Five new cobalt(II) complexes based on indazole derivatives: synthesis,DNA binding and molecular docking study

Five cobalt(II) complexes based on 1H-indazole-3-carboxylic acid (H₂L), [Co(phen)(HL)₂]·2H₂O (1), [Co(5,5′-dimethyl-2,2′-bipy)(HL)₂] (2), [Co(2,2′-bipy)₂(HL)₂]·5H₂O (3), [Co₂(2,9-dimethyl-1,10-phen)₂(L)₂] (4) and [Co₂(6,6′-dimethyl-2,2′-bipy)₂(L)₂]·H₂O (5) (2,2'-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and structurally characterized by elemental analyses, IR and UV-vis spectroscopies and single-crystal X-ray crystallography. The results indicate that 1–3 possess mononuclear Co(II) structures, while 4 and 5 exhibit binuclear structure. 1D water tape which is linked by the multiple hydrogen bonds was embedded in the 3D motif of complex 3. Complexes 4 and 5 show two orthogonal planes of motif that was constituted by phen/2,2′-bipy and indazole acid, respectively. The intermolecular interactions including hydrogen bonding and π-π stacking interactions are stabilizing these complexes. The interactions of the synthesized complexes with calf-thymus DNA (CT-DNA) have been investigated by UV-vis absorption titration, ethidium bromide displacement assay and viscosity measurements. The results reveal that the complexes could interact with CT-DNA via a groove binding mode. Their behavior rationalization was further theoretically studied by molecular docking.     

A series of new oxo-vanadium(IV) complexes with octahedral coordinated vanadium centers

A series of new oxo-vanadium(IV) complexes, [VOCl0.69(OH)0.31 (2,2′-bipy)2]Cl·2H2O (1, 2,2′-bipy?=?2,2′-bipyridine) [(VO)₂Cl₄(4,4'-bipy)₃ (H₂O)₂] (2, 4,4'-bipy?=?4,4'-bipyridine), [VO(ida)(H₂O)]_n (3, H₂ida?=?iminodiacetic acid), and [(VO)₂(oa)₄]_n·4n(H₃O)·n(H₂O) (4, H₂oa?=?oxalic acid), have been synthesized and structurally characterized. 1 contains a [VOCl_0.69(OH)_0.31(2,2′-bipy)₂]⁺ cation, Cl ^– anion and two free H₂O molecules. 2 exhibits a binuclear centrosymmetric moiety built up from two [VOCl₂(4,4'-bipy)(H₂O)] units and one bridging 4,4'-bipy ligand, which provides a rare example of a 4,4'-bipy molecule acting as monodentate ligand. 3 displays a neutral chain [VO(ida)(H₂O)]_n constructed by the linkages of [VO(H₂O)]²⁺ units and ida^2? bridging ligands, while 4 offers the only example of three kinds of oa^2- ligands coexisting within the same anionic chain [(VO)₂(oa)₄^4-]_n. Their spectroscopic properties were investigated, and the magnetic susceptibility of 4 shows antiferromagnetic behavior.     

Synthesis,structure, and catalytic bromination of supramolecular oxovanadium complexes containing oxalate

Three supramolecular complexes, [VO(phen)(C₂O₄)(H₂O)]·CH₃OH (1) [(VO)₂(u₂-C₂O₄)(C₂O₄)₂(H₂O)₂]·L·H₂O (2), and [(4,4′-bipyH₂)_0.5]⁺[VO₂(2,6-dipic)]^?·2H₂O (3) (phen?=?1,10-phenanthroline 4,4′-bipy?=?4,4′-bipyridine, 2,6-dipic?=?2,6-pyridinedicarboxylic, L?=?1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene), have been prepared and characterized by elemental analysis, IR, and UV–vis spectroscopy and single-crystal diffraction analysis. Structural analysis shows that the three complexes all contain carboxylate and V=O moiety; vanadium of 1 and 2 are six coordinate with distorted octahedral geometry with N₂O₄ and O₆ donor sets, respectively, while 3 is five coordinate with distorted trigonal bipyramidal geometry with a NO₄ donor set. The complexes exhibit catalytic bromination activity in the single-pot reaction for the conversion of phenol red to bromophenol blue in H₂O–DMF at 30?±?0.5?C with pH 5.8, indicating that they can be considered as functional model vanadium-dependent haloperoxidases. In addition, electrochemical behaviors are also studied.     

