Construction of Three Novel Coordination Complexes by 3-Nitrophthalic Acid Plus N-Donor Ligands: Synthesis,Structure, and Properties

In order to explore new coordination frameworks with novel designed 3-nitrophthalic acid and N–donor ancillary ligands, three novel coordination complexes, namely, [Co₂(3-NPA)₂(2,2′-bipy)₂(H₂O)₂]?2H₂O (1), [Mn₂(3-NPA)₂(4,4′-bipy)₃(H₂O)₆]?(4,4′-bipy) (2), and [Pb₂O(3-NPA)]_n (3) (where 3-NPAH₂ = 3-nitrophthalic acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. X-ray structure analysis reveals that 1 and 2 are dinuclear structures, while 3 is a two-dimensional (2D) network polymer. And the hydrogen bonds and π–π stacking also play important roles in affecting the final structure where complexes 1-2 have 3D and 2D supramolecular architectures, respectively. These complexes have been characterized by powder X-ray diffractions (PXRD) and thermal gravimetric analyses (TGA). In addition, their photochemical properties have also been investigated.     

A Novel Supramolecular Complex Based on Zaltoprofen Ligand: Synthesis,Crystal Structure,and Properties

A novel metal-organic supramolecular complex [Zn₂ (Zaltoprofen)₂(phen)₂] (where Zaltoprofen = 5-(1-carboxyethyl)-2-(phenylthio)phenylacetic acid, phen = 1,10-phenanthroline) has been synthesized under hydrothermal condition and characterized by single crystal X-ray diffraction, elemental analysis, spectral method (IR), powder X-ray diffraction (XRD), electronic Spectra (UV-vis), and fluorescent properties. The compound crystallizes in the monoclinic P2(1)/c space group. [Zn₂(Zaltoprofen)₂(phen)₂] features 0-D structural, the π–π stacking interactions and C?H···O hydrogen-bonds play a vital role in determining the crystal packing and construction of the extended 3-D supramolecular network.     

Synthesis,structures, and luminescent properties of a series of coordination compounds based on O,N-donor ligands

Four novel coordination compounds, namely, [Cd₂(pydc)₂(bpp)₂(H₂O)₂]? bpp?2H₂O (1), [Zn(Hpydc)₂]?3H₂O (2), [Cd(dhb)₂(phen)₂] (3), and [Zn(L)(phen) (H₂O)] (4) (H₂pydc?=?2,6-pyridinedicarboxylic acid, Hdhb?=?2,6-dihydroxybenzoic acid, H₂L?=?5-((2'-cyano-1,1'-biphenyl-4-yl) methoxy)isophthalic acid, bpp?=?1,3-bis(4-pyridyl)propane, and phen?=?1,10-phenanthroline) have been hydrothermally synthesized and characterized by IR spectroscopy, thermogravimetric analysis and X-ray single crystal diffraction analyses. Compounds 1, 2 and 3 feature zero-dimensional (0D) structures and 1 is further extended to one-dimensional (1D) chain structure through C-H???O hydrogen bonding interactions. Compound 4 exhibits 1D chain structure. The luminescent properties of compounds 3 and 4 have also been studied.     

Different complexation behavior of a proton transfer compound obtained from 1,10‐phenanthroline and pyridine‐2,6‐dicarboxylic acid with Sn(IV), Sb(III) and Tl(I)

The different complexation methods of a proton transfer compound, (phenH)₂(pydc) (phen=1,10‐phenanthroline; pydcH₂= pyridine‐2,6‐dicarboxylic acid), are discussed and formation of [Sn(pydc)(phen)(OH)₂]·3H₂O ( 1 ), {[Sb(pydc)(phen)]₂O}·2DMSO·4H₂O( 2 ) and [(Tl(pydcH)]_n ( 3 ) complexes are reported. The characterization was performed using IR spectroscopy and X‐ray diffraction. The structures of Sn(IV) and Sb(III) complexes show that both cationic and anionic fragments of the starting proton transfer compound have been involved in the complexation. Whereas the structure of Tl(I) complex demonstrates that only the anionic fragment of (phenH)₂(pydc) is contributed to the complexation. The complexes 1‐3 show a variety of structural features including mononuclear, binuclear and polymeric structures. In compounds ( 1 ), ( 2 ) and ( 3 ) a large number of hydrogen bonds are observed. These interactions play an important role in the formation and stabilization of supramolecular systems in the crystal lattices. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,Crystal Structure and Optical Properties of a Three-Dimensional Supramolecule Assembled by a Dinuclear Neodymium Cluster

