Inorganic Phosphate and Arsenate within New Tetranuclear Copper and Zinc Complexes: Syntheses, Crystal Structures, Magnetic, Electrochemical, and Thermal Studies

Three, PO43–/HPO42– and AsO43–-incorporated, new tetranuclear complexes of copper(II) and zinc(II) ions have been synthesized and fully characterized. In methanol–water, reactions of H3cpdp (H3cpdp = N,N′-Bis[2-carboxybenzomethyl]-N,N′-Bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol) with copper(II) chloride in the presence of either NaOH/Na2HPO4·2H2O or KOH/Na2HAsO4·7H2O lead to the isolation of the tetranuclear complexes Na3[Cu4(cpdp)2(μ4-PO4)](OH)2·14H2O (1) and K2[Cu4(cpdp)2(μ4-AsO4)](OH)·162/3H2O (2), respectively. Similarly, the reaction of H3cpdp with zinc(II) chloride in the presence of NaOH/Na2HPO4·2H2O yields a tetranuclear complex, Na(H3O)2[Zn4(cpdp)2(μ4-HPO4)]Cl3·121/2H2O (3). All c…

Bis(μ-alkoxo) bridged dinuclear CuII2 and ZnII2 complexes of an isoindol functionality based new ligand: Synthesis, structure, spectral characterization, magnetic properties and catechol oxidase activity

Abstract Two new dinuclear copper(II) and zinc(II) complexes of an isoindol functionality based new dinucleating ligand, H3hdpa (H3hdpa = 2-({[2-hydoxyethyl]-[2-hydroxy-3-(1-oxo-1,3-dihydro-isoindol-2-yl)-propyl]-amino}-methyl)-benzoic acid) have been synthesized and characterized. In methanol, the reaction of stoichiometric amounts of Cu(OAc)2·H2O and the ligand H3hdpa in the presence of NaOH at ambient temperature afforded a new dinuclear copper(II) complex, [Cu2(Hhdpa)2]·2CH3OH·6H2O (1). Similarly, in methanol, the reaction of stoichiometric amounts of Zn(OAc)2·2H2O and H3hdpa in the presence of NaOH yielded a new dinuclear zinc(II) complex, Na4[Zn2(hdpa)2](OAc)2 (2). Characterization of…

New cyclic tetranuclear copper(II) complexes containing quadrilateral cores: Synthesis, structure, spectroscopy and their interactions with DNA in aqueous solution

Abstract Three new cyclic tetranuclear copper(II) complexes, Tetrakis{3-[(2-pyridylmethyl)-amino]-propionato}(tetrachloro)tetracopper(II)methanolhydrate (1·CH3OH·H2O), Tetrakis{3-[(2-pyridylmethyl)-amino]-propionato}(tetrathiocyanato)tetracopper(II) (2) and Tetrakis{3-[(2-pyridylmethyl)-amino]-propionato}(tetraazido)tetracopper(II) (3) have been synthesized by exploiting the chelating ability and bridging potential of a carboxyamine functionalized tridentate ligand, HL (HL = 3-[(2-Pyridylmethyl)-amino]-propionic acid). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand HL with stoichiometric amounts of CuCl2·2H2O, CuCl2·2H2O/NH4SCN, and CuCl2·2H2O/NaN3, respec…

Water‐Soluble Heteronuclear [NaCu II 6 ] Metallomacrocyclic Sandwich Complexes: Synthesis, Structure, Properties and In Vitro Biological Studies

The water-soluble heteronuclear metallomacrocyclic sandwich clusters [NaCu6(hpnbpda)3(OH)3(OH2)3](NO3)·4H2O (1), [NaCu6(hpnbpda)3(OH)3(OH2)3](ClO4) (2), and [NaCu6(hpnbpda)3(OH)3(OH2)3](PF6) (3) [H3hpnbpda = N,N′-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N′-diacetic acid] have been synthesized in methanol at room temperature and fully characterized using several analytical techniques including single-crystal X-ray diffraction. The molecular architecture of complex 1 is built from the template assembly of three dinuclear [Cu2(hpnbpda)]+ fragments through their weak oxophillic interactions with a central sodium(I) cation. A close analysis of the single-crystal X-ray structure reveal…

Synthesis, structure and properties of new heterometallic octanuclear Li2Na2Cu4 and decanuclear Li2Zn8 complexes

