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.     

The structure of solvate [Cu2(DfH)4(4,4′-Bipy)] · 2DMF

The crystal structure of [Cu₂(DfH)₄(4,4′-Bipy)] · 2DMF prepared by the reaction of copper(II) acetate with diphenylglyoxime (DfH₂) and 4,4′-bipyridine (4,4′-Bipy) was established by X-ray diffraction. The crystals are monoclinic; a = 15.5192(9) Å, b = 16.2427(11) Å, c = 14.0753(7) Å, β = 101.36(3)°, V = 3478.5(5) ų, Z = 2, and sp. gr. P2₁/c. The crystal structure is composed of discrete dinuclear molecules [Cu₂(DfH)₄(4,4′-Bipy)] and dimethylformamide (DMF) molecules. The coordination polyhedron of the Cu atom (the coordination number is 5) is a tetragonal bipyramid formed by the nitrogen atoms of two monodeprotonated bidentate oxime groups and the bidentate bridging 4,4′-Bipy ligand. The DMF molecules occupy the cavities formed by the dinuclear molecules [Cu₂(DfH)₄(4,4′-Bipy)]. The compound was characterized by IR and NMR spectroscopy.     

Influence of Changes in the Central Core on the Mesomorphic Properties of 4,4’ -Dialkoxybenzalazines and Derivatives (II)

Two homologous series of benzalazines were synthesized, namely, the 4,4′-di-n-alkoxy-2-hydroxybenzalazines and 4,4′-di-n-alkoxybenzalazines, and their mesomorphic properties were studied.

All the prepared compounds of these series exhibit mesomorphism and some of them possess crystalline polymorphism also.

A comparative study of the mesomorphic properties of these series with those of 4,4′-di-n-alkoxy-2,2′-dihydroxybenzalazines and the analogous α,α'-dimethylbenzalazines was carried out in order to determine the influence of the central core on the mesomorphic properties.     

Growth and structural characterization of [ZnL(DMSO)]

A novel mononuclear zinc(II) complex [ZnL(DMSO)] (1) with chelating bisoxime ligand 4,4′‐dinitro‐2,2′‐[ethylenedioxybis(nitrilomethylidyne)]diphenol (H₂L) was synthesized and structurally characterized by X‐ray crystallography. The complex crystallizes in the triclinic system, space group P‐1, with unit cell parameters a = 8.9730(16), b = 11.9080(18), c = 20.701(2) Å, α = 103.893(3), β = 101.975(3), γ = 90.029(2) and Z = 4. The Zinc(II) ion is five‐coordinated by four N₂O₂ donor atoms of L^2‐ and one oxygen atom from DMSO molecule. Interestingly, the unit of cell contains two crystallographically independent but chemically identical mononuclear complexes. (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal Structure of 6,6′-dimethoxy-2,2′-diphenyl-19-crown-5 Hg(SCN)2

The crystal structure of 6,6′-dimethoxy-2,2′-diphenyl-19-crown-5 Hg(SCN)₂ has been determined from three-dimensional X-ray diffraction data. The compound crystallizes in the triclinic space group P1 (no 2) with unit cell parameters α = 9.712(6) Å, β = 11.137(7) Å, c = 14.768(12) Å, α = 86.04(5), β = 80.36(4), γ = 65.70(4), Z = 2, V= 1435(2) ų. The structure was determined by direct methods which on refinement yielded a final value of R(F) index as 0.068.     

Magnetic properties and sensitized visible and NIR luminescence of DyIII and EuIII coordination polymers by energy transfer antenna ligands

Two coordination polymers, {[Ln(2-stp)(4,4′-bipy)(H₂O)].(H₂O)}, [Ln = Dy (1) and Eu (2), 2-stp = 2-sulfoterephthalate and 4,4′-bipy = 4,4′-bipyridine] have been characterized by solid state UV-vis, FTIR spectra, X-ray single crystal diffraction and solid state photoluminescence. Variable-temperature magnetic susceptibility and isothermal magnetization as function of external magnetic field is also studied for both complexes. After ligand-mediated excitation, both complexes show the characteristic visible and NIR luminescence of the corresponding Ln^III ions (Ln = Dy, Eu) which is due to efficient energy transfer from the ligands to the central Ln^III ions via an antenna effect. The indirect energy transfer in both complexes has been investigated and discussed in detail.     

