = 1,4-bis(5,6-dimethylbenzimidazole)butane, L2 = 1,4-bis(5,6-dimethylbenzimidazole)-2-butylene, L3 = 1,3-bis(5,6-dimethylbenzimidazole)propane, H2nip = 5-nitro-isophthalic acid, H2tbip = 5-tert-butyl-isophthalic acid, H4bptc = biphenyl-3,3′,4,4′-tetracarboxylic acid), have been synthesized under hydrothermal conditions and characterized by physicochemical and spectroscopic methods as well as by single-crystal X-ray diffraction analysis. Complexes 1 and 2 both feature a two-dimensional (4,4) layer with (44 × 62) topology. Complex 3 possesses a uninodal 4-connected 2D htb network. The fluorescence spectra 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   

18.
Three Co(II) coordination polymers, namely, {Co(btbb)0.5(ndc)(H2O)}n (1), {[Co(btbb)(bpdc)]·1.5H2O}n (2), and {[Co(btbp)2(3-npa)]·2H2O}n (3) (btbb = 1,4-bis(thiabendazole)butane, btbp = 1,3-bis(thiabendazole)propane, H2ndc = 2,6-naphthalenedicarboxylic acid, H2bpdc = 4,4′-biphenyldicarboxylic acid and 3-H2npa = 3-nitro phthalic acid) were synthesized under hydrothermal conditions. Their X-ray crystal structures show that complexes 1 and 2 both have 2D uninodal 3-connected hcb (honeycomb) structures. Complex 1 is further extended into a threefold interpenetrating 3D 4,4-connected mog (moganite) supramolecular architecture with the point symbol of {4.64.8}2{42.62.82} by O–H···O hydrogen bonding interactions. Complex 2 shows a 3D supramolecular framework involving π···π stacking interactions. Complex 3 features a uninuclear structure, which is further assembled into an ordered 2D hydrogen-bonded-driven pattern with O–H···O and O–H···N hydrogen bonding interactions. The fluorescence spectra and photocatalytic properties of complexes 13 for degradation of methyl orange were investigated.  相似文献   

19.
Three metal–organic coordinate complexes based on 3-nitrophthalic acid (H2NPA), namely Cd2(H2O)(OH)2(NPA) (1), Cd2(Im)4(NPA)2 (2) and Cd2(Bim)4(H2O)(NPA)2 (3) (Im = imidazole, Bim = benzimidazole), have been obtained by hydrothermal method and characterized by X-ray single crystal structure determination. Structural analysis reveals that complex 1 exhibits 2D layers constructed by polyhedral aggregates. Complex 2 exhibits a dinuclear cadmium structural unit and assembles by hydrogen bonds into a 2D supramolecular architecture. Complex 3 is assembled by NPA2? into layers of a (3,4)-connected dinodal net topology of (4·52)(4·53·72). The fluorescent properties of complexes 13 have been investigated.  相似文献   

20.
Four new Organooxotin Clusters: [(p-MeC6H4)Sn(O)L1]6 (1) (HL1 = 2-(9H-carbazol-9-yl)acetic acid), [PhSn(O)L2]6·2C6H6·2H2O (2) (HL2 = 3-(9H-carbazol-9-yl)propanoic acid), [n-BuSn(O)L2]6 (3), [(c-Hex2Sn)2(L1)O(OH)]2·3C6H6 (4), were synthesized with benzene being used as solvent in the reaction and characterized by elemental analysis, IR, NMR spectroscopy and X-ray crystallography diffraction analyses. Complexes 13 are hexanuclear organotin complexes with drum structure. Complex 4 is dimeric carboxylate tetraorganodistannoxane and shows a ladder structure. There are four crystallographically unique Sn centers in the structure of 4, which consists of a Sn4O2(OH)2 ladder unit, and the ladder consists of four tins held together by four µ3-oxygens. All the complexes show an extensive supramolecular organization in the solid state and form 1D or 2D supramolecular assembly mediated by C–H…O, C–H…π or π…π interactions. Moreover, complexes 1 and 4 exhibit good fluorescence properties in the solid state revealed by the luminescent investigation. The experimental results show the complexes may be explored for potential luminescent materials.  相似文献   

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