Abstract  

The reaction of isonicotinic acid (IN), sodium hydroxide, 1,10-phenanthroline (phen) and neodymium nitrate leads to the formation of a novel complex [Nd(phen)(IN)₂(NO₃)(H₂O)₂]₂ 1, which has been characterized by single crystal X-ray diffraction analysis: monoclinic, space group C2/c, with a = 24.93(2) Å, b = 9.452(3) Å, c = 21.406(5) Å, β = 97.87(2)°, and Z = 4. Complex 1 consists of a centrosymmetric dinclear molecule, and neodymium atoms are bridged by two carboxyl groups of two IN ligands. The dinuclear clusters of 1 are connected each other into a three-dimensional (3D) supramolecular framework, which is stabilized by O–H···O, O–H···N hydrogen bonds as well as π–π stacking interactions. Its electronic absorption and luminescence properties have also been investigated.     

Three New Complexes Based on a Flexible Bis(benzimidazole) Ligand and Rigid/Flexible Organic Carboxylates

Abstract  

Three new polymeric frameworks, [Ni(bbbm)(L1)₂] _n (1), [Ni(bbbm)(L2)₂] _n (2), and {[Co(bbbm)(L3)]·H₂O} _n (3) (bbbm = 1,4-bis(N-benzimidazolyl) butane, HL1 = 4-bromobenzoic acid, HL2 = 3-methylbenzoic acid, and H₂L3 = glutaric acid) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 features a one-dimensional (1D) linear chain structure bridged by bbbm ligands, which is further connected into a supramolecular double chain structure through intermolecular π–π stacking interactions. Complex 2 contains 1D zigzag chain, which is further arranged into a 2D supramolecular architecture by hydrogen bonding and π–π stacking interactions. In the structure of 3, there are infinite 1D zigzag Co(II)-bbbm chains linked together by L3 ligands to generate an undulated 2D (4,4) sheet, which is further connected by intermolecular π–π stacking interactions to form a 3D supramolecular network. Furthermore, thermal stability and luminescent property of 1–3 were investigated.     

Crystal growth,structure and characterization of diglycine zinc dipicrate: Centrosymmetric crystal exhibiting second harmonic generation efficiency

A new cadmium coordination polymer, formulated as [Cd(L)(phen)]_n, were prepared by hydrothermal reactions based on 3,4-dibromothiophene-2,5-dicarboxylic acid (H₂L) and 1,10-phenanthroline (phen) mixed organic linkers. In the complex, adjacent Cd²⁺ ions are linked by L^2? anions to form a one-dimensional (1D) [CdL]_n chain with [Cd₂(COO)₂] as the secondary building unit (SBU). These adjacent chains are further stacked together by direct C?Br···Br halogen bonds interactions, generating a two-dimensional (2D) supramolecular structure. From the viewpoint of topology, the 2D supramolecular network can be rationalized to a 3,4-connected 3,4L13 net with {4.6²}₂{4².6².8²} topology.     

Two Ag(I)-Containing Supramolecular Coordination Polymers Constructed from the Multidentate N-donor Ligand 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole Based on Hydrogen-Bonding and π–π Interactions: Syntheses,Crystal Structures,Optical Band Gaps and Luminescent Properties

Two Ag(I)-based coordination polymers, namely [Ag₂(3,3′-tmbpt)(o-Hbdc)₂]·H₂O (1) and [Ag₈(3,3′-tmbpt)₄(1,2,4-Hbtc)₄(H₂O)] (2) (3,3′-tmbpt?=?1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, o-H₂bdc?=?1,2-benzenedicarboxylic acid and 1,2,4-H₃btc?=?1,2,4-benzenetricarboxylic acid), have been synthesized. Single-crystal X-ray diffraction analyses, elemental analyses, infrared spectra, powder X-ray diffraction analyses and thermogravimetric analyses have been carried out to characterize the structures of 1 and 2. Compound 1 shows a (3,4)-connected 2D layered structure with a Schläfli symbol of (4²·6)(4²·6³·8). The intermolecular O–H···O hydrogen-bonding interactions extend the 2D layer into a 3D supramolecular architecture. Compound 2 exhibits a (3,3)-connected double-layered structure with a Schläfli symbol of (4·8·10)₂(8²·10)₂. The intermolecular C–H···O hydrogen-bonding interactions link the double-layers to form a 3D supramolecular architecture. Moreover, there are intramolecular and intermolecular π–π interactions in 1 and 2, which stabilize the whole 3D supramolecular architectures. The band gaps of 1 and 2 are 3.19 and 3.09 eV, respectively, indicating the potential of 1 and 2 as semiconductive materials with wide band gaps. Moreover, 1 and 2 emit intense blue-green light, which may be potential photoactive materials.

