Tricarbonylrhenium(I) bromide complexes with N,N′-bis[1-(4-chlorophenyl)ethylidene]ethane-1,2-diamine and N,N′-bis[1-(4-nitrophenyl)ethylidene]ethane-1,2-diamine–syntheses,structures, electrochemical and spectroscopic studies

Two rhenium(I) complexes, [Re(CO)₃Br(L ⁿ )] (n = 1, 2), (L¹= N,N′-bis[1-(4-chlorophenyl)ethylidene]ethane-1,2-diamine and L² = N,N′-bis[1-(4-nitrophenyl)ethylidene]ethane-1,2-diamine) have been synthesized and characterized by CHN analyses, ¹H NMR, IR, and UV-Vis spectroscopy. The molecular structure of [Re(CO)₃Br(L¹)] is a distorted octahedron around rhenium with one Br, facial arrangement of three CO's, and one diimine. The UV-Vis spectra of the complexes have metal-to-ligand charge transfer bands increasing in wavelength when the L² ligand is replaced by L¹, in agreement with the oxidation potential of the complexes.     

Synthesis and crystal structures of Zn(II) complexes with N,N′-bis[(1-(2-pyridyl)ethylidene)propane-1,3-diamine and N,N′-bis[(1-(2-Pyridyl)ethylidene)ethane-1,2-diamine1

Two new zinc complexes, [Zn(Ppd)I]ClO₄ (I) and [Zn(Ped)I]ClO₄ (II), where Ppd and Ped are the Schiff bases N,N??-bis[(1-(2-pyridyl)ethylidene)propane-1,3-diamine and N,N??-bis[(1-(2-pyridyl)ethylidene)ethane-1,2-diamine, respectively, have been synthesized and characterized by means of elemental analysis, infrared spectroscopic, molar conductivity, and single crystal X-ray diffraction. The crystal of I is tri-clinic: space group $P\bar 1$ a = 8.421(2), b = 9.143(2), c = 13.166(3) ?, ?? = 92.521(5)°, ?? = 94.498(3)°, ?? = 94.232(4)°, V = 1006.6(4) ?³, Z = 2. The crystal of II is triclinic: space group $P\bar 1$ , a = 8.219(1), b = 8.483(1), c = 14.733(2) ?, ?? = 80.058(1)°, ?? = 81.960(1)°, ?? = 89.300(1)°, V = 1001.8(2) ?³, Z = 2. The zinc atom in the complexes assumes a distorted square pyramidal geometry through coordination by two pyridine N atoms and two imine N atoms of the Schiff base at the basal plane, and by a I atom at the apical position.     

Solvent-free synthesis and crystal structures of s-cis and s-trans N,N′-bis(2-hydroxycyclohexyl)ethane-1,2-diamine

The symmetrical amino alcohol synthesis via ring opening of cyclohexene oxide with ethylendiamine is illustrated by synthesis and characterization of β-amino alcohols s-cis-(SSSS)-cy₂en (1) and s-trans-(SSRR)-cy₂en (2) (cy₂en = N,N′-bis(2-hydroxycyclohexyl)ethane-1,2-diamine) in one step and with high yield. The reaction was carried out in a microwave reactor under solvent-free conditions. These products were characterized by IR and Raman spectroscopy, elemental analysis, thermal methods (TGA, DTG and DTA), mass spectrometry and ¹H and ¹³C NMR spectroscopy. The crystal structures of 1 and 2 were determined by single crystal X-ray structural analysis, followed by DFT calculations. Intramolecular hydrogen bond was observed in 1 with C ₂ symmetry, but not in 2 with C _i symmetry. The nature of intramolecular hydrogen bond in 1 has been investigated by AIM and NBO analyses. The molecules in 1 are linked into an infinite chain along the [001] direction, giving rise to R ₄ ⁴ (8) graph-set motif, while the molecules in 2 are linked into a 2D network in the bc plane, giving rise to R ₂ ² (10) and R ₃ ³ (12) motifs. The protonation equilibria of 1 and 2 have been studied by pH-potentiometry, with pK ₁ 9.01 and pK ₂ 5.50 determined for 1 and pK ₁ 8.58 and pK ₂ 5.26 determined for 2.     