Abstract A carboxylate containing polydentate ligand in combination with exogeneous succinate (suc) has been used to stabilize heterometallic octanuclear [Li2Na2Cu4(cpdp)2(suc)2(CH3OH)2(H2O)4]Cl2·6H2O (1) and decanuclear Na(H3O)2[Li2Zn8(cpdp)4(suc)2(H2O)4]Cl2Br3·6MeOH·19H2O (2) complexes. The reaction of ligand H3cpdp (H3cpdp = N,N'-bis[2-carboxybenzomethyl]-N,N'-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol) with stoichiometric amounts of CuCl2/sodium succinate, and ZnCl2/sodium succinate, allowed isolation of complexes 1 and 2, respectively. Analyses of single crystal X-ray structures indicate that complex 1 is capped by two [Cu2(cpdp)]+ molecular building units and two succinate linkers, w…

Linking PO43− and HAsO42− anions with a dinuclear [ZnII2] complex: Formation and stabilization of novel decanuclear metallomacrocyclic [ZnII10] and tetranuclear [ZnII4] clusters

The linkage of PO43- and HAsO42--anions with a newly synthesized five-coordinate dinuclear zinc complex, Zn-2(cpdp)(H2O)(2)]Cl (1) H(3)cpdp =N,N'-bis2-carboxybenzomethyl]-N,N'-bis2-pyridylmethyl]-1,3diamino propan-2-ol], has been explored. In methanol-water, the reaction of 1 with Na2HPO4 center dot 2H(2)O and Na2HAsO4 center dot 7H(2)O/NaBr separately, at ambient temperature, yielded the novel phosphate-bridged decanuclear zinc cluster, (H3O)(4)Zn-10(cPdP)(4)(mu(5)-PO4)(2)(H2O)(6)](6 center dot Cl)center dot 53H(2)O (2) and hydrogen arsenate bridged tetranuclear zinc cluster, Na-2Zn-4(cpdp)(2)(mu(4)-HAsO4)]ClBr center dot 13H(2)O (3), respectively. Analysis of the single crystal X-ray stru…

Structure and properties of a novel staircase-like decanuclear [CuII10] cluster supported by carbonate and carboxylate bridges

This article describes a novel staircase-like decanuclear copper(II) cluster [CuII10(cpdp)4(CO3)4(CH3OH)2]·3.33CH3OH·7.83H2O (1) (H3cpdp = N,N′-bis[2-carboxybenzomethyl]-N,N′-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol) composed of a pair of [CuII5] pentamers. In methanol, the reaction of H3cpdp with Cu(NO3)2·3H2O in the presence of K2CO3 leads to the isolation of complex 1. This complex has been characterized by various analytical techniques including single crystal X-ray crystallography. Structural analysis reveals that the two [CuII5] pentameric units are bridged together exclusively by two μ2:η2:η1 carbonate groups. Complex 1 shows a rare μ3:η2:η1:η1 bridging coordination mode of four b…

Phosphatase-like Activity of Tetranuclear Iron(III) and Zinc(II) Complexes

Three new tetranuclear iron(III) and zinc(II) complexes, [Fe4(cpdp)2(phth)2(OH)2]·8H2O (1), [Fe4(cpdp)2(terephth)2(OH)2] (2), and [Zn4(Hcpdp)2(suc)]Br2·12H2O (3), have been synthesized as models for the active site of phosphoester hydrolases by utilizing a polydentate ligand, N, N'-bis[2-carboxybenzomethyl]- N, N'-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol (H3cpdp) in combination with exogeneous phthalate (phth), terephthalate (terephth), and succinate (suc). Single crystal X-ray analyses reveal that the metallic core of complex 1 consists of four distorted octahedral iron(III) ions with average intraligand Fe---Fe separation of 3.656(2) A, while the structure 3 represents a tetranuclear m…

Dinuclear and tetranuclear complexes of copper coordinated by an anthracene-based new μ-bis(tridentate) ligand: Synthesis, structure, spectroscopy and magnetic properties

