Synthesis and characterization of some acetoxime-modified hetero-metal alkoxide precursors of zinc(II) and aluminum(III) for sol–gel transformation to nano-sized ZnAl2O4

Reactions of [ZnAl₂(OPr_i)₈] [A] with acetoxime in different molar ratios in refluxing anhydrous benzene, yield complexes of the type [ZnAl₂(OPrⁱ)_8?n{(CH₃)₂CNO}_n] {where, n = 1–4}. All the complexes are transparent viscous/foamy solids. They were characterized by elemental analyses, FT-IR and NMR (¹H, ¹³C {¹H}) spectral studies. ²⁷Al NMR spectrum of [ZnAl₂(OPrⁱ)₄{(CH₃)₂CNO}₄] [4] in CDCl₃ suggests presence of four coordination around both the aluminum atoms. IR spectra suggest that the oximato ligands bind the aluminum atoms in a side on manner in all the complexes. The ESI-mass spectrum of the representative derivative [4] suggests its monomeric nature while the thermo-gravimetric curve shows its low thermal stability. Sol–gel transformations of the precursors (A), (1), and (4) yielded nano-sized ZnAl₂O₄ samples (a), (b) and (c) at ~500 °C, respectively. The XRD patterns of (a), (b) and (c) indicate formation of cubic phase nano-sized zinc aluminate in all the samples. Surface morphologies of these samples were investigated by SEM images. IR spectra as well as EDX analyses indicate formation of pure zinc aluminate in all the cases. TEM image of sample (c) shows spherical (~5–8 nm) morphology.     

Synthesis,characterization, spectrophotometric and electrochemistry studies,and DNA cleavage of copper(II) complexes of a new azacrown bis-macrocycle and its mono-cyclic analogue

A new azacrown bis-macrocycle (5) and its mono–cyclic analogue (7) were synthesized and characterized by FT-IR, ¹H NMR, ¹³C NMR, DEPT ¹³C NMR, MS, and elemental analysis. The reaction with copper(II) nitrate yielded the corresponding complexes, formulated as Cu(5)(NO₃)₂·3H₂O (8), and Cu(7)(NO₃)₂·2.5H₂O (9). Also the stoichiometries of the complexes were determined in alcoholic solution and the results show that for both complexes the ratio of ligand to metal was 1:1 in methanol. The redox behavior of both complexes has been studied by cyclic voltammetry in DMF. Cyclic voltamogram of 8 shows quasi-reversible Cu^II/Cu^I redox couple whereas 9 shows a reversible Cu^II/Cu^I redox couple. Mono- and bis-macrocycle copper(II) complexes (8 and 9 respectively) cleaved plasmid pGS2 DNA by using an oxidative mechanism with 3- mercaptopropionic acid (MPA) as the reductant under aerobic conditions. The bis-macrocycle copper(II) complex 8 showed higher cleavage efficiency than their mono-macrocycle analogue 9 at the same Cu²⁺ concentration.     

Syntheses and characterization of a new class of zirconia precursors of oxime-modified zirconium(IV) isopropoxide

Some oxime modified complexes of the type [Zr{OPrⁱ}_4?n{L}_n] {where, n = 1–4 and LH=(CH₃)₂C=NOH (1–4) and C₉H₁₆C=NOH (5–8)} have been synthesized by the reaction of [Zr(OPrⁱ)₄·PrⁱOH] with oximes, in anhydrous refluxing benzene. These synthesized complexes were characterized by elemental analyses, molecular weight measurements, ESI-mass, FT-IR and NMR (¹H and ¹³C{¹H}) spectral studies. The ESI-mass spectral studies indicate dimeric nature for [Zr{OPrⁱ}₂{ONC(CH₃)₂}₂] (2), [Zr{OPrⁱ}₃{ONC₁₀H₁₆}] (5) and [Zr{OPrⁱ}{ONC₁₀H₁₆}₃] (7) and monomeric nature for [Zr{ONC₁₀H₁₆}₄] (8). Oximato ligands appear to bind the zirconium in side on manner in all the complexes. Thermogravimetric curves of (2) and (8) exhibit multi-step decomposition with the formation of ZrO₂, under nitrogen atmosphere. Sol–gel transformations of precursors (5), (6), (7) and (8) in organic medium, yielded nano-sized tetragonal phase of zirconia samples (a), (b), (c) and (d), respectively, on sintering at ~600 °C. All these samples were characterized by Powder XRD patterns and EDX analyses. Surface morphologies of these samples were investigated by SEM images.     