Structural and spectroscopic characterization of a cationic aquanitrato copper(II) complex with the tetradentate Schiff-base ligand N,N′-bis[1–(2–pyridyl)ethylidene]ethane-1,2–diamine

Cu(NO3)2·3H2O reacts with 1 equiv. of the tetradentate Schiff base N,N-bis[1–(2–pyridyl)ethylidene]ethane-1,2–diamine (LA) in refluxing acetone to yield the [CuLA(ONO2)(H2O)](NO3) complex in ca. 80% yield. The structure of this salt has been determined by single-crystal X-ray crystallography. The copper is six-coordinated with the LA ligand in the equatorial plane and weakly bonded aqua and nitrato ligands above and below this plane. The complex cation is hydrogen-bonded to the nitrate counter-ion. The complex was also characterized by elemental analyses, molar conductivity, room-temperature magnetic susceptibility and spectroscopic (i.r., far-i.r., u.v.–vis, e.s.r.) studies. The data are discussed in terms of the nature of bonding and the known structure.     

Syntheses and crystal structures of oxovanadium(V) complexes derived from N′-[1-(2-hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide and 2-hydroxy-N′-[1-(2-hydroxynaphthyl)ethylidene]benzohydrazide

Reactions of bis(acetylacetonato)oxovanadium(IV) with N??-[1-(2-hydroxynaphthyl)ethylidene]-4-nitrobenzohydrazide (H₂HNB) and 2-hydroxy-N??-[1-(2-hydroxynaphthyl)ethylidene]benzohydrazide (H₂HHB), respectively, product two oxovanadium(V) species with the formulas [VO(OMe)(HNB)]₂ (I) and [VO(OMe)(HHB)] (II). The complexes I and II have been characterized by elemental analysis, IR spectra, and single crystal X-ray diffraction. The crystal of I is monoclinic: space group P2₁/n, a = 8.208(2), b = 14.528(3), c = 16.418(3) ?, ?? = 97.887(3)°, V = 1939.3(7) ?³, Z = 2. The crystal of II is triclinic: space group P $P\bar 1$ a = 8.334(2), b = 10.236(2), c = 11.337(2) ?, ?? = 80.91(3)°, ?? = 75.41(3)°, ?? = 75.63(3)°, V = 902.0(3) ?³, Z = 2. Complex I is a methoxide-bridged dimeric oxovanadium(V) complex, and complex II is a mononuclear oxovanadium(V) complex. The V atom in I is in an octahedral coordination, and that in II is in a square pyramidal coordination.     

Synthesis and crystal structures of two zinc(II) complexes derived from N-isopropyl-N′-[1-(2-methoxyphenyl)methylidene]ethane-1,2-diamine

Two isostructural mononuclear zinc(II) complexes, [ZnLBr₂] (I) and [ZnLI₂] (II), derived from the Schiff base N-isopropyl-N′-[1-(2-methoxyphenyl)methylidene]ethane-1,2-diamine (L), have been synthesized and characterized by elemental analysis, IR spectra, and X-ray single-crystal diffraction. The crystal of I is monoclinic: space group P2₁/n, a = 14.476(1) Å, b = 7.327(1) Å, c = 17.528(1) Å, β = 101.153(1)°, V = 1824.0(3) ų, Z = 4. The crystal of II is monoclinic: space group P2₁/n, a = 14.482(1), b = 7.329(1), c = 17.528(1)Å, β = 101.195(2)°, V = 1825.0(3)ų, Z = 4. The Zn atom in each complex is four-coordinated in a tetrahedral coordination, with one imine N and one amine N atoms of L, and two halide atoms. Both complexes and the Schiff base were tested in vitro for their antibacterial activities.     

Crystal structure and DNA interaction of a nickel(II) complex with N-benzyl-N ′-[2-(benzylamino)ethyl]ethane-1,2-diamine

N-Benzyl-N′-[2-(benzylamino)ethyl]ethane-1,2-diamine was prepared by reduction of its Schiff base analog. Its Ni(II) complex was synthesized and characterized. The crystal structure of the complex showed a square pyramidal structure in which a chlorine atom bridges two Ni(II) atoms in the common apical position. The dinuclear complex has two identical five-coordinate Ni(II) atoms. Interaction of the complex with calf thymus DNA was investigated by UV spectroscopy and fluorescence spectroscopy, and the results suggest that the complex binds to DNA by electrostatic interactions only. The binding constant is 1.02 × 10⁴ mol⁻¹ L.     

