A mixed‐ligand quinazoline‐based Ni(II) Schiff base complex: Synthesis,characterization, crystal structure,antimicrobial investigation and catalytic activity for the synthesis of 2H–indazolo[2,1‐b]phthalazine‐triones

A tridentate Schiff base ligand, (E)‐3‐((2‐hydroxy‐3‐methoxybenzylidene)amino)‐2‐methylquinazolin‐4(3H)‐one [HL], and its mixed‐ligand Ni(II) complex [Ni(L)(imi)], were synthesized and fully characterized using elemental analysis, FT‐IR, UV–Vis and ¹HNMR spectroscopy techniques. The structure of the synthesized ligand and complex was determined with single crystal X‐ray diffraction method. In the complex, a square planner geometry was observed around the Ni(II) central atom coordinated with the donor atoms of the Schiff base ligand and one nitrogen of imidazole group. In addition, the catalytic activity of the complex on the three‐component condensation of hydrazine hydrate with phthalic anhydride and dimedone to obtain 2H–indazolo[2,1‐b]phthalazine‐triones was investigated. Furthermore, in‐vitro antimicrobial studies were performed that indicated the great antibacterial activities of the Ni(II) complex against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Bacillus cereus bacteria.     

Synthesis,spectroscopic evaluation,molecular modelling,thermal study and biological evaluation of manganese(II) complexes derived from bidentate N,O and N,S donor Schiff base ligands

Manganese(II) complexes having the general composition Mn(L)₂X₂ (where L = 3‐bromoacetophenone semicarbazone, 3‐bromoacetophenone thiosemicarbazone, 1‐tetralone semicarbazone, 1‐tetralone thiosemicarbazone, flavanone semicarbazone or flavanone thiosemicarbazone and X = Cl^? or ½SO₄^2?) were synthesized. All the complexes were characterized using elemental analyses, molar conductance and magnetic moment measurements, and mass, ¹H NMR, infrared, electron paramagnetic resonance and electronic spectral studies. The molar conductance of the complexes in dimethylsulfoxide lies in the range 10–20 Ω^?1 cm² mol^?1 indicating their non‐electrolytic nature. All the complexes show magnetic moments corresponding to five unpaired electrons. The possible geometries of the complexes were assigned on the basis of electron paramagnetic resonance, electronic and infrared spectral studies. Some of the synthesized ligands and their complexes were screened for their antifungal activities against fungi Macrophomina phaseolina, Botrytis cinerea and Phoma glomerata using the food poison technique and their antibacterial activities against Xanthomonas campestris pv. campestris and Ralstonia solanacearum using the paper disc diffusion method. They showed appreciable activities.     

Salicylaldimine‐functionalized poly(m‐phenyleneethynylene) as turn‐on chemosensor for ferric ion

A new turn on fluorescent probe for ferric ion based on poly(m‐phenyleneethynylene salicylaldimine) ( PPE‐IM ) has been developed. The preparation of PPE‐IM involves post‐polymerization functionalization of the corresponding polymeric amine, PPE‐AM , via the condensation with salicylaldehyde. The degree of polymerization of both PPE‐IM and PPE‐IM is 17 with polydispersity index of 1.5. In aqueous solution, the polymeric PPE‐IM is highly stable unlike its small molecule analog which is gradually hydrolyzed. The weak fluorescence of initial PPE ‐ IM (λ_em = 470) is greatly enhanced by 300 folds upon the addition of Fe³⁺. The ¹H NMR reveals that the fluorescence enhancement is caused by Fe³⁺‐induced hydrolysis of the imine group. The sensing system shows a detection limit of 0.14 μM of Fe³⁺. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1155–1161     

Synthesis,crystal structures and DNA/human serum albumin binding of ternary Cu(II) complexes containing amino acids and 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino

Two water‐soluble 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino (pzta)‐based Cu(II) complexes, namely [Cu(l ‐Val)(pzta)(H₂O)]ClO₄ ( 1 ) and [Cu(l ‐Thr)(pzta)(H₂O)]ClO₄ ( 2 ) (l ‐Val: l ‐valinate; l ‐Thr: l ‐threoninate), were synthesized and characterized using elemental analyses, molar conductance measurements, spectroscopic methods and single‐crystal X‐ray diffraction. The results indicated that the molecular structures of the complexes are five‐coordinated and show a distorted square‐pyramidal geometry, in which the central copper ions are coordinated to N,N atoms of pzta and N,O atoms of amino acids. The interactions of the complexes with DNA were investigated using electronic absorption, competitive fluorescence titration, circular dichroism and viscosity measurements. These studies confirmed that the complexes bind to DNA through a groove binding mode with certain affinities (K_b = 4.71 × 10³ and 1.98 × 10³ M^?1 for 1 and 2 , respectively). The human serum albumin (HSA) binding properties of the complexes were also evaluated using fluorescence and synchronous fluorescence spectroscopies, indicating that the complexes could quench the intrinsic fluorescence of HSA in a static quenching process. The relevant thermodynamic parameters revealed the involvement of van der Waals forces and hydrogen bonds in the formation of complex–HSA systems. Finally, molecular docking technology was also used to further verify the interactions of the complexes with DNA/HSA.     

Spectra Studies of Complexes Between Palladium (II), Nickel (II) and Amino Acids

The complexes of Ni (His) 2·H2O, Ni (Gly) 2·2H2O, Pd (His)Cl2·H2O and Pd(Gly) 2·2H2O were synthesized. And the IR, electronic absorption and photoacoustic spectra of these complexes were measured in solid state. The nature of the metal-carboxylate coordinate bond were deduced from the variation in the carboxyl stretching frequencies. And the d-d transition absorptions of these complexes were interpreted quantitatively with the 3d scaling radial theory. Therefore, the structural characterizations were also discussed with their spectral behaviors.     

