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1.
A new disc-like heptanuclear cluster [Ni7(immep)6(MeO)6]·(NO3)2 (1, Himmep is 2-imminomethyl-6-ethxoy-phenol) was synthesized through microwave assisted reaction of Ni(NO3)2·6H2O with 2-hydroxy-3-ethoxy-benzaldehyde and ammonium water in mixed solvent (acetonitrile:methanol = 1:1). 1 was characterized by IR spectroscopy, elemental analysis and X-ray single-crystal diffraction. Magnetic property of 1 was discussed. The core of 1 displays dominant ferromagnetic interactions from the nature of the binding modes through μ 3-OCH3. According to the 3D Hirshfeld surface and 2D fingerprint plots, the main interactions in 1 are the H···H, O···H, and C···H contacts.  相似文献   

2.
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   

3.
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   

4.
Three cobalt(II) coordination polymers {[Co(L1)(nda)(H2O)2]·2H2O} n (1), [Co(L2)(tbi)(H2O)] n (2) and [Co(L2)(bpdc)(H2O)] n (3) (L1 = 1,3-bis(5,6-dimethylbenzimidazol-1-yl)-2-propanol, L2 = 1,3-bis(benzimidazol-1-yl)-2-propanol, H2nda = 2,6-naphthalenedicarboxylic acid, H2tbi = 5-tert-butyl isophthalic acid and H2bpdc = 4,4′-biphenyldicarboxylic acid) were synthesized and characterized by physicochemical and spectroscopic methods. Complex 1 exhibits a 1D loop-like structure, which is further extended into a 3D 3,3,4T31 network through two O–H···O hydrogen bonding interactions. Complex 2 displays a 1D ladder-like chain, arranged into a 2D supramolecular network with 3,3,4L34 topology via classical O–H···O hydrogen bonding interactions, whereas complex 3 features a 2D 3,4L13 layer structure and further assembles into a 3D framework with a twofold interpenetrating sqc65 topology through O–H···O hydrogen bonding interactions. The fluorescence and catalytic properties of these complexes for the degradation of Congo red in a Fenton-like process have been investigated.  相似文献   

5.
Different molecular assemblies were compared in two new structures [4-CH3-C6H4C(O)NH]P(O)[NH]2(CH2)3, 1, and [4-CH3-C6H4C(O)NH]P(O)[NHC6H3(3,4-CH3)2]2, 2, belonging to the families of “cyclic phosphoric triamide” and “phosphoric triamide”, respectively. The differences in the hydrogen bond motifs were discussed (by single crystal X-ray diffraction) as a result of three factors: (1) action of two N atoms with a non-planar environment in 1 as an H-bond acceptor, (2) different orientations of three N–H bond vectors in two molecules and (3) different conformations of C=O and P=O groups. These differences lead to more complicated hydrogen bond pattern of 1, with respect to that of 2, as structure 1 may be considered as a model of four-acceptor–three-donor versus a two-acceptor–three-donor system in 2. The main discrepancies of 1 and 2, monitored by the Hirshfeld surface analysis, are related to the contribution portions of O···H/H···O contacts, in which compound 1 not only involves the greater existence of classical hydrogen bonds but also contains the further C–H···O weak interactions in its crystal packing with respect to compound 2. Instead, in 2, the shortage of O···H/H···O contacts has been partially compensated by the C···H/H···C interactions, due to the presence of more unsaturated carbon acceptors. The differences in assemblies are also reflected in the solid-state IR spectra, especially for the N–H vibration frequencies. The new compounds were further studied by 1D NMR experiments (1H, 13C, 31P), 2D NMR techniques [HMQC and HMBC (H–C correlation), HSQC (N–H correlation)], high-resolution ESI–MS, EI–MS spectrometry and IR spectroscopy.  相似文献   