Synthesis and Crystal Structure of 4,4′-(4-(1-Naphthyl)-4-phenyl- 1,3-butadienylidene)-bis[N,N-diethylbenzenamine]

The title compound (C40H42N2) has been synthesized by the reaction of 1-(1-naphthyl)-1-phenyl-3-chloropropylene and bis(4-(diethylamino) phenyl)methanone, and characterized by IR, 1H NMR, MS and X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 17.047(3), b = 10.807(2), c = 1&494(4) (A), β = 105.727(4)°, V=3279.4(11) A3, Mr = 550.76, Z = 4, Dc = 1.115 g/cm3, μ(MoKα) = 0.085 mm-1, F(000) = 1184, the final R = 0.0625 and wR = 0.1384 for 2276 observed reflections (I ＞ 2σ(Ⅰ)). X-ray analysis reveals that the butadiene fragment adopts a planar cisiod conformation and makes a dihedral angel of 69.4(2)° with the naphthalene ring.     

Dinuclear Nickel(II) and Zinc(II) Complexes of 2,6-[N,N′-bis(2-hydroxyphenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol

Abstract

The symmetric 'end-off' compartmental proligand 2,6-[N,N′-bis(2-hydroxy-phenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol (H₃L) has been used to generate homodinuclear nickel(II) and zinc(II) complexes. The crystal structures of the complexes reveal that the di-nickel(II) complex is donor asymmetric and the di-zinc(II) complex is coordination number asymmetric. In both complexes non-coordinated acetic acid molecules are tightly hydrogen-bonded to the pendant phenols of the ligand generating a double acid salt of the type[CH₃COO…H…L…H…OOCCH₃]^3? in the dinickel complex and a single acid salt of the type [CH₃COO…H…L]^3? in the dizinc complex. In both cases the ligand periphery has been extended to provide a supraligand in which the donor potential of the original ligand has been enhanced.     

Host selectivity behaviour of trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,2-diamine and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,2-diamine when presented with six-membered heterocyclic guest mixtures

Two compounds, trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,2-diamine (1,2-DAX) and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,2-diamine (1,2-DAT), were assessed for their host ability in the presence of four heterocyclic guest species, namely pyridine (PYR), piperidine (PIP), morpholine (MOR) and dioxane (DIO). Each of these guests formed single solvent complexes with both host compounds. When 1,2-DAX and 1,2-DAT were recrystallized from various guest mixtures, it was shown that their selectivity orders were identical, DIO (46.6%)?>?MOR (23.0%)?>?PYR (18.9%)?>?PIP (11.5%) and DIO (85.9%)?>?MOR (23.7%)?>?PYR (8.9%)?>?PIP (8.5%), respectively, but that the thio host derivative possessed a significantly enhanced preference for DIO compared with its oxygen analogue. Additional experiments in order to investigate the various parameters at play in these complexation experiments involved single crystal diffraction experiments and thermal analyses.

     

Synthesis,Crystal Structure and Spectroscopic Properties of N,N′-Diphenyl-N,N′-bis(2-fluorophenyl)-1,1′-biphenyl-4,4′-diamine

A fluorinated tetraphenylbenzidine derivative, N,N′-diphenyl-N,N′-bis(2-fluorophenyl)-1,1′-biphenyl-4,4′-diamine (C36H26F2N2, Mr = 524.59) was synthesized via the palladiumcatalyzed Buchwald-Hartwig reaction of N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine with 2-fluoroiodobenzene (yield: 75%) and structurally characterized. It crystallizes in monoclinic, space group P21/n with a = 9.820(7), b = 14.305(11), c = 10.233(8) , β = 108.973(9)o, V = 1359.3(18) 3, Z = 2, Dc = 1.282 g/cm3, μ(MoKα) = 0.084 mm-1, F(000) = 548, S = 1.018, the final R = 0.0439 and wR = 0.0928. It presents a linear centrosymmetric framework constituted by a linkage of biphenyl as a bridge and two fluorinated diphenylamine moieties. The UV-Vis absorption and fluorescence spectra of the title compound were also investigated. This compound emits intense blue fluorescence with a peak wavelength of 406 nm in film.     