Syntheses and characterization of a new class of vanadia precursors of oxime-modified oxovanadium(V) isopropoxide,crystal and molecular structure of [VO{ONC10H16}3]

Modification of [VO(OPrⁱ)₃] with oximes in different molar ratios, yielded new class of vanadia precursors, [VO{OPrⁱ}_3?n{L}_n] {where, n = 1–3 and LH = C₉H₁₆C=NOH (1–3) and (CH₃)₂C=NOH (4–6)}.All the products are yellow in colour. (1) and (2) are liquid/viscous liquid, while others are solids. Molecular weight measurements of all these derivatives and the ESI-mass spectral studies of (1), (2), (3) and (5) indicate their monomeric nature. ¹H and ¹³C{¹H} NMR spectra suggest that the oximato moieties are monodentate in solution which was further confirmed by the ⁵¹V NMR signals, appeared in the region expected for tetra-coordinated oxo-vanadium atoms. On ageing, a disproportionation reaction occurs in (1) and some crystals appeared. Single crystal X-ray diffraction analyses of the crystals obtained from (1) as well as from (3) were found to be the same and indicate the presence of side-on {dihapto η ²-(N, O)} binding modes of the oximato ligands, leading to the formation of seven coordination environment around the vanadium atom. Thermogravimetric curve of (1) exhibits multi-step decomposition with the formation of V₂O₅ as the final product at ~850 °C. Sol–gel transformation of (3) yielded (a) VO₂ sintered at 300 °C and (b) V₂O₅ at 600 °C. Similarly, sol–gel transformations of (1) and (2) yielded V₂O₅ (c) and (d) at 600 °C, respectively. Formation of monoclinic phase in (a) and orthorhombic phase in (b), (c) and (d) were confirmed by powder XRD patterns.     

Synthesis, spectroscopic studies of new water-soluble Co(II) and Cu(II) macrocyclic complexes of 4,15-bis(2-hydroxyethyl)-2,4,6,13,15,17-hexaazatricyclodocosane: their interaction studies with calf thymus DNA and guanosine 5′ monophosphate

New water soluble Co(II) 1, Ni(II) 2 and Cu(II) 3 complexes of 4,15-bis(2-hydroxyethyl)-2,4,6,13,15,17-hexaazatricyclodocosane Co(II) were synthesized and characterized by various techniques, viz. elemental analysis, conductivity measurements, infrared, electronic, ESI-MS, ¹H and ¹³C NMR spectroscopy. Molar conductance measurements in aqueous solution showed that complexes 1, 2 and 3 are ionic in nature. On the basis of spectroscopic data, a square planar geometry was assigned to the complexes involving four N-atoms of the two cyclohexane moieties. Interaction studies of 1 and 3 with CT-DNA were carried using UV/Visible absorption spectroscopy, fluorescence spectrophotometry, cyclic voltammetry and viscosity measurements. Absorption spectral traces reveal 27.7 and 23.3% hyperchromism for complexes 1 and 3, respectively indicative of strong binding to CT-DNA. These results were authenticated by fluorescence quenching experiments and viscosity measurements. The intrinsic binding constants K _b of 1 and 3 are 2.94 × 10⁴ and 2.71 × 10⁴ M^?1, respectively. Early transition metals show preference for O6 position while later ones copper and cobalt prefer N7 position of DNA base guanine. To validate this hypothesis, interaction studies of copper (II) and cobalt (II) complexes were carried out with 5′GMP, which revealed electrostatic interactions are more favored along with hydrogen bonding than coordinate covalent interaction to N7 position of guanine.     