6.
We report the preparation of bromo-aryl functionalized bis(diphenylphosphino)amine ligands of the type Ph2PNArPPh2 (1, Ar = p-BrC6H4; 2, Ar = p-BrC6H4–C6H4) and their coordination properties. Mono- and dinuclear complexes were formed with Cu(I), Au(I), Pd(II), Pt(II) and tetranuclear cobalt carbonyl clusters were obtained. The crystal structures of [PdCl2(1)] (3), [PdCl2(2)] (4), [(AuCl)(μ-1)] (6), [Co4(CO)5(μ-CO)3(μ-dppa)(μ-1)] (dppa = Ph2PNHPPh2) (8) and [Co4(CO)5(μ-CO)3(μ-dppm)(μ-1)] (dppm = Ph2PCH2PPh2) (9) have been determined by X-ray diffraction. Whereas the diphosphine ligands chelate the metal center in 3 and 4, and in the Pt(II) complex 5 which is analogous to 3, ligand 1 acts as a bridge in 6 where the separation between the two Au(I) centers is 3.0402(5) Å. In the tetranuclear clusters 8 and 9, and in the cluster 10 analogous to 9 with 2 as bridging ligand, two orthogonal Co–Co edges are bridged by a diphosphine ligand and each cobalt center is thus coordinated by one P donor. Complex 3 was shown to react with the Pd(0) complex [Pd(dba)2] (dba = dibenzylideneacetone) to afford a tetranuclear complex resulting from both the insertion of Pd(0) into the ligand C–Br bond and Pd(II)/Pd(0) comproportionation to form a doubly ligand-bridged Pd(I)–Pd(I) core.  相似文献   

7.
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   

8.
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   

9.
Two new organotin(IV) carboxylate complexes, [PhSnO(L1)]6 ·4(toluene) (1) (HL1 = 2-(4-methylbenzoyl)benzoic acid) and [PhSnO(L2)]6 (2) (HL2 = 2-(4-ethylbenzoyl)benzoic acid), were synthesized by the reaction of ligand acids with mono-organotin complex in 1:1 molar ratio. The synthesized complexes have been structurally characterized by elemental analysis, IR, 1H, 13C, 119Sn NMR spectroscopy and X-ray crystallography diffraction analyses. Both 1 and 2 are hexanuclear organotin complex with drum-shaped structure. In the solid state of 1 and 2, 1D and 2D supramolecular networks are formed by hydrogen bonds, C–H···π or π···π interactions. Furthermore, the preliminary antitumor activities of 1 and 2 have been studied. The antitumor results show they exhibit good biological activities and may be explored for potential antitumor drugs.  相似文献   

10.
Two ternary cobalt(II) coordination polymers (CPs), namely [Co(L1)(npht)] n (1) and {[Co2(L2)2(npht)2(H2O)]·H2O} n (2) (L1 = 4,4′-bis(benzimidazol-1-ylmethyl)biphenyl, L2 = 1,2-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, and H2npht = 4-nitrophthalic acid) have been synthesized and structurally characterized by X-ray crystallography. Both CPs feature similar 1D infinite chains containing two distinct loops. CP 1 further forms a 3D supramolecular network via weak C–H···O hydrogen bond interactions. CP 2 shows a 1D two-layer chain structure, assembled through ππ stacking interactions. The electrochemical, luminescence, and photocatalytic activities of the two CPs for the removal of methylene blue under visible or UV light were investigated. Possible photocatalytic mechanisms are discussed.  相似文献   

11.
In situ lead-MOF derived from 2-Methyl-3-acetylnaphtho[2,3-b]furan-4,9-dione (MAFD), [Pb7O2(OH)2(1,2-BDC)4(H2O)] 1, 1,2-BDC = C6H4(COOH)2, phthalic acid, has been synthesized and characterized by elemental analysis, IR, TG-DTA, powder X-ray diffraction (XRD) and single crystal X-ray diffraction. Compound 1 possesses 2-D inorganic layer structure built from rare tetranuclear unit [(μ 4-O)Pb4]. In 1, both crystallographic distinct Pb(1) and Pb(4) ions adopt six-coordination geometry, and the other two crystallographic distinct Pb(2) and Pb(3) ions display eight-coordination geometry under the condition of Pb–O bond length extended to 3.10 Å. A 3-D supramolecular network is also formed by hydrogen bonds (C–H···O). Result of photoluminescence measurement indicates an emission band at 385 nm (λ excitation = 209 nm).  相似文献   