Synthesis and characterization of palladium(II) complexes [PdX2(p-diben)] (X = Cl,Br, I,N3, or NCO; p-diben = N,N′-bis(4-dimethylaminobenzylidene)ethane-1,2-diamine): crystal structure of [Pd(N3)2(p-diben)]

Five new complexes of general formula [PdX₂(p-diben)], where p-diben = N,N′-bis(4-dimethylaminobenzylidene)ethane-1,2-diamine) (1) and X = Cl (2), Br (3), I (4), N₃ (5), or CNO (6), were synthesized and characterized by physicochemical and spectroscopic methods. The crystal structure of compound (5) was determined by single-crystal X-ray diffraction. Complexes 2–6 were characterized as N,N-chelated products. The crystal structure confirmed this formulation for [Pd(N₃)₂(p-diben)], besides showing the isomerism inversion of one of the C=N bonds, caused by Pd(II) coordination.     

Ring Closure of N,N′:N,N′-bis(decamethylene)-1, 4-diamino-2,5-bis(10-cyanodecyloxy)benzene (IV)

Recently, β-chloro-α,β-unsaturated carbonyl compounds have become increasingly useful as intermediates in organic synthesis. For example, reactions involving a number of different cyclic β-chloro-α,β-unsaturated ketones with a variety of reagents (a malonate anion², the anion of the dithiolane derivative of ethyl glyoxalate³, zinc-silver couple in methanol⁴, dimethylsulfoxonium methylide^5,6) have produced a series of structurally diverse and potentially fruitful synthetic intermediates. The second-mentioned reagent has also been successfully reacted with a β-chloro-α,β-unsaturated ester³.     

Synthesis of N,N′-bis[4-(1H-1,2,3-triazol-1-yl)furazan-3-yl]-methylenediamine derivatives

[3+2] Cycloaddition of azide groups of N,N′-bis(4-azidofurazan-3-yl)methylenediamine to 1,3-dicarbonyl compounds and malonodinitrile was shown to proceed regioselectively with the formation of the corresponding N,N′-bis[4-(1H-1,2,3-triazol-1-yl)furazan-3-yl]methylenediamine derivatives. The reactions of N,N′-bis(4-azidofurazan-3-yl)methylenediamine with cyanoacetic acid ethyl ester and amide led to the formation of the product of transformation of the azide group in the starting compound to the amino groups.     

{Di-μ-bromotetra [N,N′-bis(3,5-dimethylanil)-4-methyl-2,6-bis(imino)phenoxy]-dinickel}bromide

A new bis-Schiff base ligand, N,N-bis(3,5-dimethylanil)-4-methyl-2,6-bis(imino)phenol was prepared by reacting 2,6-diformyl-4-methylphenol with 3,5-dimethylaniline. Treatment of the ligand with (DME)NiBr₂ (DME = 1,2-dimethoxyethane) gave the novel dinuclear bromo-bridged complex, {di--bromotetra [N,N-bis(3,5-dimethylanil)-4-methyl-2,6-bis(imino)phenoxy]dinickel} bromide, whose crystal structure was confirmed by single crystal X-ray analysis. The calculation, via the molecular mechanics method, performs well to reproduce the crystal structure. The complex shows some activity in respect of ethene oligomerization under mild conditions with methylaluminoxane (MAO) as a co-catalyst.     

Synthesis,characterization, and X-ray crystal structures of zinc(II) complexes with schiff bases 2-[(2-isopropylaminoethylimino)methyl]-5-methoxyphenol and N,N-dimethyl-N′-(1-pyridin-2-ylethylidene)ethane-1,2-diamine