Synthesis and characterization of new metal-free and metallophthalocyanines fused α-methylferrocenylmethoxy units

Synthesis of metal-free and metallophthalocyanines bearing α-methylferrocenylmethoxy units was described. Precursor 3 required for the preparation of phthalocyanines 4–9, was synthsized by the nucleophilic aromatic substitution reaction between α-methylferrocenylmethanol and 4-nitrophthalonitrile in dry DMF. The metal-free phthalocyanine 4 was prepared from 4-(α-methylferrocenylmethoxy)phthalonitrile 3 in 1-pentanol with a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Metallophthalocyanines (M = Zn, Cu, Co, Ni and Pb) were prepared by cyclotetramerization reaction of phthalonitrile with appropriate materials. The phthalonitrile, metal-free and metallophthalocyanines were characterized by ¹H and ¹³C NMR, FT-IR UV–Vis and mass spectral data, as well as elemental analyses, which were consistent with the proposed structures.     

Synthesis,characterization, and thermal behavior of palladium(II) complexes containing 4-iodopyrazole

The mononuclear pyrazolyl complexes [PdCl₂(HIPz)₂] (1), [PdBr₂(HIPz)₂] (2), [PdI₂(HIPz)₂] (3), [Pd(SCN)₂(HIPz)₂] (4), and [Pd(NHCOIPz)₂] (5) have been prepared. Compound 1 was obtained from the displacement of acetonitrile from [PdCl₂(CH₃CN)₂] precursor by the 4-iodopyrazole (HIPz) ligand, whereas 2–5 were synthesized by substitution of the chlorido in 1 by the respective anionic group. The compounds were characterized by elemental analysis, infrared spectroscopy, and ¹H NMR spectroscopy. The thermal behavior of 1–5 has been studied by TG and DTA. The thermal stability of [PdX₂(HIPz)₂] compounds varies according to the trends X = Cl^? < I^? ? SCN^?< Br^?. No stable intermediates were isolated during the thermal decompositions due to the overlap of the degradation processes. The final products of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.     

Synthesis and characterization of novel calix[4]arene piperazine derivative for the extraction of transition metals and dichromate ions

This article displays the synthesis of N-(2-tosylato)ethylpiperazine (ii) and 5,11,17,23-tetra-tert-butyl-25,27-bis-(2-piprazinoethyl)-26,28-dihydroxycalix[4]arene (3). Compounds (ii) and 3 were characterized through elemental analysis, FT-IR, ¹H NMR and/or ¹³C NMR studies. The transition metal cations (Hg²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Cd²⁺) and dichromate anion were studied by liquid–liquid extraction experiment. The results showed that compound 3 has moderate but selective extraction ability for Hg²⁺ and dichromate anion. Comparison between extraction properties of compound 3 with previously reported 5,11,17,23-tetra-tert-butyl-25,27-bis(isoniazidylcarbonylmethoxy)-26,28-dihydroxy-calix[4]arene (4) and protonated pyridinium form of 4 (5) is also described.     

Preparation and structures of some new 1H-pyrazole derivatives

Some new 3,5-diaryl-1H-pyrazoles were prepared from aryl methyl ketones via Claisen condensation with aromatic esters and followed by cyclization with hydrazine monohydrate. Their structures were confirmed by IR, ¹H NMR spectroscopy, mass spectrometry and elemental analysis. The X-ray structure for 3(5)-(4-tert-butylphenyl)-5(3)-(4-methoxyphenyl)-1H-pyrazole (2b) was presented. The results show that compound 2b exists as tautomers I and II, and its molecules are connected by the N–H···N intermolecular hydrogen bonds to form cyclic dimers consisting of the tautomers I and II.     

