Two transition metal supramolecular compounds based on 2-(4-isopropylbenzoyl)benzoic acid: syntheses,crystal structures,and luminescent properties

Two new supramolecular compounds, [Zn₂(L)₃(4,4′-bpy)(OH)]_n (1) and [Cd(L)₂(2,2′-bpy)(H₂O)]·2H₂O (2) (HL?=?2-(4-isopropylbenzoyl)benzoic acid, 4,4′-bpy?=?4,4′-bipyridine, 2,2′-bpy?=?2,2′-bipyridine), have been hydrothermally synthesized and characterized by elemental analysis, infra-red spectroscopy, thermal gravimetric analyzes, and single-crystal X-ray diffraction. 1 exhibits 1-D chain and 2 is 0-D mononuclear. They are both linked into 2-D supramolecular layers by non-covalent interactions. Luminescence properties were also investigated.     

Structural and luminescent properties of a tetranuclear cage-type cadmium(II) carboxylate cluster containing a V-shaped water trimer

The structural characterization of tetranuclear cage-type cadmium(II) carboxylate [Cd₄(2-cpida)₂(2,2′-bpy)₆]·(2,2-bpy)·(ClO₄)·3H₂O (1) (2-H₃cpida = N-(2-carboxyphenyl)iminodiacetic acid, 2,2′-bpy = 2,2′-bipyridine) is described. H-bonding interactions between three lattice water molecules form a V-shaped trimer (H₂O)₃, which is stabilized by 1. In addition, luminescence investigations revealed that 1 shows enhanced emissions as compared with free 2-H₃cpida in the liquid state.     

Self-assembly of reduced molybdophosphate-based supramolecular architectures and the study of their magnetic properties

Reduced molybdophosphate-based supramolecular compounds, such as (4,4′-H₂bipy)[Co(H₂O)₂]₂[Co(H₂PO₄)₂(HPO₄)₄(PO₄)₂(MoO₂)₁₂(OH)₆] · 17H₂O (1), [Co(2,2′-bipy)₂(H₂O)]₄[Co(H₂O)₂][Co(HPO₄)₆(PO₄)₂(MoO₂)₁₂(OH)₆] · 2H₂O (2), and [Co(2,2′-bipy)₂(H₂O)]₄[Co(H₂PO₄)(H₂O)₂]₂[Co(HPO₄)₆(PO₄)₂(MoO₂)₁₂(OH)₆] · 8H₂O (3) (4,4′-bipy=4,4′-bipyridine, 2,2′-bipy=2,2′-bipyridine), have been synthesized under hydrothermal conditions and characterized. Compound 1 exhibits a three-dimensional supramolecular twofold interpenetrating architecture built up of one-dimensional [P₄Mo₆]-based infinite covalent chains and free 4,4′-bipy molecules. Compound 2 also shows a three-dimensional supramolecular network constructed from one-dimensional covalent [P₄Mo₆]-based chains. Unlike compounds 1 and 2, compound 3 exhibits an interesting three-dimensional ‘honeycomb-like’ supramolecular network constructed by the stacking of [Co(2,2′-bipy)₂(H₂O)] units with one-dimensional channels, in which the [P₄Mo₆]-based polyoxometalate chains are located. The magnetic properties of compounds 2 and 3 are reported. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Effect of auxiliary ligand on the crystalline architectures of copper(II)-sparfloxacin complexes via coordinative and supramolecular interactions

Reactions of sparfloxacin (Hsf) with Cu(II), in the absence or presence of auxiliary ligands (bpy, 2,2′-bipyridine; dmbpy, 4,4′-dimethyl-2,2′-bipyridine) under similar conditions, afforded three coordination complexes, [Cu(Hsf)₂(ClO₄)](ClO₄)(CH₃OH)₂(H₂O)_3.75 (1), [Cu(Hsf)(bpy)(ClO₄)](ClO₄)(H₂O) (2), and [Cu₂(Hsf)₂(dmbpy)₂(ClO₄)₃](ClO₄)(C₂H₅OH)₃(H₂O)_0.75 (3). All three complexes have been structurally characterized by single-crystal X-ray diffraction. In their crystal structures, distinct extended metallosupramolecular architectures, specifically 3D (for 1), 2D (for 2), and 2D + 1D (for 3), are constructed with the aid of secondary interactions involving H-bonding and aromatic stacking.     