Synthesis,structural characterization,and photocatalytic study of transition metal coordination polymers constructed from mixed ligands

Three 3-D coordination polymers, [Cu(cca)(4,4′-bipy)]_n (1), [Co₃(pda)₃(1,10′-phen)₂]_n (2), and [Co(pda)(1,10′-phen)]_n (3), have been synthesized from 4-carboxycinnamic acid (cca), 1,4′-phenylenediacrylic acid (pda), 4,4′-bipyridine (4,4′-bipy), 1,10′-phenanthroline (1,10′-phen), and Cu and Co salts under different conditions. The X-ray crystal structures of these three complexes are presented. Complex 1 exhibits a threefold 3-D α-Po interpenetration network. Complex 2 with a 3-D framework with six-connected single α-Po framework constructed from Co₃ unit has been synthesized and characterized. Complex 3 shows a 3-D framework with bcu topology composed of 1-D rod-shaped secondary building units. Furthermore, the photocatalytic properties of 2 were studied. When excited by UV light, 2 exhibits photocatalytic activity, in 300?min, about 71% Rhodamine B decomposes.     

Four anthraquinone-1,5-disulfonate-based metal complexes incorporating N-heterocyclic coligands: synthesis,crystal structures,and fluorescence

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.     

Synthesis and magnetic studies of phthalato-bridged oxovanadium(IV) binuclear complexes

Six new μ-phthalato binuclear oxovanadium(IV) complexes, namely [(VO)₂(PHTH)-(L)₂]SO₄ (L denotes 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me₂ bpy); 5-nitro-1,10-phenanthroline (NO₂-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 5-methyl-1,10-phenanthroline (CH₃-phen), where PHTH is the phthalate dianion), have been synthesized and characterized by elemental analyses, IR, electronic spectra, magnetic moments at room temperature and molar conductivity measurements. The temperature dependence of the magnetic susceptibility of complexes [(VO)₂(PHTH)(phen)₂]SO₄ (1) and [(VO)₂(PHTH)(CH₃-phen)₂]SO₄ (2) was measured in 4—300 K range and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, ?=?2J?₁·?₂, giving the exchange integrals J=?12.8 cm^?1 for 1 and J=?7.9 cm^?l for 2. This indicates an antiferromagnetic spin-exchange interaction between the metal ions within each molecule.     

Complexes based on ferrocenecarboxylate ligands: steric hindrance induced by ferrocenyl groups

Three metal complexes with ferrocenecarboxylate ligands, [M₂(η ²-FcCOO)₂(μ₂-η ²-FcCONHCH₂COO)₂(phen)₂]?·?nH₂O [M?=?Pb, n?=?6 (1) and M?=?Cd, n?=?2 (2)] and [Cd(FcCONHCH₂COO)(μ₂-FcCONHCH₂COO)(2,2′-bipy)(H₂O)] _n (3) (FcCOOH?=?ferrocenemonocarboxylic acid, FcCONHCH₂COOH?=?N-ferrocenylformylglycine, phen?=?1,10-phenanthroline, 2,2′-biby?=?2,2′-bipyridine), were synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction analysis. Structural studies revealed that 1 and 2 have similar binuclear structures, but 3 exhibits a 1-D chain structure. The difference in the structures of ferrocenylcarboxylate-containing cadmium(II) complexes is due to steric hindrance of ferrocenyl groups.     

Syntheses,structures, and fluorescent properties of two uranium coordination polymers with carboxylic acids

Two U(VI)-containing coordination polymers, (UO₂)₂O₂(Suc)(2,2′-bipy)₂ (1) and UO₂(BC)₂(DMF) (2) (2,2′-bipy?=?2,2′-bipyridine, H₂Suc?=?succinic acid, HBC?=?benzoic acid, DMF?=?N,N-dimethylformamide), have been synthesized and characterized via elemental analysis, infrared spectroscopy, UV-Vis spectroscopy, and single-crystal X-ray diffraction. Structural analyses show that 1 is a 1-D chain coordination polymer in which U(VI) ions are connected by succinic acid ligand and the 1-D chain is connected into a 3-D supramolecular network by C?H···O hydrogen bonds between carbon of 2,2′-bipyridine and uranyl oxygen. For 2, monomeric entities are further assembled into a 1-D supramolecular network by C–H···O hydrogen bonds between carbon of DMF molecule and coordinated carboxylate oxygen. Thermogravimetric analyses and photoluminescent properties of 1 and 2 are discussed.     