12.
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   

13.
One new trinuclear nickel(II) cluster with a Ni3(μ 3-OH) core was synthesized by the method of in situ one pot synthesis. The complex [Ni3(μ 3-OH)(cpza)3]Cl2·H2O (1) (where Hcpza is N-(4-cyano-1H-pyrazol-3-yl)acetamide) was characterized by single-crystal X-ray diffraction methods, elemental analyses, IR spectroscopy and Hirshfeld surface analysis. For complex 1, the crystal structure is extended into 3D structure through N–H···O and O–H···Cl hydrogen bonds. According to the 3D Hirshfeld surface and 2D fingerprint plots, the main interactions in the cluster are the H···H, N···H and O···H contacts.  相似文献   

14.
Hydrogen bonding in the Cu5(PO4)2(OH)4 polymorphs pseudomalachite, ludjibaite and reichenbachite has been studied by low-temperature single-crystal X-ray diffraction (XRD; pseudomalachite) and solid-state density functional theory (DFT; pseudomalachite, ludjibaite, reichenbachite) calculations. Pseudomalachite at 100 K is monoclinic, P21/c, a = 4.4436(4), b = 5.7320(5), c = 16.9300(15) Å, β = 91.008(8)°, V = 431.15(7) Å3 and Z = 2. The structure has been refined to R 1 = 0.025 for 1383 unique observed reflections with |F o| ≥ 4σF. DFT calculations were done with the CRYSTAL14 software package. For pseudomalachite, the difference between the calculated and experimental H sites does not exceed 0.152 Å. Structural configurations around hydroxyl groups in all three polymorphs show many similarities. Each OH5 group is involved in a three-center (bifurcated) hydrogen bond with the H···A distances in the range of 2.141–2.460 Å and the D–H···A angles in the range of 122.41°–139.30°, whereas each OH6 group forms a four-center (trifurcated) bond (H···A = 2.093–2.593 Å; D–H···A = 122.79°–137.71°). The crystal structures of the Cu5(PO4)2(OH)4 polymorphs are based on three-dimensional frameworks of Cu and P polyhedra. The copper-centered octahedra share edges to form two-dimensional layers parallel to (100) in all three structures. The layers have square voids above and beneath PO4 tetrahedra that link adjacent layers by sharing O atoms with two CuO6 octahedra each. From the topological point of view, none of the polymorphs can be obtained from another by a displacive transformation, and therefore pseudomalachite, ludjibaite and reichenbachite can be viewed as combinatorial polymorphs. According to information-based structural complexity considerations, the three phases are very similar in their configurational entropies and preferential crystallization of one phase over another cannot be entropy driven and is probably governed by other mechanisms that may involve such factors as structures of prenucleation clusters, chemical admixtures, etc.  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.
Four Ag(I) coordination polymers, formulated as [Ag(L1)(tpa)0.5] n (1), {[Ag(L2)(ndc)0.5]·0.5H2ndc} n (2), [Ag(L3)0.5(ndc)0.5] n (3) and {[Ag(L3)]·H3bptc} n (4) (L1 = 4,4′-bis(pyrazole-1-ylmethyl)-biphenyl, L2 = 4,4′-bis(3,5-dimethylpyrazol-1-ylmethyl)-biphenyl, L3 = 1,4-bis(3,5-dimethylpyrazol-1-ylmethyl)benzene, H2tpa = terephthalic acid, H2ndc = 2,6-naphthalenedicarboxylic acid, H4bptc = 3,3′,4,4′-biphenyltetracarboxylic acid), have been hydrothermally synthesized and structurally characterized. Complex 1 features the rare binodal (4,4)-connected 2D 4,4L10 topological network with a point symbol of {32·4.62·7}2{32·62·72}. Complex 2 has a folded ladder-like chain structure, which is further extended into a 3D supramolecular network via O–H···O hydrogen bonding and π···π stacking interactions. Complexes 3 and 4 both possess 1D zigzag chain structures. Complex 3 is further extended into a binodal (3,4)-connected network with the point symbol of {4.84·10}{62·82}2 by Ag···O weak interactions, while complex 4 is further connected through O–H···O hydrogen bonding and π···π interactions to afford a 2D supramolecular structure. The photoluminescence spectra and photocatalytic properties of these complexes for degradation of methylene blue and methyl orange are reported.  相似文献   