Polymeric Coordination Compounds Derived from Transition Metal(II) with Tetradentate Schiff‐base: Synthetic,Spectroscopic, Magnetic and Thermal Approach

The polymeric coordination compounds have been synthesized using the dipotassium salt of N,N′‐di(carboxymethylene)terephthalaldehydediimine (K₂SB¹) or N,N′‐di(carboxyethylene)terephthalaldehydediimine (K₂SB²) with manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), and cadmium(II). The ligands have been characterized by ¹H‐NMR, and ¹³C‐NMR spectra. The polychelates have been characterized by elemental analyses, magnetic measurements, thermogravimetric analyses, electronic spectra and infrared spectra. The coordination compounds are colored, and the central metal ions are octahedrally coordinated with two water molecules and the Schiff bases. The Schiff bases act as di‐negative tetradentate ligands, in which bonding occurs through two oxygen and two nitrogen atoms. The polymers are insoluble in all common organic solvents such as acetone, methanol, ethanol, N,N‐dimethylformamide and dimethylsulfoxide.     

Tuning Ruthenium Carbene Complexes for Selective P−H Activation through Metal-Ligand Cooperation

The use of iminophosphoryl-tethered ruthenium carbene complexes to activate secondary phosphine P−H bonds is reported. Complexes of type [(p-cymene)-RuC(SO₂Ph)(PPh₂NR)] (with R = SiMe₃ or 4-C₆H₄−NO₂) were found to exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Hence, the electron-rich silyl-substituted complex undergoes cyclometallation or shift of the imine moiety after cooperative activation of the P−H bond across the M=C linkage, depending on the electronics of the applied phosphine. Deuteration experiments and computational studies proved that cyclometallation is initiated by the activation process at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates. Consistently, replacement of the trimethylsilyl (TMS) group by the electron-withdrawing 4-nitrophenyl substituent allowed the selective cooperative P−H activation to form stable activation products.     

SYNTHESIS,CHARACTERIZATION, AND REACTIONS OF MONOMERIC TITANIUM COMPLEXES CONTAINING A CHELATING BIS(PHENOLATE) LIGAND [1, 2]

Abstract

The synthesis of Ti(iso)Cl₂ (iso = the dianion of 2, 2′-ethylidenebis(4, 6-di-rert-butylphenol)) is described. Metathesis reactions of this complex with Grignard reagents, as well as alkali metal salts, yielded Ti(iso)X₂ (X = CH₃, CH, Ph, CH₂SiMe₃, OCMe₃, or NMe₂). Reactions of the Ti-C bond in Ti(iso)(CH₃)₂ toward halogens, active hydrogen compounds, and acetone were studied. In addition. Ti(iso)(X)(Y) (X = CI or CH₃; Y = OC₆H₂-2, 6-^tBu₂-4-Me) could be prepared with the formation of only one coordination isomer. The new complexes have been thoroughly characterized by ¹H and ¹³C NMR spectroscopies. The solid state structure of Ti(iso)Cl₂ was determined via single crystal X-ray diffraction methods. The complex is monomeric, with approximately tetrahedral geometry about the titanium ion. The structure of Ti(iso)Cl₂ is compared to that of Ti(ultra)Cl₂ (ultra = the dianion of 2, 2′-mefhylenebis(6-tert-butyl-4-mefhylphenol)), which was redetermined to greater precision.     

Hybrid EuIII Coordination Luminophore Standing on Two Legs on Silica Nanoparticles for Enhanced Luminescence

In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent Ln^III-silica nanomaterials. A novel Eu^III-silica hybrid nanoparticle was developed by using a doubly binding TPPO−Si(OEt)₃ (TPPO: triphenyl phosphine oxide) linker. The TPPO−Si(OEt)₃ was confirmed by ¹H, ³¹P, ²⁹Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)₃ and Eu(tfc)₃ moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO−Si(OEt)₃-modified silica nanoparticles, producing Eu(hfa)₃(TPPO−Si)₂-SiO₂ and Eu(tfc)₃(TPPO−Si)₂-SiO₂, respectively. Eu(hfa)₃(TPPO−Si)₂−SiO₂ exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported Eu^III-based hybrid materials. Eu(tfc)₃(TPPO−Si)₂−SiO₂ showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)₃(TPPO−Si(OEt)₃)₂ was found to be 39 %. These results confirmed that the TPPO−Si(OEt)₃ linker is a promising candidate for development of Eu^III-based luminescent materials.     

Metal complexes of novel Schiff base derived from the condensation of 2‐quinoline carboxaldehyde and ambroxol drug with some transition metal ions

A new Schiff base was prepared as the condensation product of the reaction of 2‐quinoline carboxaldehyde and ambroxol drug. The Schiff base ligand thus obtained (HL; trans‐4‐[(2‐(2‐quinolinoimino)‐3,5‐dibromobenzyl)amino]cyclohexanol) was further employed as a tridentate ligand for the synthesis of new complexes through reaction with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) metal ions. The synthesized HL and its metal complexes were characterized using various physicochemical techniques including elemental analysis, Fourier transform infrared and UV–visible spectroscopies, conductimetric and magnetic susceptibility measurements, mass spectrometry and thermal analyses. ¹H NMR data indicated that complex formation was through the amino group rather than the aliphatic hydroxyl group. Thermal analysis gave an idea about the decomposition pattern of HL and its complexes. Also, it revealed the number of water molecules in the inner and outer spheres of the complexes. An octahedral geometry for all the complexes has been suggested. HL and its complexes were screened for their antimicrobial activity against various species of bacteria and fungi using the disc diffusion method. The Cr(III) complex had the highest antimicrobial activity.