Aggregation of a Cationic Cyanine Dye Intercalated in the Interlayer Space of a Layered Titanate Na2Ti3O7

Abstract

A cationic cyanine dye. 1,1′-diethyl-2,2′-cyanine (PIC), was successfully intercalated into Na₂Ti₃O₇ by a guest-exchange method using a propylamine/Ti₃O₇ intercalation compound as the intermediate. Based on the XRD and chemical analytical results, it was presumed that PIC was densely packed in the interlayer space with the short axis of its quinoline-ring almost perpendicular to the host layer. Spectroscopic results revealed that the PIC formed J-aggre-gates even in the restricted space between the titanate layers.     

The Crystal Structure of [La(NO3)6{Cu(2,2′-bipy)2}2][La(NO3)6Cu(2,2′-bipy)2]CH3CN with the Most Profuse Modes of Nitrate Coordination

The title compound [La(NO₃)₆{Cu(2,2′-bipy)₂}₂][La(NO₃)₆Cu(2,2′-bipy)₂] CH₃CN was synthesized, the crystal and molecular structures were determined at room temperature. The complex formed monoclinic crystals, space group P21/n (No.14), a = 10.354 (3) A, b = 23.440 (9) A, c = 32.817 (9) A, b = 90.39 (2)°, Z = 4. The crystal structure consisted of a discrete [La(NO₃)₆{Cu(2,2′-bipy)₂}₂]⁺ cation and [La(NO₃)₆Cu(2,2′-bipy)₂]^- anion and a non-coordinated CH₃CN molecule. Each La(III) ion was 12-coordinate with twelve oxygen atoms from six chelating nitrate ligands. There were four modes of nitrate coordination and the coordination geometry of all three copper ions was different in the crystal structure.     

Influence of Changes in Central Core on the Mesomorphic Properties of 4,4′-Dialkoxy-2,2′-Dihydroxybenzalazine and Derivatives

Two new series of compounds that have mesomorphic properties were synthesized: the 4,4′-dialkoxy-2,2′-dihydroxy-a-methylbenzalazines and the 4,4′-dialkoxy-2,2′-dihy-droxybenzalazines. The first series shows crystalline and smectic polymorphism.

A comparative study of the mesomorphic properties of these series with those of the 4,4′-dialkoxy-2,2′-dihydroxy-α,α'-dimethylbenzalazines was carried out to establish the influence of the central groups on the mesomorphic properties.     

Synthesis,crystal structure and photophysical studies on a ruthenium(II) carbonyl hydrido compound based on 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid (H2bpdc)

A novel complex, namely [Ru^II(PPh₃)(CO)(H)(Hbpdc)]·2MeOH ( 1 ) (H₂bpdc = 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid), has been synthesized from the reaction of H₂bpdc with [Ru^II(PPh₃)₃(CO)(H)₂] in methanol under mild condition and characterized by elemental analysis, IR spectrum, ESI mass spectrometry, and single crystal X‐ray diffraction. The structure shows that the complex crystallizes in the monoclinic space group P2₁/c with unit cell parameters a = 11.8984(13) Å, b = 16.5180(18) Å, c = 25.5322(19) Å, β = 115.302(4)°, V = 4536.6(8) ų, Z = 4. This compound features a 1‐D supramolecular chain constructed via hydrogen bonds. Its photophysical properties have been investigated in MeOH solution and in the solid state at room temperature.     

EDA complex stability constants and formation enthalpies in a binary liquid crystalline system with induced smectic phase

In the binary system 4,4′-bis-[n-butylamino]-biphenyl/-(2,2-dicyano-ethenyl)-phenyl 4-n-nonyloxybenzoate which due to EDA complex formation exhibits an induced S_A phase, measurements of the charge transfer band, the molar volumina and transition enthalpies were done. By the concentration and temperature dependence, resp., of the charge transfer absorption and the strongly negative excess volumina we estimated the stability constant and the formation enthalpy of the complex. The data obtained by the two independent methods agree sufficiently.     

Synthesis and characteristics of multi-aryl substituted molecular glasses bearing biphenyl core

Two novel compounds based on biphenyl structure, 2,2′-di(3,5-di(tert-butylcarbonate)phenyl)-4,4′-di(tert-butylcarbonate)biphenyl (A) and 2,2′,4,4′-tetra(3,5-di(tert-butylcarbonate)phenyl)biphenyl (B) were synthesized by commercially available materials. The products were fully characterized by FTIR, NMR and elemental analysis. The thermal stability and the phase transition of these compounds had been studied by TGA and DSC techniques. For compound A, thermal decomposition temperature was of 176 °C and glass transition temperature (T_g) was of 105 °C. While for compound B, the thermal decomposition occurred at 186 °C and T_g was of 122 °C. The synthesized compounds were found to be amorphous materials by XRD analysis and good film-forming ability by AFM analysis. These results indicated that the synthetic molecular glasses would be suitable for low molecular weight photo resists in EUV lithography.     

