Two new dinuclear complexes with flexible bipyrazole ligand bridged via μ-Cl or μ1,1-N3

Two dinuclear complexes, {[Cd(bdpp)Cl₂](CH₃OH)}₂ (1) and [Cd(bdpp)(N₃)(NO₃)]₂ (2), have been synthesized by reactions of bdpp with cadmium salts (bdpp?=?1,3-bis(3′,5′-dimethylpyrazol-1′-yl)propane), and characterized by IR, element analysis, fluorescence properties and single crystal structural analysis. Cd in 1 has a trigonal bipyramidal coordination geometry and two such units form a dimer through two μ-Cl bridges. Each Cd in 2 has a distorted octahedral coordination geometry and two Cd units form a dimer through μ_1,1-N₃ bridges. The emission spectra show λ_em?=?413?nm for 1 and λ_em?=?338?nm for 2.     

Zirconium complexes with versatile β-diketiminate ligands: Synthesis, structure, and ethylene polymerization

A series of zirconium complexes (2c, 2d, 2f, 2g, 2h, 2i) containing symmetrical or unsymmetrical β-diketiminate ligands were synthesized by the reaction of ZrCl₄ · 2THF with lithium salt of the corresponding ligand in 1:2 molar ratio. X-ray crystal structures reveal that complexes 2d and 2g adopt distorted octahedral geometry around the zirconium center. These complexes showed moderate activities for ethylene polymerization, when methylaluminoxane (MAO) was used as cocatalyst. The steric and electronic effects of the substituents at the phenyl rings had considerable influence on the catalytic activities of the metal complex, as well as the molecular weights and molecular weight distributions (MWD) of produced polymers. Introduction of electron-withdrawing CF₃ group to phenyls in the ligand led to a significant increase of catalytic activities, and complex 2f (p-CF₃) exhibited the highest catalytic activity of 7.45 × 10⁵ g PE/mol-Zr · h among the investigated complexes. Complexes 2a-d could produce ultra-high molecular weight polyethylenes (UHMWPE) that were hardly dissolvable in decahydronaphthalene or 1,2-dichlorobenzene under the molecular weight measurement conditions. Nevertheless, polyethylenes with broad MWD could be afforded by complexes 2g-i, which was probably due to the introduction of bulky unsymmetrical ligands leading to the formation of multi active species under polymerization conditions. High-temperature ¹³C NMR data indicate the linear structure of obtained polyethylenes.     

Magnesium complexes containing β-ketiminate and β-diketiminate ligands with dimethylamino substituents on the ligand core nitrogen atoms

Treatment of dibutylmagnesium with two equivalents of 4-(2,2-dimethylhydrazino)dimethylhydrazone-3-penten-2-one (L¹H) in diethyl ether afforded Mg(L¹)₂ (76%), which contains η²-L¹ ligands with tetrahedral coordination at the magnesium ion. Similar treatment of dibutylmagnesium with 4-(2,2-dimethylhydrazino)-3-penten-2-one (L²H) or 5-(2,2-dimethylhydrazino)-2,6-dimethyl-4-hepten-3-one (L³H) and 4-tert-butylpyridine (4-tBupy) in diethyl ether afforded the octahedral complexes Mg(L²)₂(4-tBupy)₂ (85%) and Mg(L³)₂(4-tBupy)₂ (79%). Treatment of dibutylmagnesium with two equivalents of L²H or L³H in the absence of 4-tBupy afforded [Mg(L²)₂]₂ and Mg(L³)₂, however, these complexes were difficult to isolate due to the sticky nature of the crude products. A better synthetic approach entailed sublimation of Mg(L²)₂(4-tBupy)₂ or Mg(L³)₂(4-tBupy)₂ at 95-100 °C/0.05 Torr, which afforded [Mg(L²)₂]₂ (94%) and Mg(L³)₂ (80%) as colorless crystalline solids that were easily isolated. Treatment of [MgCp(CH₃)(OEt₂)]₂ with two equivalents each of 4-tBupy and L¹H afforded MgCp(L¹)(4-tBupy) (65%). Similar treatment of [MgCp(CH₃)(OEt₂)]₂ with two equivalents of L²H or L³H afforded the dimeric complexes [MgCp(L²)]₂ (81%) and [MgCp(L³)]₂ (84%), respectively. [MgCp(L²)]₂ and [MgCp(L³)]₂ decompose upon attempted sublimation at 125-130 °C/0.05 Torr to afford Cp₂Mg (47-53%) and [Mg(L²)₂]₂ (67%) or Mg(L³)₂ (74%). The X-ray crystal structures of Mg(L¹)₂, Mg(L³)₂(4-tBupy)₂, [Mg(L²)₂]₂, Mg(L³)₂, MgCp(L¹)(4-tBupy), [MgCp(L²)]₂, and [MgCp(L³)]₂ are described. The thermal stability and volatility of the complexes were determined through preparative sublimation experiments. Many of the complexes sublime without decomposition at moderate temperatures and low pressures, and thus represent new potential precursors for thin film growth using chemical vapor deposition and related techniques.     