17.
One new trinuclear Fe(III) cluster with a Fe3(μ 3-O) core was synthesized by the method of hydrothermal synthesis. The complex [Fe3(μ 3-O)(pmta)6(H2O)3]FeCl4·2H2O (1) (where Hpmta is 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid) was characterized by single-crystal X-ray diffraction methods, elemental analyses, IR spectroscopy, fluorescence and Hirshfeld surface analysis. For complex 1, the crystal structure is extended into 3D structure through N–H···O and O–H···O hydrogen bonds. According to the 3D Hirshfeld surface and 2D fingerprint plots, the main interactions in the cluster are the H···H, N···H and C···H contacts.  相似文献   

18.
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   

19.
Three new compounds [Mn(H2O)2(bimb)2(H3SiW12O40)2](bimb)4 (1), [Zn2(bimb)4(H2O)4][SiW12O40] (2), and [Ni2(bimb)4(H2O)4][SiW12O40] (3) (bimb = 1,3-bis(1-imidazoly)benzene) have been synthesized under the same hydrothermal reaction except for tuning the metal cations (Mn2+, Zn2+, and Ni2+). Structural characterizations show that the three compounds possess distinct structural motives. Compound 1 displays a supramolecular one-dimensional (1 D) chain formed by π···π interactions that occur among the almost parallel bimb ligands from adjacent [Mn(H2O)2(bimb)2(SiW12O40)2] dimers. Compound 2 shows a supramolecular two-dimensional (2D) layer achieved by intermolecular (C–H···O) hydrogen bondings between the Zn2(bimb)4 molecular loops and the SiW12 anions. Compound 3 also exhibits a supramolecular 2D layer, but it is different from 2, which is generated by the π···π interactions among adjacent 1D polymeric chains. The distinct structural features of the three compounds suggest that the metal cations should play a significant role in the process of assembly. Additionally, the electrochemical properties of compounds 13 have been investigated, and the results indicate that compounds 13 possess excellent electrocatalytic activity toward reduction of both iodated and nitrite molecules.  相似文献   

20.
Two tetranuclear complexes, [M(H3L)]4·X (1, M = Cu, X = 4,4′-dpdo; 2, M = Ni, X = DMF, H5L = 2-[(3,5-dibromo-2-hydroxybenzyl) amino]-2-(hydroxymethyl)propane-1,3-diol, 4,4′-dpdo is 4,4′-bipyridine-N,N′-dioxide, DMF = N,N′-dimethyl formamide), have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Compound 1 features a centrosymmetric tetranuclear copper cluster which further constructed a 1D chain through a tetra-acceptor hydrogen bonds of 4,4′-dpdo molecule. Compound 2 having a P21 /n space group also exhibits a tetranuclear nickel cluster with a cubane topology in which the central Ni(II) ion and oxygen atoms from H3L2? occupy the alternate vertices of the cube. Magnetic properties of 1 and 2 in the 2–300 K have also been discussed. The tetranuclear cubanes cores display dominant ferromagnetic interactions.  相似文献   

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