Syntheses,crystal structures,and magnetic properties of two new manganese(II) complexes based on biphenyl-2,5,2′,5′-tetracarboxylic acid

Two new complexes, [Mn(H₂bptc)(2,2′-bpy)₂]?·?2H₂O (1) and [Mn₃(Hbptc)₂(2,2′-bpy)₃(H₂O)₈]?·?2H₂O (2) (H₄bptc?=?biphenyl-2,5,2′,5′-tetracarboxylic acid, 2,2′-bpy?=?2,2′-bipyridine), have been synthesized under hydrothermal conditions. Their structures have been characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, powder X-ray diffraction, and thermogravimetric analyses. Complexes 1 and 2 are both linked into 3-D supramolecular networks by non-covalent interactions (O–H?···?O, C–H?···?O, C–H?···?π, and π?···?π). Complexes 1 and 2 exhibit weak antiferromagnetic interactions.     

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.     

Dinuclear vanadium complexes with rigid phenylpolycarboxylate ligands: synthesis,structure, and catalytic bromination reaction with potential detection of hydrogen peroxide

Vanadium complexes (VO)₂(2,2′-bipy)₂(bta)(H₂O)₂ (1) and (VO)₂(1,10-phen)₂(bta)(H₂O)₂ (2) (H₄bta?=?1,2,4,5-benzenetetracarboxylic acid, 2,2′-bipy?=?2,2-bipyridine and 1,10-phen?=?1,10-phenanthroline) have been synthesized by the reaction of V₂(SO₄)₃, H₄bta, 2,2′-bipy (for 1) and 1,10-phen (for 2) by hydrothermal methods. The complexes were characterized by elemental analysis, IR, UV–vis, thermogravimetric analyses, and single-crystal X-ray diffraction. Structural analyses indicate that 1 and 2 are both VO-bta-N-heterocycle system complexes. The central vanadium is coordinated by N₂O₄ donors to form a distorted octahedral geometry. The complexes exhibit catalytic bromination activity in a single-pot reaction with conversion of phenol red to bromophenol blue in a mixed solution of H₂O-DMF at 30?±?0.5?°C with pH 5.8, indicating that they can be considered as a functional model of vanadium-dependent haloperoxidases. The practical application of H₂O₂ detection has also been studied.     

Mononuclear manganese and tetranuclear copper compounds and their supramolecular networks constructed from hexafluoroglutaric acid and 2,2′-bipyridine

Mn(2,2′-bpy)₂(HFGA) (1) and [Cu₄(μ₃-OH)₂(μ₂-OH)₂(H₂O)₂(2,2′-bpy)₄]?·?2HFGA?·?4H₂O (2) (H₂HFGA?=?hexafluoroglutaric acid and 2,2′-bpy?=?2,2′-bipyridine) have been synthesized and characterized by X-ray structural analyses. 1 is a monomer with six-coordinate Mn²⁺ from two oxygens of HFGA and four nitrogens of two 2,2′-bpy. Complex 2 is tetranuclear with four Cu²⁺ ions bridged by triple-bridging μ₃-OH and double-bridging μ₂-OH. There are two crystallographically independent Cu²⁺ ions in different five-coordinate environments. Cu1 is coordinated by 2,2′-bpy and three OH ligands. Cu2 is coordinated by 2,2′-bpy, two μ₃-OH ligands, and one water molecule. The mononuclear and tetranuclear molecules as building blocks are connected to construct different 3-D supramolecular architectures via noncovalent interactions. Particularly, the lone pair (lp)–π (F···π) interaction in 1 is observed. A hybrid water-anionic tape by linkage of {[(H₂O)₄(HFGA)]₂ ^4?} _n fragments consisting of water dimers and HFGA anions in 2 is observed.     