Abstract Copper(II) complexes of an anthracene-based new μ-bis(tridentate) ligand, N,N′-bis[anthracene-2-ylmethyl]-N,N′-bis[carboxymethyl]-1,3-diaminopropan-2-ol (H3acdp) with mixed donating groups, have been studied in solid state as well as in solution. The reaction of stoichiometric amounts of CuSO4·5H2O and the ligand H3acdp in the presence of NaOH at ambient temperature in methanol-dichloromethane, afforded a new dinuclear copper complex, [Cu2(acdp)(MeO)(MeOH)2] (1). On the other hand, the reaction of stoichiometric amounts of Cu(OAc)2·H2O and the ligand H3acdp in the presence of NaOH at ambient temperature in methanol-dichloromethane yielded, a novel tetranuclear copper complex, [Cu4(…

Aromatic dicarboxylate incorporated new di- and tetranuclear cobalt(II) complexes: Synthetic and structural aspects, and evaluation of properties and catalytic activity

Abstract The synthetic and structural aspects as well as evaluation of magnetic properties and catalytic activity toward aerial oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylbenzoquinone of three new, two di- and one tetranuclear cobalt(II) complexes, [Co2(cpdp)(Hphth)]∙5H2O (1), [Co2(cpdp)(Hisophth)] (2) and [Co4(cpdp)2(terephth)]∙4.5CH3OH·5.5H2O (3), based on a symmetrical multidentate ligand, N,N'-Bis[2-carboxybenzomethyl]-N,N'-Bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol (H3cpdp) in combination with exogeneous aromatic dicarboxylic acids, such as phthalic acid (H2phth), isophthalic acid (H2isophth) and terephthalic acid (H2terephth) are reported. All three coordination compl…

Exploring new water soluble bridged dicopper(II) assemblies: Synthesis, structure, spectroscopic characterization, properties, and their interactions with d-glucosamine

Abstract Three new water soluble dimetallic copper(II) complexes, [Cu(H2O)5][Cu2(cpdp)(µ-O2As(CH3)2)]2Br2·13.83H2O·0.67CH3OH (1), [Cu2(Hcpdp)(µ-SO4)]·5H2O (2) and [Cu2(cpdp)(µ-pz)]·16H2O (3) (H3cpdp = N,N′-Bis[2-carboxybenzomethyl]-N,N′-Bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol; (CH3)2AsO2− = cacodylate; SO42− = sulfate; pz− = pyrazolate) have been successfully synthesized and characterized for the investigation of coordination/binding aspects with biologically significant monosaccharide, d -glucosamine. Preparation of 1, 2 and 3 has been achieved by carrying out reaction of H3cpdp with stoichiometric quantities of CuCl2·2H2O/NaO2As(CH3)2·3H2O, CuSO4·5H2O and CuCl2·2H2O/1H-pyrazole, respe…

Carboxylate Bridge Controlled Formation of Tetra‐ and Pentanuclear Nickel(II) Complexes: Synthesis, Crystal Structure, Spectroscopy and Magnetic Properties

New symmetrical dinucleating ligand based assembly of bridged dicopper(II) and dizinc(II) centers: Synthesis, structure, spectroscopy, magnetic properties and glycoside hydrolysis

Two dinuclear copper(II) complexes Li(H2O)(3)(CH3OH)](4)Cu2Br4]Cu-2(cpdp)(mu-O2CCH3)](4)(OH)(2) (1), Cu (H2O)(4)]Cu-2(cpdp)(mu-O2CC6H5)](2)Cl-2 center dot 5H(2)O (2), and a dinuclear zinc(II) complex Zn-2(cpdp)(mu-O2CCH3)] (3) have been synthesized using pyridine and benzoate functionality based new symmetrical dinucleating ligand, N, N'-Bis2-carboxybenzomethyl]-N, N'-Bis2-pyridylmethyl]-1,3-diaminopropan-2-ol (H(3)cpdp). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H3cpdp with stoichiometric amounts of Cu-2(O2CCH3)(4)(H2O)(2)], CuCl2 center dot 2H(2)O/C6H5COONa, and Zn(CH3COO)(2)center dot 2H(2)O, respectively, in methanol in the presence of NaOH at amb…

Synthesis, structure, spectral characterization and DNA binding affinity of new water soluble trinuclear copper(II) complexes with partial cubane Cu3O4 cores