Synthesis and fluorescence properties of novel pyrazine-boron complexes bearing a β-iminoketone ligand

A novel fluorescence dye based on pyrazine-boron complexes bearing a β-iminoketone ligand has been synthesized by using a simple two-step reaction. Synthesized complexes exhibited fluorescence in solution (F(max): 472-604 nm) and in the solid state (F(max): 496-624 nm). These complexes showed a larger Stokes shift (3690-4900 cm(-1)) than well-known boron dipyrromethene dyes (400-600 cm(-1), in most cases).     

Mixed ligand complexes of trivalent lanthanide ions with β-diketones and heterocyclic amines and their use as possible shift reagents

Sixty new complexes of the trivalent lanthanides (except Pm and Lu) and Yttrium of the general formulae, Ln(TFAA)₃o-phen, Ln(TFAA)₃dipy·2H₂O, Ln(dpm)₃im, Ln(dpm)₃pz, and Ln(fod)₃o-phen where TFAA = trifluoroacetyl-acetone-H, dpm = 2,2,6,6-tetramethyl 3,5-heptane dione-H, fod = 1,1,1,2,2,3,3-heptafluoro, 7,7-dimethyl 4,6-octane dione-H, o-phen = 1,10-phenathroline, dipy = 2,2′dipyridyl, im = imidazole and pz = pyrazole, have been synthesised and characterised by elemental analyses, melting points, molar conductance, magnetic susceptibility, thermogravimetric analysis, and IR spectral studies. The trivalent lanthanide ions have a coordination number of ten in the series Ln(TFAA)₃dipy·2H₂O. Their avidity to enhance their coordination number is so great that een in the presence of three such bulky ligands as heptafluorooctane dione the Ln(fod)₃ still coordinates with o-phen. Hexacoordinated trivalent lanthanides act as LIS reagents but it has been observed that even the eight coordinated and very bulky Pr(fod)₃o-phen produces dipolar shifts in the proton resonances of organic moities.     

Unexpected results of the reactions of manganese and vanadium β-diketiminate halide complexes with Na[HBEt3]