Syntheses,structures, thermal stabilities and bacteriostatic activities of four lanthanide complexes

Four lanthanide complexes, [La₂(2,4-DClBA)₆(5,5′-DM-2,2′-bipy)₂(H₂O)₂]·2C₂H₅OH (1) and [Ln(2,4-DClBA)₃(5,5′-DM-2,2′-bipy)(C₂H₅OH)]₂ (Ln = Pr(2), Sm(3), Gd(4); 2,4-DClBA = 2,4-dichlorobenzoate; 5,5′-DM-2,2′-bipy = 5,5′-dimethyl-2,2′-bipyridine), were synthesized and characterized via elemental analysis, infrared spectra and thermogravimetric analysis (TG). The crystal structures of 1 and 2–4 are different; Each La³⁺ is nine-coordinate adopting a distorted mono-capped square antiprism, while the Ln³⁺ ions of 2–4 are all eight-coordinate with a distorted square antiprismatic molecular geometry. There are subtle changes in the local coordination geometry of the lanthanide–5,5′-DM-2,2′-bipy complexes. Binuclear 1 complexes are stitched together via two kinds of hydrogen bonding interactions (OH?O and CH?O) to form 1-D chains along the y axis, while the units of 2–4 are stitched together via CH?O to form 1-D chains along the x axis. TG analysis revealed thermal decomposition processes and thermal stabilities of the complexes. The bacteriostatic activities of the complexes were evaluated against Candida albicans, Escherichia coli, and Staphylococcus aureus.     

Synthesis,structure, and character of two rare earth carboxylic acid complexes

Two rare earth carboxylic acid complexes, [Sm(MeBA)₃(2,2′-bipy)]₂·2(2,2′-bipy) (MeBA = 3-methylbenzoic acid; 2,2′-bipy = 2,2′-bipyridine) (1) and [Pr(MeBA)₃(H₂O)₂]_n?n(4,4′-bipy) (4,4′-bipy = 4,4′-bipyridine) (2), have been synthesized under hydrothermal conditions and structurally determined by single-crystal X-ray diffraction. Compound 1 is a dimer and further assembles into an infinite chain, two-dimensional net and three-dimensional supramolecular structure via weak π–π and C–H···π interactions. Some 2,2′-bipy coordinates with Sm and some exist by non-covalent C–H···π interactions. Compound 2 is a 1D infinite chain structure, with adjacent 1D chains connected into a 2D layer structure by O–H···N hydrogen bonds. The two complexes were characterized by elemental analyses, IR, photoluminescence, and TGA. In order to illustrate subtle structural characteristics of intermolecular interactions and magnetic sensitivity of the complex, 2D-IR correlation spectra (2D-IR COS) under magnetic perturbation for 1 were performed.     

1D and 3D supramolecular structures exhibiting weak ferromagnetism in three Cu(II) complexes based on malonato and di-alkyl-2,2’-bipyridines

Three new Cu(II) complexes composed of malonato (mal), methylmalonato (memal), 4,4′-di-tert-butyl-2,2′-bipyridine (tbpy) and 5,5′-dimethyl-2,2′-bipyridine (mebpy) ligands, Cu(H₂O)(mal)(tbpy) (1), Cu(H₂O)(memal)(tbpy) (2) and Cu₄(H₂O)₄(memal)₄(mebpy)₄·11H₂O (3) were synthesized by simple one-pot solution reactions at ambient conditions. Single-crystal X-ray diffraction analyses reveal that the Cu(II) ions exhibit a distorted five-coordinate square pyramidal geometry. These three complexes display supramolecular arrays due to hydrogen-bonding interactions. Complexes 1 and 2 show 1-D supramolecular structures; 1 forms a double-ion chain, unlike 2, which only generates a single-ion chain. In 3, there are two identical monomers in the asymmetric unit with Z″ = 2; its high number of noncoordinated water molecules, along with hydrogen-bonding interactions between aqua ligand and memal ligand, generate a supramolecular tetramer, which mimics to produce a 3-D supramolecular framework. Besides this fascinating and yet uncommon crystallographic phenomenon in 3, the structural differences found in these complexes arise from the substituted groups in the malonato dianion and in the bipyridine ligands. These compounds exhibit weak ferromagnetic-exchange interactions.     

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.     