Two new water soluble trinuclear copper(II) complexes, [Na 6 (H 3 O) 4 ][Cu 3 (cbal) 3 (μ 3 -OH)(H 2 O) 3 ] 4 (ClO 4 ) 6 ·3H 2 O ( 1 ) and [K(H 2 O) 2 ][Cu 3 (cbal) 3 (μ 3 -OH)(H 2 O)]·3.75H 2 O ( 2 ) have been synthesized in good yield via the reaction of an unsymmetrical amino dicarboxylic ligand, N-(2-carboxybenzomethyl)-β-alanine (H 2 cbal), Cu(ClO 4 ) 2 ·6H 2 O and NaOH/K 2 CO 3 in methanol at room temperature. Complexes 1 and 2 have been characterized by elemental analysis, room temperature magnetic susceptibility measurements, FTIR, UV–Vis, mass spectrometry and single crystal X-ray crystallography. Both complexes contain a partial cubane [Cu 3 O 4 ] core consisting of the trinuclear…

Synthesis, structure and properties of a novel self-assembled tetranuclear copper(II) complex derived from carboxylate-based multidentate ligand

Abstract A novel tetranuclear copper(II) complex, [Cu(H2O)5][Cu4(cpdp)2(adip)]ClBr∙2CH3OH·8H2O (1) of carboxylate-based symmetrical multidentate ligand, H3cpdp [H3cpdp = N,N'-Bis[2-carboxybenzomethyl]-N,N'-Bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol; adip = adipate], has been synthesized and fully characterized. Complex 1 has been synthesized by carrying out reaction of ligand H3cpdp with stoichiometric amounts of CuCl2·2H2O/Na2(CH2CH2COO)2 in methanol-water in the presence of NaOH at room temperature. The solid state structure of 1 consists of a [Cu4(µ4-adip)] core unit which is held together by two multidentate bridging ligands, cpdp3−. In fact, complex 1 can be viewed as a “dimer-of-dime…

Hydrolytically active tetranuclear [NiII2]2 complexes: synthesis, structure, spectroscopy and phosphoester hydrolysis

Three tetranuclear nickel(II) complexes, [Ni4(H2chdp)2(H2O)4]Br2·4CH3OH·3H2O (1), [Ni4(H2chdp)2(H2O)4](PF6)2 (2) and [Ni4(H2chdp)2(H2O)4](ClO4)2·3.2CH3OH·0.8H2O (3) have been synthesized by exploiting the flexibility, chelating ability and bridging potential of a new symmetrical μ-bis(tetradentate) ligand, H5chdp (H5chdp = N,N′-bis[2-carboxybenzomethyl]-N,N′-bis[2-hydroxyethyl]-1,3-diaminopropan-2-ol). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H5chdp with stoichiometric amounts of NiCl2·6H2O/NaBr, NiCl2·6H2O/NH4PF6, and Ni(ClO4)2·6H2O, respectively, in methanol–water in the presence of NaOH at ambient temperature. Characterizations of the complexes ha…

Mixed phenoxo and azido bridged dinuclear nickel(II) and copper(II) compounds with N,N,O-donor schiff bases: Synthesis, structure, DNA binding, DFT and molecular docking study

Abstract Two dinuclear complexes, µ-phenoxo, µ1,1-azido bridged [Ni2(L)2(µ1,1-N3)(N3)(CH3OH)] (1) and µ-phenoxo, µ1,1-azido bridged [Cu2(L)2(µ1,1-N3)(N3)] (2) bearing HL as a blocking co-ligand produced by the 1:1 condensation of N-methyl 1,3 propanediamine with o-vanillin have been synthesized and successfully characterized by elemental analyses, IR and electronic spectroscopy, single-crystal X-ray diffraction for 1 and DFT optimization for 2. X-ray crystal structure discloses that the asymmetric unit of 1 consists of two nickel(II) ions exhibiting a six-coordinate octahedral coordination with µ-phenoxo, µ1,1-azido bridging dimeric structure. The DFT optimization of 2 reveals the five-coor…

CCDC 1566878: Experimental Crystal Structure Determination

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CCDC 1908063: Experimental Crystal Structure Determination

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CCDC 1033416: Experimental Crystal Structure Determination

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CCDC 861462: Experimental Crystal Structure Determination

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CCDC 890493: Experimental Crystal Structure Determination

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CCDC 1016613: Experimental Crystal Structure Determination

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CCDC 1016615: Experimental Crystal Structure Determination

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