Nicolae Stanica

Synthesis, characterization antibacterial and antiproliferative activity of novel Cu(II) and Pd(II) complexes with 2-hydroxy-8-R-tricyclo[7.3.1.0.(2,7)]tridecane-13-one thiosemicarbazone.

Synthesis and biological activity investigation of complex compounds of Cu(II) are challenging issues because of the metal is not a xenobiotic one and the activity of ligands could be modulated by complexation. Complex combinations of Cu(II) and Pd(II) with thiosemicarbazone derivatives of 2-hydroxy-8-R-tricyclo[7.3.1.0.(2,7)]tridecane-13-one (where R=C(3)H(7), C(4)H(3)O) were synthesized. The characterization of the ligands and the newly formed compounds was done by (1)H NMR, (13)C NMR, UV-vis, IR, ESR spectroscopy, elemental analysis, molar electric conductibility and thermal studies. Experiments performed to identify the structures proved that the ligands coordinate to metal ions in different ways - neutral bidentate or mononegative bidentate. Also, if copper(II) acetate, copper(II) nitrate, copper(II) chloride and copper(II) thiocyanate were used, the ligands coordinated in a mononegative bidentate fashion. If copper(II) sulfate was used, the ligands coordinated in a neutral bidentate fashion. The biological activity for the copper(II) synthesized compounds was assessed in terms of antibacterial or antiproliferative activity. The antibacterial activity of the complexes against Staphylococcus aureus var. Oxford 6538, Escherichia coli ATCC 10536, Klebsielle pneumoniae ATCC 100131 and Candida albicans ATCC 10231 strains was studied and compared with that of free ligands. The effect of complex compounds on the proliferation of HeLa cells was tested. For all tested complexes an antiproliferative activity was noted at concentrations higher than 1 microM, but lower than 10 microM. Therefore, complex compounds of copper(II) were synthesized, structurally characterized and tested for biological activity, proving both antibacterial and antiproliferative activity.

Alkoxo-bridged copper(II) complexes as nodes in designing solid-state architectures. The interplay of coordinative and d10-d10 metal-metal interactions in sustaining supramolecular solid-state architectures

Four novel polymeric coordination networks have been obtained through self-assembly processes involving alkoxo-bridged copperII species as nodes, and anionic cyano-complexes as linkers: infinity2[{Cu2(pa)2}{M(CN)2}2](M=Ag, 1; Au, 2), (infinity)3[{Cu4(mea)4}{Au(CN)2}4.H2O]3, and (infinity)3[{Cu2(pa)2}{Ni(CN)4}](pa = deprotonated propanolamine; mea = deprotonated monoethanolamine). The supramolecular architectures of compounds 1, and 2 are sustained by argentophilic or strong aurophilic interactions. The solid-state architectures of 1 and 2, which are isomorphous, consist of infinite layers, constructed from binuclear alkoxo-bridged nodes and [M(CN)2]- spacers. The layers are stacked in an offset parallel mode, and are further interconnected through Ag...Ag or Au...Au contacts (1: Ag...Ag 3.015 A; 2: Au....Au 3.069 A). Compound 3 consists of unique fourfold interpenetrating diamondoid nets. The diamondoid topology is built of heterocubane {Cu4O4} nodes, which are connected by [Au(CN)2]- rods. The Cu-O distances within the {Cu4O4} node vary between 1.927(2) and 2.679(1) A, showing unsymmetric bridging of the copper atoms. Aurophilic interactions are established between the bridging and terminal [Au(CN)2]- metalloligands, and connect the interpenetrating nets, resulting in infinite chains of gold atoms (the Au...Au distances vary between 3.253 and 3.305 [Angstrom]). Compound 4 exhibits a 3-D network constructed from {Cu2(pa)2]2+ nodes connected by square-planar [Ni(CN)4]2- ions. Compounds 1, 2 and 4 are weakly paramagnetic. The cryomagnetic investigation of reveals a gradual increase, followed by a decrease of the chiMT product, as the temperature is lowered. A superposition of ferro- (J1=+20.8 cm(-1)) and antiferromagnetic (J2=-6.4) interactions within the tetranuclear node was found. Antiferromagnetic interactions are established between the tetranuclear nodes (theta=-2.99 K).