Hydrothermal synthesis and structural characterization of two new reduced phosphomolybdates based on an organoamine template and copper ion

Two new compounds, (H₂en)₃(H₂enMe)₄(H₃O){Cu^I[Mo^V ₆O₁₂(OH)₃(HPO₄)(PO₄)₃]₂}?·?6H₂O (1) and (H₂enMe)₄{Cu^ICu^II[Mo^V ₆O₁₂(OH)₃(PO₄)(HPO₄)₂(H₂PO₄)]₂}?·?3H₂O (2), were hydrothermally synthesized and characterized by elemental analysis, IR, TGA, and single-crystal X-ray diffraction analysis. Crystallographic analysis reveals that 1 is constructed from cluster anions {Cu^I[Mo^V ₆O₁₂(OH)₃(HPO₄)(PO₄)₃]₂}^15?, protonated organic amines, and water molecules. Each cluster is bridged through hydrogen bonds to form a 3-D supermolecular structure. For 2, {Cu^I[Mo^V ₆O₁₂(OH)₃(PO₄)(HPO₄)₂(H₂PO₄)]₂}^11? are connected by Cu^II cations to form an infinite chain. The formation of 1 and 2 reveals that organoamines influence the structures of the crystals.     

Synthesis,crystal structure,and photoluminescence of a new Zn(II) molecular box compound derived from a two-armed bis-terdendate ligand

The dinuclear compound Zn₂(HL²)₂(ClO₄)₂(C₂H₅OH)_0.5(H₂O)₂ (1) based on di(2-acetylpyridyl)-6,6′-dicarboxylic acid hydrazone-2,2′-bipyridine (H₂L²) has been obtained via self-assembly. X-ray crystallography indicated the formation of a molecular box rather than a helicate. The photoluminescence properties of 1 in the solid state have an emission at ca 500 nm with excitation at 400 nm at room temperature.     

Ancillary ligand-controlled assembly of three coordination polymers: synthesis,characterization, luminescent,and catalytic properties

Abstract

By changing the ancillary ligands, three new zinc-based coordination polymers (CPs), {[Zn(4,4′-bpy)(H₂O)₄]·(TDC)·(H₂O)}_n (1), [Zn(2,2′-dmbpy)(TDC)]_n (2), and [Zn₂(3,3′-dmbpy)(TDC)₂]_n (3) (H₂TDC =2,5-thiophenedicarboxylic acid, 4,4′-bpy =4,4′-bipyridine, 2,2′-dmbpy =2,2′-dimethyl-4,4′-bipyridine, 3,3′-dmbpy =3,3′-dimethyl-4,4′-bipyridine) have been synthesized under the same reaction conditions (H₂O, pH =7–8, and 140°C) and were structurally characterized. 1 is a linear chain structure and further connected into a 3-D structure through hydrogen bonds. 2 shows a 2-D (4,4) network when the dinuclear [Zn₂(COO)₄N₂] building unit is regarded as a six-connected node. 3 has a twofold-interpenetrating 3-D zinc-organic framework pcu topology. Furthermore, 1–3 show strong photoluminescence at room temperature in the solid state, and the catalytic activities of 1–3 for degradation of methyl orange in a Fenton-like process have been investigated. The results suggest that the ancillary ligands influence the final resulting CPs.     

Two-dimensional layer polyoxometalate-based inorganic metal–organic hybrid supramolecular networks woven by Cu ··· Opolyoxoanion short contact weak interactions

Two polyoxometalate-based inorganic metal-organic hybrid supramolecular complexes [Cu(2,2′-bpy)₂]₂[V^IV ₂Mo^V ₅Mo^VI ₇O₃₈(PO₄)] (1) (2,2′-bpy?=?2,2′-bipyridine) and [Cu(2,2′-bpy)₂]₂[Mo^VMo^VI ₁₁O₃₆(PO₄)]?·?3H₂O (2), have been hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction. Both complexes are constructed from polyoxoanions (the bivanadyl capped α-Keggin polymolybdate anion [V^IV ₂Mo^V ₅Mo^VI ₇O₃₈(PO₄)]^4? for 1 and the reduced 12-molybdophosphate anion [Mo^VMo^VI ₁₁O₃₆(PO₄)]^4? for 2) and copper(II) complex cations [Cu(2,2′-bpy)₂]²⁺, forming two-dimensional (2D) layer network structures, in which the polyoxoanion and the complex fragment cation connect with each other through Cu?···?O_polyoxoanion short contact weak interactions, which mediate ferromagnetic interaction.     