Graphic Abstract

Two Ag(I)-based 3D supramolecular coordination polymers constructed from a multidentate N-donor ligand and two aromatic polycarboxylate anions via hydrogen-bonding and π–π interactions have been synthesized and characterized. The band gaps and photoluminescent properties of the compounds have been studied.

     

CoL(SO4)0.5 ?·?4H2O and MnL2 ?· 2H2O (L = 1,10-Phenanthroline-4,5- f -triazolate): Synthesis, Crystal Structures and Hydrogen-Bonded Networks

Abstract  Two metal complexes of 1H-triazo-4,5-f-1,10-phenanthroline (HL), CoL(SO₄)_0.5 · 4H₂O (1) and MnL ₂ · 2H₂O (2) have been synthesized on hydrothermal conditions and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction analysis. Complex 1 was further assembled into a three-dimensional (3D) supramolecular network through the hydrogen-bonding interactions and inter-molecular π···π stacking interaction, 2 further assembled into a two-dimensional (2D) layer structure. This result shows that hydrogen-bonding interactions and π···π stacking interaction play important roles in the formation of coordination networks, especially in the aspect of linking the multinuclear discrete subunits or low-dimensional entities into high-dimensional supramolecular frameworks. Index abstract  Two metal complexes of 1H-triazo-4,5-f-1,10-phenanthroline (HL), CoL(SO₄)_0.5 · 4H₂O (1) and MnL₂ · 2H₂O (2) have been synthesized on hydrothermal conditions. Complex 1 was further assembled into a three-dimensional (3D) supramolecular network through the hydrogen-bonding interactions and inter-molecular π···π stacking interaction, 2 further assembled into a two-dimensional (2D) layer structure.      

Pyridine-2,6-Dicarboxylic Acid (Dipic): Crystal Structure from Co-Crystal to a Mixed Ligand Nickel(II) Complex

Abstract  

Pyridine-2,6-dicarboxylic acid (dipic) was used for the synthesis of a co-crystal with 1,10-phenanthroline-5,6-dione (phen-dione) and a nickel(II) complex. The co-crystal dipic·phen-dione·4H₂O (1) has been synthesized and studied by X-ray crystallography. The structure is stabilized with hydrogen bonds between dipic, H₂O and phen-dione. It is surprising that there is no direct hydrogen bonding between phen-dione and dipic and yet the molecules co-crystallize in aqueous solution. A new complex of nickel(II), [Ni(phen)(dipic)(H₂O)]·4H₂O (2), (where phen = 1,10-phenanthroline) has been synthesized and characterized by elemental and thermogravimetric analyses, FT-IR, UV–Vis and ¹H-NMR spectroscopy. The structure of (2) has been studied by X-ray crystallography. The coordination around Ni(II) is a distorted octahedron. The crystal packing shows that the dimensionality of (2) is enlarged to 3D, through hydrogen bonds and π–π interactions. Cyclic voltammetry of (2) shows that the Ni(II/I) couple is irreversible.     

Synthesis and characterization of a lead(II) complex [Pb(phen)(H<Subscript>2</Subscript>O)(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>] (phen = 1,10-phenanthroline)

The monomeric lead(II) complex, [Pb(phen)(H₂O)(NO₃)₂] was prepared by a hydrothermal reaction of Pb(NO₃)₂, nitrilotriacetic acid, NaOH, 1,10-phenanthroline, and H₂O. The structure was determined by X-ray crystallography. It crystallizes in monoclinic P2(1)/n space group with the crystal cell parameters of a = 6.3568(6), b = 20.2345(19), c = 11.2722(9) Å, β = 98.337(4)^°, V = 1434.6(2) ų, and Z = 4. The crystal X-ray analysis shows that the lead atom is six-coordinated by two N atoms of phen ligand, three oxygen atoms of nitrate anions and one water molecule. Owing to the presence of a lone pair of electrons of lead atom, a significant gap occurs in the coordination geometry around Pb ion. A 3D architecture is formed through the strong hydrogen bonding and π–π stacking interactions.     

Syntheses,Structures and Luminescent Properties of Zinc(II) and Cadmium(II) Complexes With the Ditopic Ligand 1,3-Bis(imidazol-1-ylmethyl)benzene

Abstract  

Three new complexes, namely [Zn(mbix)(SO₄)]·CH₃OH (1), Cd(mbix)₂(NO₃)₂ (2) and [Cd(mbix)₂(H₂O)₂]·(NO₃)₂ (3), have been obtained by reactions of flexible bidentate ligand 1,3-bis(imidazol-1-ylmethyl)benzene (mbix) with corresponding zinc(II) and cadmium(II) salts. The structures of these complexes have been determined by the X-ray single crystal diffraction analysis. Complex 1 features a 2D wavy network with (4,4) topology. Complex 2 has a 2D grid network with left- and right-handed helical chains, while complex 3 exhibits twofold parallel interpenetration structure. The differences of three complexes demonstrate that the coordination geometry of metal ions and the ratio of reactants have a great impact on the structure of the supramolecular architectures. The luminescent properties of three complexes are also investigated.     