The reaction of [(^Menacnac^Dipp)Mn(μ-Cl)]₂(2) (^Menacnac^Dipp = HC(C(Me)NDipp)₂; Dipp = 2,6-Prⁱ₂C₆H₃) with sodium triethylborohydride in a toluene—THF mixture afforded the complex [(^Menacnac^Dipp)Mn(μ-H)₂BEt₂(THF)] (3). The reaction of 2 with Na[HBEt₃] in toluene under THF-free conditions gave a mixture of products. The set and the ratio of these products in the resulting crystalline mixture were established by quantitative powder X-ray diffraction analysis: [(^Menacnac^Dipp)Mn(μ-H)]₂(1), [(^Menacnac^Dipp)?Mn(μ-H)₂BEt₂] (4), and unreacted compound 2 in the ratio of 15:4:1 and traces of an unknown crystalline phase. The reaction of [(^Menacnac^Dipp)VCl₂] (5) with Na[HBEt₃] yielded the compound [(^Menacnac^Dipp)V(μ-H)(μ,κ^1:1?C:C′?C₂H₄)BEt₂] (6) containing the unusual ligand [HBEt₂(CH₂CH₂)]^2?. The vanadium analog of compound 3, [(^Menacnac^Dipp)V(μ-H)₂BEt₂(THF)] (7), was isolated in one experiment. Besides. a small amount of the complex [(^Menacnac^Dipp)V(μ-H)BEt₃(THF)] (8) was detected in the mixture of crystalline products. The structures of compounds 3, 4, 6, 7, and 8 were determined by single-crystal X-ray diffraction.

     

Structure and emission spectra of dinuclear lanthanide(III) β-diketonate complexes with a bridging 2,2′-bipyrimidine ligand

The 2,2′-bipyrimidine (bpm) adducts of the β-diketonate complexes of Eu(III), Sm(III), or Yb(III) with 2,2′,6,6′-tetramethyl-2,4-heptanedione (tmhd) resulted in the formation of dinuclear species. The synthesis and X-ray structure of these three new dinuclear lanthanide complexes are found to be similar. Each lanthanide ion is eight coordinate, bound to six O-atoms from the β-diketonates and 2N atoms from the bridging bpm ligand. They exhibit Ln–Ln distances (Sm(III): 6.935 Å, Eu(III): 6.901 Å, Yb(III): 6.679 Å) and Ln–ligand distances that are consistent with the decrease in radii across the lanthanide series. Absorption spectra of the complexes are dominated by ligand absorptions. Both the solution and solid state emission spectra of the complexes resemble ordinary monomeric lanthanide species, indicating independent ions in the dinuclear species. Cyclic voltammetry of all the complexes appear almost identical with discernable ligand centered redox reactions. The complex with Eu(III) ions, having the lowest possible lanthanide redox potential, was not found to display a signal corresponding to metal reduction.     

Mixed ligand complexes of β-diketonates: synthesis,characterization, and FAB mass spectral analysis

Complexes of the type MLL′ · nB (where M = Ni(II) and Cu(II); LH and L′H = 2,4-pentanedione (acacH), 1-phenyl-1,3-butanedione (bacH), and 1,3-diphenyl-1,3-propanedione (dbmH); n = 0 to 2 and B = water or pyridine) have been synthesized and characterized. IR spectra are consistent with uninegative bidentate ligands. Magnetic moments and electronic spectral studies reveal high-spin octahedral geometry for nickel(II) complexes and distorted octahedral stereochemistry for copper(II) complexes. Frozen chloroform solution ESR spectra of the copper(II) complexes display significant Jahn–Teller distortion and dimeric behavior of the complexes in solution. FAB mass spectra of the copper(II) complexes also exhibit peaks corresponding to dimers. Molecular, pseudo-molecular, dimeric pseudo-molecular, and fragment ion peaks in unit resolution mass spectra have been identified with the help of their isotope distribution pattern expected due to natural abundances of the ⁶³Cu and ⁶⁵Cu isotopes. All the FAB mass spectral peaks from the fragment ions containing copper have been interpreted on the basis of isotope distribution pattern.     