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.     

Solvothermal syntheses,crystal structures and properties of four polymers built by p-methoxyphenyl imidazole dicarboxylates

By employing 2-(4-methoxyphenyl)-1H-imidazole-4,5-dicarboxylic acid (p-MOPhH₃IDC) to react with Cd(II), Zn(II) and Sr(II) ions, four polymers, [Cd(p-MOPhHIDC)(2,2′-bipy)]_n (2,2′-bipy = 2,2′-bipyridine) (1), [Zn_0.5(p-MOPhH₂IDC)·H₂O]_n (2), {[Cd₄(p-MOPhHIDC)₄(C₂H₅OH)₂(H₂O)₂]·4C₂H₅OH·2H₂O}_n (3) and {[Sr₂(H₂MOPhIDC)₂(C₈H₄O₄)(H₂O)₆]·6H₂O}_n (4) have been solvothermally synthesised and structurally characterised by single-crystal X-ray diffraction. Polymer 1 is a chain with 2,2′-bipy appending in the same side. Polymer 2 is a 2D rhombus grid structure. The π?π interactions between the aromatic groups supply the additional stabilisation for the solid-state structures of 1 and 2. Polymer 3 shows a 3D framework bearing 1D open channels. Polymer 4 exhibits a 2D latticed plane. The thermal and photoluminescence properties of 1–4 have been investigated as well.     

Design and syntheses of two threefold interpenetrating 2-D networks

Two new interpenetrating networks, [Ni(2,2′-bpy)(5-npa)(bpe)_0.5(H₂O)] _n (1) and [Ni(2,2′-bpy)(5-npa)(bpa)_0.5(H₂O)] _n (2) (2,2′-bpy?=?2,2′-bipyridine, 5-npa?=?5-nitroisophthalato, bpe?=?1,2-bis(4-pyridyl)ethylene, bpa?=?1,2-bis(4-pyridyl)ethane), have been synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, X-ray powder diffraction, and single-crystal X-ray diffraction. Complexes 1 and 2 have similar structures and show a threefold interpenetrating topology constructed by three 2-D wave-like networks. Secondary building unit (SBU), [Ni(2,2′-bpy)(5-npa)(H₂O)] _n , was used as starting material of the multistep reaction. Replacing one coordination bond of chelating carboxyl group of SBUs by bpe and bpa afford the two threefold interpenetrating complexes.     

Heteroleptic ruthenium(II) polypyridine complexes with a series of substituted 2,2′-bipyridine ligands

Five substituted-2,2′-bipyridine ligands L, (4-(p-methylphenyl)-6-phenyl-2,2′-bipyridine (L1), 4-(p-bromophenyl)-6-(p-bromophenyl)-2,2′-bipyridine (L2), 4-(p-bromophenyl)-6-phenyl-2,2′-bipyridine (L3), 4-phenyl-6-(p-bromophenyl)-2,2′-bipyridine (L4), and 4-(p-fluorophenyl)-6-(p-fluorophenyl)-2,2′-bipyridine (L5) were synthesized by stepwise formation. Reaction of cis-[RuCl₂(bpy)₂]?2H₂O or cis-[RuCl₂(phen)₂]?2H₂O and the substituted-2,2′-bipyridine ligands in the presence of KPF₆ afforded the corresponding cationic polypyridine-ruthenium complexes of the type [(bpy)₂Ru(L)](PF₆)₂ (bpy = 2,2′-bipyridine, 1–5) or [(phen)₂Ru(L)](PF₆)₂ (phen = 1,10-phenanthroline, 6–10), respectively. All complexes have been spectroscopically characterized by UV–vis, luminescence, and electrogenerated chemiluminescence. The structures of 1?CH₃COCH₃, 3?CH₃COCH₃, 5?2CH₃COCH₃, 6, 8, 9, and 10 have been determined by single-crystal X-ray diffraction.