Synthesis and spectroscopic studies of some new oxazepine derivatives throughout [2+5] cycloaddition reactions (III)

The present work included condensation reactions of o-tolidine with different aromatic aldehydes in absolute ethanol to give Schiff bases (w ₉ –w ₁₂ ) in high yield which, on reaction with maleic and phthalic anhydride by [2+5] cycloaddition reactions in the presence of suitable solvents, give the corresponding [1,3]oxazepine-4,7-dione (w ₉ m–w ₁₂ m) and [1,3]oxazepine-1,5-dione (w ₉ ph–w ₁₂ ph), respectively. The structure of the newly synthesized compounds were monitored by TLC and established on the basis of elemental analysis, FT-IR, and ¹H NMR.     

Non-aqueous synthesis of nano-sized aluminium(III) isopropoxide derivatives with 8-hydroxyquinoline and their sol–gel transformation to nano-sized δ-alumina

Non-aqueous reactions of aluminum isopropoxide with 8-hydroxyquinoline (Hq = HONH₆C₉) in 1:1, 1:2 and 1:3 molar ratios in anhydrous benzene yield complexes of the type [q_nAl(OPrⁱ)_3?n] {where n = 1 (1), n = 2 (2), n = 3 (3)}. Progress of the reactions were monitored by estimating liberated 2-propanol in benzene-2-propanol azeotrope by oxidimetric method. All the products were fluorescent green powders, sparingly soluble in CHCl₃. They were characterized by elemental analysis, FT-IR and (¹H, ¹³C and ²⁷Al) NMR studies. The ESI mass spectral studies indicate dimeric nature for (1) and (2) and monomeric nature for the compound (3). The XRD spectra of (1–3) showed crystalline nature with the average particle size of 45, 32 and 27 nm respectively, as evaluated from Debye–Scherrer equation. The XRD spectrum of (3) also suggests the formation of β-crystalline polymorphs of Alq₃. The SEM images appear to indicate granular morphology for (1) and formation of cylindrical shaped rods for (2) and (3). Sol–gel hydrolysis of (1), (2) or (3) in presence of a strong acid as well as of the precursor, Al(OPrⁱ)₃,without acid or base catalyst, followed by sintering at 950 °C yielded tetragonal primitive phase of nano-sized δ-alumina in all the cases, as reflected by their powder X-ray diffraction pattern. The IR, SEM and EDX studies also support the formation of transition alumina.     

Synthesis and fluorescence properties of 7-hydroxy-3-(2-pyridyl)coumarin derivatives

Three coumarin derivatives, 7-hydroxy-3-(2-pyridyl)coumarin (HPC), 7-(4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)benzyloxy)-3-(2-pyridyl)coumarin (Ox-PC), and 7-(4-(9H-carbazol-9-yl)butoxy)-3-(2-pyridyl)coumarin (Cz-PC), were synthesized and characterized by elemental analysis, ¹H NMR, FT-IR, and UV?Cvis absorption spectra. The fluorescence behaviors of the compounds in methanol solutions and solid states were investigated. HPC exhibits weak green emission, whereas Cz-PC and Ox-PC show strong blue emissions in dilute solutions.     

Dipyrrolylquinoxaline-bridged hydrazones: a new class of chemosensors for copper(II)

Novel 2,3-bis(1H-pyrrol-2-yl)quinoxaline-functionalized hydrazones were prepared and characterized as new chemosensors for copper(II) ion. The binding properties of the compounds 4, 5, 6 and 7 for cations were examined by UV–vis, fluorescence spectroscopy, and linear sweep voltammetric experiments (LSV). The results indicate that a 1:1 stoichiometric complex is formed between compound 4 (or 5, 6, 7) and copper(II) ion, and the association constant is 1.3?×?10⁵ M^?1 for 4, 2.1?×?10⁶ M^?1 for 5, 4.1?×?10⁵ M^?1 for 6 and 8.0?×?10⁵ M^?1 for 7, respectively. The recognition mechanism between compound 4 (or 5, 6, 7) and metal ion was discussed based on their electrochemical properties, absorbance changes, and the fluorescence quenching effect when they interact with each other. Control experiments revealed that compound 4 (or 5, 6, 7) has a highly selective response to copper (II) ion.     