Two zinc(II) complexes based on indole-3-acetic acid: crystal structures,fluorescence sensors,and ion exchange with mercury(II)

Two new coordination complexes, [Zn(IA)₂(phen)] (1) and [Zn(IA)₂(4,4′-bipy)] _n ?·?C₂H₅OH (2) (IAH?=?indole-3-acetic acid, phen?=?1,10-phenanthroline, 4,4′-bipy?=?4,4′-bipyridine), have been prepared and characterized by single-crystal X-ray diffraction. Complex 1 is mononuclear and 2 presents a 1-D zigzag chain, in which 4,4′-bipy connects the Zn(II) ions. Both complexes show fluorescence emissions and exhibit fluorescence quenching when Hg²⁺ ions are present. ICP, EDS, and SEM experiments reveal that zinc in both complexes can be exchanged by toxic mercury ions.     

Supramolecular interactions in high molecular weight bisdithiocarbamate adducts of divalent Zn(II), Cd(II), and Hg(II): spectral,VBS, and single crystal X-ray structural studies on MS4N2 chromophores

This article describes supramolecular interactions induced in a high molecular weight dithiocarbamate, padtc, by its design. Synthesis, spectral studies involving zinc, cadmium and mercury, padtc, and adducts with tmed, such as [Zn(padtc)₂] (1), [Zn(padtc)₂(tmed)]?·?C₆H₅CH_3?·?0.5(H₂O) (2), [Cd(padtc)₂] (3), [Cd(padtc)₂(tmed)]?·?C₆H₅CH₃?·?0.36(H₂O) (4), [Hg(padtc)₂]?·?H₂O (5), [Hg(padtc)₂(2,2′-bipy)]?·?H₂O (6), [Hg(padtc)₂(1,10-phen)]?·?H₂O (7), and [Hg(padtc)₂(oxine)]?·?H₂O (8) (where padtc^??=?N,N′-(iminodiethylene)bisphthalimidedithiocarbamate, 1,10-phen?=?1,10-phenanthroline, tmed?=?tetramethylethylenediamine, 2,2′-bipy?=?2,2′-bipyridine, oxine?=?8-hydroxyquinoline) along with the single crystal X-ray structural analysis of [Zn(padtc)₂(tmed)]?·?C₆H₅CH₃?·?0.5(H₂O) (2) and [Cd(padtc)₂(tmed)]?·?C₆H₅CH₃?·?0.36(H₂O) (4) are reported. All the complexes were characterized by IR, NMR (¹H and ¹³C), and thermogravimetric study. The IR spectra of the complexes show the contribution of the thioureide form to the structures. In ¹³C NMR spectra, the most important thioureide (N¹³CS₂) carbon signals are observed at 210–212?ppm. Single crystal X-ray structural analyses of 2 and 4 show the presence of extensive supramolecular interactions stabilizing the solid-state structure. Both zinc and cadmium are in a distorted octahedral environment with MS₄N₂ chromophores. VBS of Zn and Cd are 1.76 and 1.98, respectively, supporting the correctness of the determined structure and the valence of the central metal ions.     

Synthesis,characterization and property study of new coordination polymers constructed from flexible dicarboxylates and bidentate nitrogen mixed ligands

Five new coordination polymers, [Cd(1,2′-cy)_0.5(bix)H₂O]_n (1), [Cd₂(1,2′-cy)₂(1,10′-phen)₂(H₂O)₂] (2), {[Co(1,2-cy)(2,2′-bipy)(H₂O)₂]·2H₂O}_n (3) {[Cd(succ)(1,10′-phen)H₂O]·H₂O}_n (4), and {[Cd(succ)(2,2′-bipy)H₂O]·2H₂O}_n (5) (1,2-cy = 4-cyclohexene-1,2-dicarboxylate, succ = succinic acid, bix = 1,4-bis(imidazol-1-ylmethyl)benzene, 1,10′-phen = 1,10-phenanthroline, 2,2′-bipy = 2,2′-bipyridine), have been synthesized and characterized by single-crystallographic X-ray diffraction. Complex 1 shows a two-dimensional covalent layer structure. Complex 2 exhibits a two-dimensional supramolecular layer network composed from discrete fundamental units. Complex 3 exhibits a one-dimensional covalent chain-like structure, which further extends to a two-dimensional supramolecular structure with hydrogen bonding and π-π interactions respectively. Complexes 4 and 5 show three-dimensional supramolecular networks composed from one-dimensional chain-like covalent structures. Furthermore, the magnetic property of complex 3 and fluorescent properties of complexes 1, 2, 4 and 5 have also been studied.     