Synthesis and Crystal Structure of 2D Supramolecular Compound [Co(phth)(phen) (H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]·H<Subscript>2</Subscript>O

Abstract  

A 2D supramolecular compound [Co(phth)(phen) (H₂O)₃]·H₂O has been synthysized by the reactions of Co(NO₃)₂·6H₂O, 1, 10-phenanthroline(phen) and phthalate acid(H₂phth) in NaOH solution with pH 7.0.The complex has been characterized by elemental analysis, IR, and single-crystal X-ray diffraction analysis which shows it belongs the monoclinic space group P2(1)/n, a = 7.571(2) ?, b = 13.737(3) ?, c = 20.015(4) ?, β = 95.56(1)°. V = 2071.9(8) ?³, Mr = 475.31, Dc = 1.524 g/cm⁻³, Z = 4, F(000) = 980, μ(MoKa) = 0.879 mm⁻¹. The final R1 and wR2 are 0.0348 and 0.0711, respectively. The cobalt(II) ion is six-coordinated in a distorted octahedron to form a unit. Every unit is connected by hydrogen bonds forming 1D chain and 2D supramolecular network by π–π stacking interaction between adjoining chains.     

Two novel two-dimensional frameworks with channels built from hydrogen bonds: Structures and properties study on copper(II) and nickle (II) complexes of the macrocyclic ligand 1,4,7-triazacyclodecane (tacd)

Two novel supramolecular complexes [Cu(tacd)₂](C₄H₃O₄)₂ (1) and [Ni(tacd)₂]Cl₂·4H₂O (2) were synthesized and their structures were characterized by elemental analysis, IR spectrum, TGA and single-crystal X-ray analysis. The results indicated that the complexes 1 and 2 assemble into different 2D supramolecular net-work structures with channels via hydrogen bonds interaction. TGA curves showed the steps of weight-loss for 1 and 2.     

Syntheses and Crystal Structures of Two New Cadmium(II) and Nickel(II) Complexes with 1,4-Phenylenediacetate and 2,2′-Bipyridyl-Like Ligands

Abstract  

Two new complexes, namely [Cd(PDA)_0.5(2,2′-bpy)Cl](H₂PDA) (1) and [Ni(PDA)(phen)(H₂O)]₂ (2) (H₂PDA = 1,4-phenylenediacetic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized by elemental analysis, IR spectra and X-ray crystal diffraction. Single-crystal X-ray diffraction analysis shows that complex 1 crystallizes in the triclinic space group P-1 with unit cell dimensions a = 8.760 (4) ?, b = 11.190 (5) ?, c = 13.917 (7) ?, α = 110.383 (5)°, β = 101.736 (5)°, γ = 100.612 (5)°, V = 1202.8 (10) ?³, Z = 2, R ₁ = 0.0314 and wR ₂ = 0.0898. Complex 2 crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 9.911 (3) ?, b = 17.924 (6) ?, c = 10.638 (4) ?, β = 94.998 (5)°, V = 1882.7 (11) ?³, Z = 2, R ₁ = 0.0397 and wR ₂ = 0.1150. In complex 1, Cd(II) ions are alternately bridged by PDA ligands and chloride ions into 1D chains and the PDA ligands display trans-configuration. Complex 2 is a dimer and two Ni(II) ions are linked by two PDA ligands with cis-configuration, resulting in a cyclic structure. In spite of these differences, both in complexes 1 and 2 there are π–π stacking interactions and hydrogen bonding to make them 3D supramolecular frameworks.     