Synthesis and characterization of glycol ether and oxime modified precursors of niobium(V) for soft transformation to niobia

A glycol ether modified precursor, [Nb{O(CH₂CH₂O)₂}(OPrⁱ)₃] (A) was prepared by the reaction of Nb(OPrⁱ)₅ with O(CH₂CH₂OH)₂ in 1:1 molar ratio in anhydrous benzene. Further reactions of A with a variety of internally functionalized oximes in different molar ratios, yielded heteroleptic complexes of the type, [Nb{O(CH₂CH₂O)₂}(OPrⁱ)_3?n{ON = C(CH₃)(Ar)}_n] (1–9) {where Ar = C₄H₃O-2, n = 1 [1], n = 2 [2], n = 3 [3]; C₄H₃S-2, n = 1 [4], n = 2 [5], n = 3 [6]; C₅H₄N-2, n = 1 [7], n = 2 [8], n = 3 [9]}. All the above derivatives have been characterized by elemental analyses, FT-IR, NMR (¹H, ¹³C {¹H}) and FAB mass studies. Spectral studies of 1–9 suggest the presence of mono- and bi-dentate mode of oxime moieties, in the solution and in the solid states, respectively. FAB mass studies indicate monomeric nature for 3 and dimeric nature for A. TG curves of A and 6 show their low thermal stability. Soft transformation of A and 3 to pure niobia, a and b, respectively have been carried out by sol–gel technique. The XRD patterns of niobia a and b suggest the formation of nano-size crystallites of average size of 10.8 and 19.5 nm, respectively. The XRD patterns also indicate the formation of monoclinic phase of the niobia in both the cases. Absorption spectra of a and b suggest energy band gaps of 4.95 and 4.39 eV, respectively.     

Characterization of tetraene intermediates formed in the [3+2]-photocycloaddition of 1,4-dicyano-6-methylnaphthalene with styrene

The early stages of the [3+2]-photocycloaddition of 1,4-dicyano-6-methylnaphthalene (6) with styrene (7) were investigated by UV–visible absorption and ¹H NMR spectroscopy. An intermediate species was detected and characterized as 8-methyl-2-phenyl-1,2,2a,8-tetrahydroacenaphthylene-2a,5-dicarbonitrile (9). Computational studies explained the regioselective [3+2]-photocycloaddition at the 4,5-position of 6 to form zwitterion 8, and subsequent thermal transformation to form 9.     

Synthesis of aryl-substituted or aryl-fused N-hydroxyethyl and N-hydroxymethypyrazole derivatives as potential ligands for the estrogen receptor

A new series of N-hydroxyethylpyrazole (12a–f) and N-hydroxymethylpyrazole derivatives (15a–f) were designed for their estrogenic activities, having a 11.0 ± 0.5 Å distance between their two hydroxyl groups, aliphatic–OH and phenolic–OH similar to 17β-estradiol (E2) as an endogenous hormone. To synthesize the title compounds, the key intermediate 1,3-dicarbonyl derivatives (2 and 8), were treated with hydrazine hydrate to produce the pyrazole ring 5 and 9. Further hydroxyalkylation of the latter produced the title pyrazoles. The position of hydroxyethyl or hydroxymethyl substituents in the products was determined through 2D NOE NMR spectroscopy.     

Synthesis and thermal behavior study of complexes of the type [Pd(μ-X)(4-eb-p-phen)]2 (X = Cl,Br, I,N3, NCO,SCN) and 4-eb-p-phen [bis(4-ethylbenzyl)p-phenylenediimine]

The Schiff base bis(4-ethylbenzyl) p-phenylenediimine, 4-eb-p-phen (1), and six new dimeric Pd(II) complexes of the type [Pd(μ-X)(4-eb-p-phen)]₂ {X = Cl (2), Br (3), I (4), N₃ (5), NCO (6), SCN (7)} have been synthesized and characterized by elemental analysis, IR spectroscopy, and ¹H and ¹³C{¹H}-NMR experiments. The thermal behavior of the complexes 2–7 has been investigated by means of thermogravimetry and differential thermal analysis. From the final decomposition temperatures, the thermal stability of the complexes can be ordered in the following sequence: 3 > 4 > 7 > 2 ≈ 5 > 6. The final products of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction (XRD).     