A DFT study of transition metal complexes with 1,10-phenanthroline,C-C-dimeric 2,2′-bi-1,10-phenanthroline,and its tetraaza chromophore anion

Quantum-chemical calculations of the 1,10-phenanthroline complexes [M(en)(1,10-phen)]²⁺ (M = Pt, Pd, Ni; en = NH₂C₂H₄NH₂) were performed by the DFT B3LYP method in the 6-31G** basis set using the GAMESS-2006 program package. The calculations were also performed for the nickel complexes with 2,2′-bi-1,10-phenanthroline, [Ni(2,2′-bi-1,10-phen)]²⁺, and with its electron-excessive analog, [Ni(2,2′-bi-1,10-phen)]⁰, and also for the octahedral complex cation [Ni(2,2′-bi-1,10-phen)Cl(H₂O)]⁺ characterized by single crystal X-ray diffraction. For the Ni(II) complexes, the stabilities of their high-and low-spin isomers were evaluated, and the structural features were revealed. The barriers to mutual transformations of the low-and high-spin Ni(II) complexes are low.     

两种3D微孔Zn-MOF对水溶液中Fe3+、Cr2O72-和丙酮分子的荧光传感(英文)

通过溶剂热法合成了2种三维微孔锌金属有机框架材料,其分子式为[Zn₃(DBA)(OH)(1,10-phen)₂]_n (1)和{[Zn₂(HDBA)(4,4′-bipy)_1.5]·H₂O}_n (2)(H₅DBA=3,5-二(2′,4′-对羧基苯基)苯甲酸;1,10-phen=1,10-菲咯啉;4,4′-bipy=4,4′-联吡啶)。结构分析表明,配合物1为三核锌基金属单元的三维微孔骨架,配合物2为双核锌基的微孔结构。与2相比,配合物1在水中具有较强的发光性能,可作为检测Fe³⁺、Cr₂O₇^2-和丙酮分子的发光传感器,具有较高的选择性和灵敏度。     

Two cadmium(II) addition compounds with 3-hydroxy-2,7-naphthalenedisulfonate containing aromatic diamines and their 3-D net

{[CdCl(2,2′-bipy)₂(H₂O)]⁺·[Cd(3-O^?-2,7-NDS)(2,2′-bipy)₂]^?·3H₂O} (1) and {[Cd(phen)₃]²⁺·2[Cd(3-O^?-2,7-NDS)(phen)₂]^?·8.5H₂O} (2) (3-OH-2,7-NDS?=?3-hydroxy-2,7-naphthalenedisulfonate, phen?=?1,10-phenanthroline, and 2,2′-bipy?=?2,2′-bipydine) were prepared and characterized by X-ray single-crystal diffraction. Compound 1 contains a discrete coordination cation [CdCl(2,2′-bipy)₂(H₂O)]⁺ and a coordination anion [Cd(3-O^?-2,7-NDS)(2,2′-bipy)₂]^?; 2 contains a discrete coordination cation [Cd(phen)₃]²⁺ and two coordination anions [Cd(3-O^?-2,7-NDS)(phen)₂]^?. There are numerous weak interactions among the coordination cation, coordination anion, and free water molecules, such as O–H?···?O hydrogen bonds, π?···?π stacking, and Cl^??···?π interactions in 1 and π?···?π stacking and C–H?···?π interactions in 2. The cations and anions as building blocks are connected to construct different 3-D supramolecular architectures via weak intermolecular interactions. Particularly, the capsule structure of 1 was observed.     

Synthesis,structures, and catalytic oxidation of three aqua-coordinated and oxo-bridged diruthenium(III) complexes with sulfobenzoate and 2,2′-bipyridine