Crystal structures of 1,1′-di(methylacetato)- and 1,1′-di(chloroethoxyethyl)-2,2′-biimidazole

1,1′-Di(methylacetato)-2,2′-biimidazole, C₁₂H₁₄N₄O₄, crystallizes from methanol in the space groupP2 ₁/c, wherea=9.535(2),b=13.385(2),c=5.1208(8) Å,V=652.2(2) ų, andZ=4.1,1′-Di(chloroethoxyethyl)-2,2′-biimidazole, C₁₄H₂₀Cl₂N₄O₂, crystallizes from cyclohexane in the space groupPbca, wherea=12.372(2),b=8.959(2),c=14.840(2) Å,V=1644.9(5) ų, andZ=8. The structures were refined toR=0.041 (1380 observed reflections) andR=0.043 (3243 observed reflections), respectively. Both molecules crystallize with coplanar rings and the substituents assume atrans configuration with a center of inversion between the bridging carbon atoms.     

Syntheses, Structures, Fluorescence and Magnetic Property of Two Complexes with the Asymmetric dpa Ligand

Abstract  

Two compounds [Zn(Hdpa)₂(2,2′-bipy)]₂ (1) and [Mn(dpa)(4,4′-bipy)] _n (2) (H₂dpa=2,2′-biphenyldicarboxylate, bipy=dipyridine) are synthesized by hydrothermal reactions and structurally characterized by Single crystal X-ray diffraction analyses. Compound 1 is a dual-core molecular structure of two Zn ions in the same coordination environment, we studied the fluorescence of compound 1. Compound 2 is a layer structure based on the one-dimensional chains bridged by 4,4-bipy, it displays weak antiferromagnetic interactions between the inter-chain Mn²⁺ ions.     

Preparation and Reactivity of 4,4′-diaminostilbene-2,2′disulphonate

The precursor compound 4,4′-diaminostilbene-2,2′disulphonic acid DAS-(SO₃H)₂ was successfully deprotonated through reactions with (n-Bu₄N)(OH) and NaOH to produce the corresponding salts sodium 4,4′-diaminostilbene-2,2′disulphonate Na₂(DAS-(SO₃)₂) (1) and tetrabutylammonium 4,4′-diaminostilbene-2,2′disulphonate (n-Bu₄N)₂(DAS-(SO₃)₂) (2). The structure of (n-Bu₄N)₂(DAS-(SO₃)₂) (2) was confirmed through the use of single crystal X-ray diffraction. Compound (2) crystallizes in the monoclinic space group P2₁/n with the lattice parameters of a = 10.0645(6), b = 14.2573(9), c = 17.6053(11), and β = 94.3160(10). The reaction of Cu²⁺(aq) with (n-Bu₄N)₂(DAS-(SO₃)₂) resulted in the crystallization of the molecular organocopper cluster, [CuDAS-(SO₃)₂]₂·3H₂O (3), that resembles a molecular parallelogram as revealed by single crystal X-ray diffraction. Compound (3) crystallizes in the monoclinic space group P2₁/n with the lattice parameters of a = 8.8647(6), b = 10.5247(7), c = 21.2265(14), and β = 93.1730(10). Within the structure of (3) each [DAS-(SO₃)₂]²⁻ ligand is shown to bind two copper atoms through interactions with three of the five available metal binding sites.

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Graphical abstract Preparation and Reactivity of 4,4′-diaminostilbene-2,2′disulphonate Natalie C. Rader, Heather A. Nees, Paul S. Szalay*, Matthias Zeller and Allen D. Hunter The preparation of 4,4′-diaminostilbene-2,2′disulphonic and its reactivity with copper(II) are described.

     

Synthesis and crystal structure of a new organic compound: Bis(4,4′-diaminodiphenylmethane) (4,4′-diammoniodiphenylmethane) dichloride monohydrate

A new organic compound with the formula C₃₉H₄₆Cl₂N₆O was synthesized from aqueous solution of 4,4′-diaminodiphenylmethane and hydrochloric acid at room temperature. This compound crystallizes in the monoclinic space group C2: a = 25.6525(16), b = 5.7107(3), c = 13.7777(8) Å, β = 118.862(2)°, V = 1767.64(22) ų and Z = 2, giving D _x = 1.288 g cm^?3. The refinement converged to R ₁ = 0.027 and wR ₂ = 0.0649. The structural arrangement can be described as infinite layers parallel to bc plane. In these layers cations and non protonated molecules are linked with N-H...N hydrogen bonds building [C₃₉H₄₄N₆]²⁺ organic clusters. These clusters, in turn, are linked by N-H...Cl and O-H...Cl hydrogen bonds.     