Facile Preparation of Mn3O4 Hausmanite Nanoplates from a New Octahedral Manganese (III) Schiff Base Complex

A novel bidentate Schiff base ligand L (L = N-(4-amino-2-chloro-phenyl)-2-hydroxybenzaldehyde) and the subsequent octahedral manganese(III) Schiff base complex MnL ₃ have been synthesized and characterized by, FT-IR spectroscopy and elemental analyses (CHN). Additionally, Schiff base ligand has been characterized by ¹H NMR spectroscopy. Thermogravimetric analysis of the ligand and its metal complexes reveals their thermal stability and decomposition pattern. Thus, the MnL ₃ complex has been investigated as a novel precursor for the facile preparation of Mn₃O₄ nanoparticles via solid-state thermal decomposition under aerobic conditions, at a temperature of ca. 450 °C The resulting Mn₃O₄ nanocrystals were characterized by FT-IR spectroscopy, X-ray powder diffraction (XRPD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The XRPD studies reveal the characteristic diffraction peaks indexed to the Mn₃O₄ hausmanite structure, while the absence of additional peaks tends to clearly indicate the high purity of the sample. In addition, the TEM/SEM investigations displayed the nanoplate shape of the rather monodisperse crystalline Mn₃O₄ nanoparticles, with an average diameter of ca. 10 nm. The statistical distribution of the nanoparticles size has to be provided with an histogram graphic.     

Paramagnetic properties and molecular structure of coordination saturated inclusive lanthanide complexes with 18-crown-6 using NMR

Earlier NMR spectra of lanthanide complexes [Ln(18-crown-6)(NO₃)₃] have been analyzed by us (Babailov in Inorg Chem 51(3):1427–1433, 2012), where Ln³⁺ = La³⁺ (I), Ce³⁺ (II), Pr³⁺ (III) and Nd³⁺ (IV). The NMR signal assignment and conformational molecular dynamic have been found by 1D NOE and relaxation spectroscopy as well as on 2D NOESY and EXSY experiments at 170 K. In the present paper the ¹H NMR method is used to study the features of paramagnetic properties of complexes I–IV and [Eu(18-crown-6)(NO₃)₃] (V) at ambient temperature. The investigation was carried out by special method based on analysis of Δδ/z> on k(Ln)/z> (where k(Ln) is Bleaney’s constant, Δδ is paramagnetic contribution to the lanthanide-induced shifts). The obtained results indicate that the structure of the complexes (in CDCl₃ and CD₂Cl₂) are very similar.     

The structure and thermal properties of novel DOPO-containing 1,3-benzoxazines

Three DOPO (9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide)-containing benzoxazin (3a–3c) were successfully prepared from 2-hydroxybenzaldehyde, p-substituted aniline, and DOPO by a three-step procedure. Since the phosphorus and the adjacent aliphatic carbon are both chiral centers, two pairs of enantiomers exist in 3a, 3b, or 3c. Compound 3a′, which is a pair of enantiomers existing in 3a, was isolated using recrystallization in ethyl acetate solvent. All the structures were confirmed by FT-IR, NMR, and MS spectra. The X-ray analysis indicated that the 3a′ is the RR/SS enantiomers and belongs to the monoclinic crystal system, its space group being P2₁/c. The thermal properties were investigated by DSC and TG. It has been found that the peak temperature of thermally induced ring-opening reaction was around 260–270 °C. Compounds (3a–3c, 3a′, and 3c′) had two similar thermal processes from 50 to 600 °C in TG, whereas the compound 3b′ had three thermal processes. The char yields of 3a–3c were 18.10, 16.84, and 16.34 %, respectively, while those of 3a′–3c′ were 26.00, 31.80, and 19.21 %, respectively. The results indicated that compounds 3a′–3c′ had better char properties than 3a–3c.