Three new diruthenium(III) complexes, [Ru₂O(2-sb)₂(2,2′-bipy)₂(H₂O)₂]·2.5H₂O (1), [Ru₂O(3-sb)₂(2,2′-bipy)₂(H₂O)₂]·9H₂O (2), and [Ru₂O (4-sb)₂(2,2′-bipy)₂(H₂O)₂]·9H₂O (3), where sb^2? is sulfobenzoate dianion and 2,2′-bipy is 2,2′-bipyridine, were synthesized using hydrothermal methods and characterized by IR, elemental analysis, thermogravimetric analysis, UV–vis, and fluorescence spectra. The single crystal X-ray analysis showed that each of these complexes has a dinuclear core stabilized by two bridging carboxylates and one bridging O^2?. Variable sb^2? ligands (2-sb, 3-sb, and 4-sb) in these complexes lead to diverse electronic spectroscopic behavior. The efficiency of activating methyl phenyl sulfide oxidation utilizing H₂O₂ in 3 equiv. was studied at 23?±?2?°C. The effect of the amount of catalyst and solvents on activities was investigated. Under optimized reaction conditions, the major product was sulfoxide. Complex 1 gave significant conversion of 100 and 98% selectivity for sulfoxide after 4?h.     

Hydrothermal synthesis and structural characterization of two unprecedented photoluminescent coordination polymers constructed from Cd salt and mixed ligand

Two new Cd-containing coordination polymers {Cd₂(succ)₂(1,10′-phen)₂} _n (1) and {Cd(glut)(1,10′-phen)(H₂O)} _n (2) are described. Complex 1 exhibits an interesting 2-D structure in which the binuclear Cd centers are linked by succinate anions. Complex 2 possesses an interesting 1-D chain-like structure. The IR and TG properties of the two compounds are studied. Furthermore, these two complexes exhibit photoluminescence.     

Synthesis and crystal structure of two praseodymium 2-iodobenzoic acid complexes

Two new complexes, {[Pr(2-IBA)₃?·?2,2′-bipy]₂·[Pr(2-IBA)₃?·?2,2′-bipy]₂?·?0.5C₂H₅OH?·?H₂O} (1) and [Pr(2-IBA)₃?·?phen]₂ (2) (2-IBA?=?2-iodobenzoate; 2,2′-bipy?=?2,2′-bipyridine; phen?=?1,10-phenanthroline) were synthesized, and their crystal structures were determined by X-ray diffraction. Complex 1 consists of two binuclear molecules [Pr(2-IBA)₃?·?2,2′-bipy]₂ (a) and [Pr(2-IBA)₃?·?2,2′-bipy]₂ (b), half uncoordinated ethanol and one uncoordinated water. In the two molecules (a) and (b), the coordination environment of central ions is similar. The Pr1³⁺ ion in molecule (a) and Pr2³⁺ ion in molecule (b) are nine-coordinate with seven oxygen atoms from five 2-IBA ligands and two nitrogen atoms from one 2,2′-bipy molecule. The crystal structure of complex 2 is similar to that of binuclear [Pr(2-IBA)₃?·?2,2′-bipy]₂ in complex 1.     

Synthesis,characterization, and crystal structures of two Ag (I) coordination polymers based on biphenyl-2,2′,4,4′-tetracarboxylate

In this article, [Ag₈(btc)₂(2,2′-bpy)₂] _n (1) and [Ag₄(btc)(phen)₂] _n (2) (H₄btc?=?biphenyl-2,2′,4,4′-tetracarboxylic acid, 2,2′-bpy?=?2,2′-bipyridine, phen?=?1,10-phenanthroline) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, thermogravimetric analyses, and single-crystal X-ray diffraction. Complex 1 shows a 3-D framework containing a 2-D bilayer network constructed from (btc)^4? with Ag (I), whereas 2 features a 2-D supramolecular bilayer network. The differences of the two complexes demonstrate that nitrogen-containing chelating ligands have a significant effect on the formation and structure of the resulting complexes. Electrochemistry properties of 1 were also studied.     

The construction of two lanthanide coordination polymers based on 5-hydroxyisophthalate and bipyridine

Two lanthanide coordination polymers, [Tm₂·(5-IPA)₄·(2,2′-Hbipy)₂]·3H₂O (1, 5-H₂IPA?=?5-hydroxyisophthalic acid, 2,2′-bipy?=?2,2′-bipyridine) and [Er·(5-HIPA)₃·(4,4′-bipy)₃·(H₂O)₂]·3H₂O (2, 4,4′-bipy?=?4,4′-bipyridine), have formed by hydrothermal synthesis. Complex 1 exhibits a 2-D coordination network containing parallelepiped-shaped voids occupied by guest 2′2-bipy molecules. Complex 2 possesses a 1-D linear chain structure. The 1-D chains are linked by 4,4′-bipy molecules to form a 3-D supramolecular framework. IR spectroscopy, elemental analysis, and thermogravimetric analysis were also investigated.