Synthesis and X-ray crystal structures of a series of 3d–4f lanthanide complexes: lanthanide(III)–copper(II) coordination polymers with 2,5-pyridinedicarboxylic acid ligand

A series of lanthanide–transition metal (Ln–M) complexes, namely, {[Ln₂Cu(pydc)₄(H₂O)₃]·H₂O} _n (Ln = Tb, Eu, Sm or Gd) (H₂pydc = 2,5-pyridinedicarboxylic acid) have been synthesized hydrothermally by self-assembly of the lanthanide ions, copper(II) ions and 2,5-pyridinedicarboxylic acid. All the complexes were characterized by physicochemical and spectroscopic methods; in addition, structural analyses revealed that all four complexes crystallized in monoclinic space group P2₁ /c. The molecular structure contains both Cu and Ln atoms, with pydc ligands bridging the four coordinate Cu(II) centers and eight coordinate lanthanide centers to form a 3-D net structure. Hence, copper is oxidized from Cu(I) to Cu(II) during the preparation. In addition, the thermogravimetric analysis of 1 is discussed. Contrary to expectations, compounds 1–3 show no photoluminescent properties. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Syntheses,structures, and luminescent properties of lanthanide complexes with N,N′-bis(p-methoxyphenyl)-3-oxapentanediamide

An amide-type acyclic polyether, N,N′-bis(p-methoxyphenyl)-3-oxapentanediamide (L), and its three lanthanide coordination compounds, [Ln(NO₃)(L)₂(H₂O)₂]?·?(NO₃)₂ [Ln?=?Pr (1), Nd (2), and Dy (3)], have been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis, and X-ray diffraction. Single crystal X-ray structure analyses reveal that 1 and 2 have the same structure and crystallize in the monoclinic crystal system with C2/c space group. The coordination geometry around the central atom is a distorted bicapped square antiprism. Extensive intermolecular hydrogen bonds in 1 and 2 result in 3-D supramolecular networks. Complex 3 exhibits luminescence in the visible region upon excitation with UV-rays.     

Inclusion complexes of Sulconazole with β-cyclodextrin and hydroxypropyl β-cyclodextrin: characterization in aqueous solution and in solid state

Complexation between sulconazole (SULC), an imidazole derivative with in vitro antifungal and antiyeast activity, and β-cyclodextrins (β-CD and HP-β-CD) was studied in solution and in solid states. Complexation in solution was evaluated using solubility studies and nuclear magnetic resonance spectroscopy (¹H-NMR). In the solid state, differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM) and RX diffraction studies were used. Solubility studies suggested the existence of inclusion complex between SULC and β-CD or HP-β-CD. ¹H-NMR spectroscopy studies showed that the complex formed occurs by complexation of imidazole ring into inner cavity. DSC studies showed the existence of a complex of SULC with β-CD. The TGA and RX studies confirmed the DSC results of the complex. Solubility of SULC in solid complexes was studied by the dissolution method and it was found to be much more soluble than the uncomplexed drug.     

Synthesis and structure of novel copper(II) complexes with pyrazole derived ligands and metal–ligand interaction in solution

Two new ligands of the coumarin type have been synthesized and characterized by ¹H, ¹³C NMR, IR and MS. The crystal and molecular structures of ligand 2, determined by the X-ray diffraction method, are presented. With copper(II) these ligands create solid complexes of the type CuLCl₂, where L is 5-(2-hydroxybenzoyl)-3-methyl-1-(2-pyridinyl)pyrazol-4-carboxylic acid methyl ester (2) or 3-methyl-1-(2-pyridinyl)-1H-chromene[4,3-c]pyrazol-4-on (3). The new copper(II) complexes have been characterized by elemental analysis and solid state FT-IR. The protonation constants of ligands 2 and 3 have been determined in 5% v/v 1,4-dioxane–water solution (25 °C). The coordination modes in the complexes with copper(II) are discussed for 2 on the basis of potentiometric and UV–Vis data.     