Two new zinc(II) complexes, [ZnBr₂L¹] (I) and [ZnBr₂L²] (II), where L¹ is 2-[(2-isopropylaminoethylimino)methyl]-5-methoxyphenol and L² is N,N-dimethyl-N′-(1-pyridin-2-yl-ethylidene)ethane-1,2-diamine, were prepared and characterized using elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction. In complex I, the Zn(II) atom is coordinated by one phenolic O and one imino N atoms of L¹ and two Br atoms, forming a tetrahedral coordination geometry. In complex II, the Zn(II) atom is in a trigonal bipyramidal coordination geometry with the equatorial plane formed by the imino N atom of L² and two Br atoms and with the two axial positions occupied by one pyridine N and one amino N atoms of L². In the crystal structure of I, the mononuclear zinc complex molecules are linked through intermolecular N-H…O and N-H…Br hydrogen bonds, forming chains running along the y axis. The chains are further linked via intermolecular C-H…Br hydrogen bonds. In the crystal structure of II, the mononuclear zinc complex molecules are linked through intermolecular C-H…Br hydrogen bonds, forming a 3D network.     

Synthesis and Crystal Structure of Bisaqua-[N,N′-bis(3,5-dichlorosalicylidene)-1,3-diaminopropano]zinc(Ⅱ)

The title mononuclear zinc(Ⅱ) complex [Zn(BCDP)(H2O)2] (BCDP = N,N′-bis(3,5-dichlorosalicylidene)-1,3-diaminopropane) was prepared and characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system,space group Pnma with a = 7.887(1), b = 23.788(2), c = 10.295(4) (A), Z= 4, V= 1931.5(8) (A)3, Dc =1.786 g/cm3, Mr = 519.49, λ(MoKα) = 0.71073 (A), μ = 1.853 mm-1, F(000) = 1048, R = 0.0464 and wR = 0.0918. A total of 2273 unique reflections were collected, of which 1570 with 1 ＞ 2σ(Ⅰ) were observed. The molecule of the complex has crystallographic mirror symmetry. The Zn atom is sixcoordinated in an octahedral geometry. In the crystal, the molecules are linked through intermolecular O-H…O and O-H…C1 hydrogen bonds, forming chains running along the a axis.     

Synthesis and Crystal Structure of 4,4'-(4-(1-Naphthyl)-4-phenyl-1,3-butadienylidene)-bis[N,N-diethylbenzenamine]

1 INTRODUCTION Organic photo-conductors (OPCs), due to their great advantages over inorganic ones, have been widely used in xerography and holography and aroused considerable interest in the past several de- cades. Recently, almost all OPCs are of a layered structure with a thin charge generation layer (CGL) and a charge transport layer (CTL). Current resear- ches are directed to both improving the chara- cteristics of existing OPCs and developing new ma- terials for future applicati…     

Efficiency and Aging Comparison Between N,N′-Bis (3-methylphenyl)-N,N′-diphenylbenzidine (TPD) and N,N′-Di-[(1-naphthalenyl)-N,N′-diphenyl]-1,1′-biphenyl-4,4′-diamine (NPD) Based OLED Devices

In this paper we present and discuss experimental results to evaluate performances and aging behaviour of two Hole Transporting Material (HTM), TPD and NPD, in Organic Light Emitting Device (OLED) with structure: ITO/HTM/Alq3/Al. For each of these HTMs, devices with several thicknesses have been built, to measure and emphasize behaviours of material-geometry combinations. Electro-optical properties have been measured to estimate and compare brightness, power efficiency and aging decays.     

Dichlorotriethylphosphine-[N-formyl-N,N′-bis(3,4-dimethoxy)benzyl-trimethylenediamine] platinum(II)

By treatment of 1,3-bis(3,4-dimethoxybenzyl)-3,4,5,6-tetrahydropyrimidinium chloride (1) with KOBu ^t and [PtCl₂(PEt₃)₂]₂ N-coordinated platinum complex (2) is obtained. The Pt atom is coordinated in square planar arrangements by two chloride ions in a trans-configuration, the N-formyl-N,N′-bisaryltrimethylenediamine nitrogen atom, and the phosphine P atom. An extensive three-dimensional network of three C-H…O hydrogen bonds, two C-H…π and one π…π interactions are responsible for the crystal stabilization. Intermolecular hydrogen bonds and C-H…π interactions produce R ₂ ² (6), R ₂ ² (22), R ₂ ² (24), R ₃ ³ (23), R ₄ ⁴ (26), and R ₄ ⁴ (32) rings.