Hydrogen-Bonded Molecular Ladders and Interlaced Networks in Complexes Built of V-Shaped Molecules 4,4′-Isopropylidenediphenol or 4,4′-Oxydibenzoic Acid with 4,4′-Bipyridine

Abstract  

The title compounds, C₁₀H₈N₂·C₁₅H₁₆O₂ (1) and C₁₀H₈N₂·C₁₄H₁₀O₅ (2), were synthesized by 4,4′-bipyridyl and two similar V-shaped molecules. The two complexes both crystallized in the same space group P2₁/n with the crystal cell parameters: a = 16.0536(3) ?, b = 6.42730(1) ?, c = 21.2717(4) ?, β = 102.330°, V = 2144.21(7) ?³, Z = 4 in compound 1 and a = 7.45020(10) ?, b = 10.0784(2) ?, c = 26.9430(5) ?, β = 92.1140(10)°, V = 2021.67(6) ?³, Z = 4 in compound 2. Compound 1 forms regular molecular chains containing alternative 4,4′-bipyridyl and 4,4′-isopropylidenediphenol units; the molecular components are linked by two types of O–H···N hydrogen bonds. Additionally, every two neighboring chains are connected to be a ladder structure by means of weak C–H···O interactions. In compound 2, 4,4′-bipyridyl and 4,4′-oxydibenzoic acid first construct one-dimensional architecture by strong O–H···N hydrogen bonds, which are similar with the interactions in compound 1. Secondly, two types of weak C–H···O contacts formed between 4,4′-bipyridyl and the acid link one-dimensional chains to be interlaced three-dimensional hydrogen-bonded networks.     

Electrochemical Deposition of CdTe Layers. Their Structure and Electrical Properties

CdTe layers have been deposited catodically on nickel substrates from an aqueous solution of CdSO₄ and TeO₂. The degree of erystallinity increases with increasing temperature and decreasing deposition potential. The structure of the layers is cubic with 〈111〉 or 〈110〉 texture which is determined by TeO₂ concentration predominantly. Amorphous phase is found in deposits prepared at higher deposition potential or at lower temperatures of bath (60 °C). After annealing at 200 °C the amorphous deposits crystallized and pure tellurium appeared in diffraction spectra. The resistivity of the films was determined by means of I—V characteristics. Films with deposition potentials (−500 to −400) mV vs SCE are p-type conductivity whereas at lower potentials (down to − 700 mV vs. SCE) the n-type material is formed.     

Synthesis and Crystal Structures of Two Metal Complexes Formed in the Solvothermal Decomposition Reactions of <Emphasis Type="Italic">N</Emphasis>-Carboxyphenylenesulfonyl-S-Carboxymethyl-<Emphasis Type="SmallCaps">l</Emphasis>-Cysteine

Abstract  

The reactions of a new compound of N-Carboxyphenylenesulfonyl-S-Carboxymethyl-l-Cysteine (Cs-cmc) with Zn(II) or Co(II) salts in the presence of 4,4′-bipyridine (4,4′-bipy) led to the decomposition of Cs-cmc and produced [Zn(4,4′-bipy)(H₂O)₄]X₂ (X = p-sulfamoylbenzoate) 1 and [Co(4,4′-bipy)(H₂O)₄]Y·H₂O (Y = p-sulfonatobenzoate) 2, in which the decomposition products of Cs-cmc exist as free counter-anions. The single crystal X-ray diffraction analyses revealed that compound 1 crystallizes in monoclinic C2/c space group with a = 18.748(4) ?, b = 11.520(2) ?, c = 12.751(3) ?, β = 90.290(4)°, V = 2753.9(10) ?, Z = 4 and compound 2 crystallizes in orthorhombic Pca2₁ space group with a = 12.114(3) ?, b = 11.369(2) ?, c = 14.770(3) ?, V = 2034.1(7) ?, Z = 4. It was revealed that 1D chains were constructed from metal ions and 4,4′-bipy in both compounds. The 1D chains interact with the counter-anions by hydrogen bonds, forming 3D supramolecular structures.