Synthesis and study of the trypanocidal activity of catechol-containing 3-arylcoumarins,inclusion in β-cyclodextrin complexes and combination with benznidazole

American trypanosomiasis or Chagas disease is caused by the protozoan parasite Trypanosoma cruzi, and is considered a neglected disease, being an important problem for public health. Benznidazole (BZN) is the drug used to treat the disease. However, it has limited efficacy and adverse side effects. Therefore, the development of new therapeutic alternatives is necessary. In this work, the trypanocidal activity and cytotoxicity of a series of catechol-containing 3-arylcoumarins, their combination with BZN, and the inclusion in β-cyclodextrins (β-CDs), were evaluated. The results obtained showed that the entire series has moderate trypanocidal activity on the trypomastigote form of the parasite, being the 3-(4′-bromophenyl)-6,7-dihydroxycoumarin (8) the most active compound (IC₅₀ = 34 μM) and the most cytotoxic in Vero cells (IC₅₀ = 162 μM) as well. By forming the inclusion complex 8-β-CDs, the trypanocidal activity and cytotoxicity decreased. In addition, the formation of inclusion complexes increased the solubility. The possible mechanism of action of 8 was evaluated and proved to be through the generation of oxidative stress. The combination with BZN presented a synergistic effect on the trypanocidal activity, reducing the necessary dose of BZN. The presence of a catechol in the studied scaffold seems to modulate the trypanocidal activity, and the combination of drugs proved to be a promising alternative strategy for treating the disease.     

Theoretical study of β- and γ-cyclodextrin complexes with ferrocene-containing azoles

The interaction between cyclodextrins (β- and γ-CD) and ferrocenyl azoles (i.e., pyrazole ferrocenes (I, III–V) and benzimidazole ferrocenes (VI, VII)), along with 1-ferrocenylethanol (II), each in the form of (R)- and (S)-enantiomers, in forming inclusion complexes is studied for the first time using detailed quantum chemical calculations. Compounds are calculated in terms of the density functional theory (DFT), using the Becke–Lee–Yang–Parr (B3LYP) approach in the 6-31G* basis sets. For the considered CD complexes with enantiomers of I–VII, structures in which a guest partially enters a host cavity from the side of the heterocyclic substituent (pyrazole or benzimidazole) are found to be energetically advantageous. It is shown that for successful resolution of (R,S)-enantiomers on chiral phases containing cyclodextrins, we must consider the interaction between outer hydroxyl groups on the CD cone’s surface, in addition to the correspondence of geometric dimensions. The calculated data correlate well with the data from the chromatographic separation of guest enantiomers on cyclodextrin sorbents.     

Transition metal complexes with thiosemicarbazide-based ligand – Part LV: Synthesis and X-ray structural study of novel Ni(II) complexes with pyridoxal semicarbazone and pyridoxal thiosemicarbazone

Reaction of aqueous solutions of Ni(NO₃)₂ and pyridoxal semicarbazone (PLSC) in the presence of NaN₃ afforded two complexes, viz. green, paramagnetic binuclear octahedral [Ni₂(PLSC)₂(μ_1,1-N₃)₂(N₃)₂] · 2H₂O (1) and, as admixture, red, octahedral [Ni(PLSC–H)₂] · 2H₂O (2) complex. Under the same reaction conditions, pyridoxal thiosemicarbazone (PLTSC) gave only one diamagnetic square-planar, red complex [Ni(PLTSC–H)N₃] · H₂O (3). In the absence of NaN₃, the reaction of PLTSC and Ni(NO₃)₂ yielded brown paramagnetic octahedral complex [Ni(PLTSC)₂](NO₃)₂ · H₂O (4).     

Synthesis and characterization of yttrium,europium, terbium and dysprosium complexes containing a novel type of triazolyl–oxazoline ligand

We report the synthesis of a novel type of bidentate chiral ligand which structurally derives from the association of a 1,2,3-triazole ring with a chiral oxazoline. Yttrium and lanthanide nitrato-complexes of the new triazolyl–oxazoline ligand were prepared and characterized. The coordination mode of the ligand was ascertained by means of DFT calculations. Trivalent europium and terbium derivatives resulted appreciably photoluminescent upon excitation with UV light, showing the typical ⁵D₀ → ⁷F_J and ⁵D₄ → ⁷F_J emissions, respectively. These species were successfully used for the preparation of luminescent-doped polymeric materials.