Synthesis, crystal structures, and properties of two manganese(II)-nitroprusside complexes

Two new manganese(II)-1,10-phenanthroline-nitroprusside complexes, [Mn(phen)₃][Fe (CN)₅(NO)]⋯2H₂O⋯0.25CH₃OH (1) and [Mn(phen)₂(H₂O)₂][Fe(CN)₅(NO)]⋯H₂O (2) (where phen is 1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction, electronic paramagnetic resonance (E.P.R.) and IR analyses. Complex 1 crystallizes in the monoclinic space group P2₁/n, with lattice parameters a = 10.0441(15) Å, b = 19.668(2) Å, c = 19.938(3) Å,  β =100.427(14)°, V = 3873.7(10) ų, Z = 4; complex (2) crystallizes in the monoclinic space group C2/c, with a = 17.120(2) Å, b = 13.7925(19) Å, c = 14.4362(17) Å, β = 107.962(12)°, V = 3242.6(7) ų, Z = 4. In the two compounds, three phen ligands 1, or two phen ligands and two cis-related aqua molecules 2, are in a distorted octahedral arrangement around the Mn(II) ion. The nitroprusside anion, [Fe(CN)₅(NO)]²⁻, acts as a counterion. It is intriguing that in complex 2 no cyano bridges are present with two water molecules coordinated to the Mn(II) ion considering that usually the cyano nitrogen atoms are strong donors and could readily replace the coordinating solvent water molecules. Abundant hydrogen bond interactions and π–π stacking between the phen rings in two complexes lead to three-dimensional supramolecular networks.     

Crystal and molecular structure of adduct of 6-benzylaminopurine and 5-sulfosalicylic acid

The crystal structure of adduct of 6-benzylaminopurine and 5-sulfosalicylic acid C₁₉H₂₅N₅O₁₀S 1 is studied using single-crystal diffraction (R = 0.0482 for 2852 reflections with I > 2σ(I)). The asymmetric unit of 1 contains one 6-benzylaminopurine molecule and one 5-sulfosalicylic acid molecule, as well as four lattice water molecules. Hydrogen bonds, formed by 6-benzylaminopurine and 5-sulfosalicylic acid, link the two molecules into one-dimensional chain (omitting four water molecules), further joined to two-dimensional layer network. Short ring-interactions with intra-chain π-π stacking are observed. The data of IR spectroscopy confirm the formation of the two-dimensional supramolecular layer structure. At last, a 3D supramolecular network constructs via hydrogen bonds.     

Hydrothermal Syntheses and Structures of Lanthanide Coordination Polymers with 5-Aminoisophthalate and 1,10-Phenthroline

Abstract  

Two new lanthanide coordination polymers, [Ln₂(APA)₂(HAPA)₂(phen)₂] _n [Ln = Pr (1), Eu (2); H₂APA = 5-aminoisophthalic acid, phen = 1,10-Phenanthroline] have been synthesized by hydrothermal method, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Crystallographic data show that complexes 1 and 2 both crystallize in a triclinic system, space group P[`1] P\bar{1} . The titled compounds own 2-D herringbone structures which are further constructed to form 3-D supramolecular structures by N–H···O and O–H···O hydrogen bondings. The thermogravimetric analyses were carried out to examine the thermal stability of the title complexes. And the photoluminescence property of 2 was investigated.     

Synthesis and Crystal Structure of a 1D Coordination Polymer [Cd(pydc)(phen)]<Subscript>n</Subscript> (H<Subscript>2</Subscript>pydc = pyridine-2,3-dicarboxylic acid,phen = 1,10-phenanthroline)

Abstract  A new 1D coordination polymer, [Cd(pydc)(phen)]_n (1) (pydc = pyridine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline), has been hydrothermally synthesized and characterized by the elemental analysis, IR spectroscopy and single crystal X-ray diffraction. X-ray diffraction analysis reveals that 1 (C₁₉H₁₁CdN₃O₄) crystallizes in triclinic space group P-1, features an interesting 3D zipper-like network constructed from 1D ribbons via π–π stacking interactions. Unit cell parameters for 1: a = 7.681(1) ?, b = 10.546(2) ?, c = 11.358(2) ?, α = 107.12(2)°, β = 99.50(2)°, γ = 109.12 (2)° and Z = 2. Index Abstract  The title compound, [Cd(pydc)(phen)]n (1) (pydc = pyridine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline), has been hydrothermally synthesized and characterized. X-ray diffraction analysis reveals that 1 features an interesting 3D zipper-like networks constructed by 1D ribbons via π–π stacking interactions.      

Synthesis,crystal structure,thermal behavior and luminescence property of a cobalt(II) complex of pyridine-2,6-dicarboxylic acid containing benzimidazole as auxiliary ligand

The new cobalt(II) complex [Co(pydca)(bim)₃] (1) (where H₂pydca = pyridine-2,6-dicarboxylic, bim = benzimidazole) has been synthesized and characterized by elemental analysis, Infrared spectroscopy, X-ray single crystal analysis, thermogravimetric and fluorescent analysis. Single crystal X-ray diffraction analysis reveals that the mononuclear complexes are linked by N–H…O hydrogen bonds. Fluorescent analysis reveals that complex 1 exhibits intense luminescence in ethanol solution at room temperature.