A novel cyano-bridged pentanuclear complex: [{Mn3(MAC)3(H2O)2}{Fe(CN)6}2].6H2O.2CH3OH-synthesis, crystal structure and magnetic properties (MAC = pentaaza macrocyclic ligand)

Abstract The reaction between K3[Fe(CN)6] and [Mn(MAC)(H2O)2]Cl2·4H2O (MAC=2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene) in a water/methanol mixture affords a pentanuclear complex with the formula [{Mn3(MAC)3(H2O)2}{Fe(CN)6}2]·6H2O·2CH3OH (1), whose crystal structure has been solved. It consists of discrete [MnIIFeIIIMnIIFeIIIMnII] entities. The three {Mn(MAC}2+ moieties are connected by two [Fe(CN)6]3− anions, each one involving two cis cyano bridging groups. The manganese ions display a distorted pentagonal–bipyramidal geometry, with the macrocyclic ligand forming the equatorial plane. The axial positions are occupied by two nitrogen atoms arising from the cyano bridges, for the central manganese atom, and by one aqua ligand and one nitrogen atom from the cyano bridge, for the terminal manganese atoms. The cryomagnetic properties of 1 have been investigated and reveal a new case of irregular spin-state structure.

Some Polynuclear Coordination Compounds Precursors of Chromites Synthesis, Physicochemical Characterization and Thermal Stability

The polynuclear coordination compounds LnCr(tartrate)3·nH2O where Ln(III)=La-Er, obtained through a precipitation method, were characterized on the basis of elemental analysis, their electronic and vibrational spectra and magnetic susceptibility measurements. The possibility of obtaining chromites through the transformations of the polynuclear coordination compounds in the solid state was considered. The thermal decompositions of these compounds, studied by TG and DTA methods, were found to follow an almost uniform pattern. The decompositions occurred in six-eight steps. The first two steps involved dehydration, and the third the transformation of tartrate anions to oxalate, followed by conversion to carbonate and oxocarbonate intermediates. The final product in each case was LnCrO3. A non-isothermal kinetic analysis of the first decomposition steps was performed, the most probable decomposition mechanism being selected and the kinetic parameters evaluated. The final products of the transformations were characterized.

Polynuclear coordination compounds as precursors for CuFe2O4

The possibility of obtaining copper ferrite through the thermal decomposition of the two polynuclear coordination compounds: (NH4)8[Fe2Cu(C2O4)8] (I) and [Fe2Cu(C2O4)2(OH)4]·4H2O (II) was considered. The polynuclear compounds were characterized by various physical chemical techniques, e.g., IR, UV-VIS, EPR, Mossbauer spectra, thermal analysis and magnetic measurements. The final products obtained after thermal decomposition of the complex compounds were analysed by X-ray diffraction. A mixture of tetragonal CuFe2O4, α-Fe2O3 and CuO is generated from the thermolysis of compound I, while a clean tetragonal CuFe2O4 with saturation magnetization of 26.89 emu g−1 is obtained from compound II.

The first coordination compound containing three different types of spin carriers: 2p-3d-4f (TCNQ.-, Cu2+ and Gd3+)

A novel heterospin system, [(CuL)2Gd(TCNQ)2].TCNQ-.CH3OH.2CH3CN, is obtained by reacting the mononuclear complex, [CuL], with gadolinium(III) nitrate, followed by the substitution of the nitrato ions with anionic organic radicals.

Spectral, magnetic and thermal characterisation of new Co(II), Ni(II) and Cu(II) complexes with Schiff base 5-bromo-N,N′-bis-(salicylidene)-o-tolidine

Starting from 5-bromo-N,N′-bis-(salicylidene)-o-tolidine (H2L) new complexes with Co(II), Ni(II) and Cu(II) were synthesised and characterised. The features of complexes have been assigned from microanalytical, IR, UV–Vis–NIR and EPR spectra, magnetic data at room temperature as well as thermal analysis. IR data are in accordance with bischelate nature of the deprotonated ligand that coordinates through azomethinic nitrogen and phenolic oxygen. The electronic spectra display the characteristic pattern of tetrahedral stereochemistry for [CoL]·H2O complex and octahedral one for [NiL(OH2)2]·H2O complex. The electronic spectra correlated with magnetic susceptibility measurements indicate a square-planar surrounding for [ML] (M:Ni, Cu) species, while the EPR spectrum of copper complex sustains the proposed stereochemistry. The thermal analysis evidenced that thermal transformations are complex processes according to TG, DTA and DTG curves including (crystallization or coordination) water elimination, thermolyses and oxidative degradation of Schiff base. All these processes lead to the most stable metallic oxides as final product.

Synthesis and structural studies of Co(II), Ni(II) and Cd(II) complexes with 2-acetylpyridine

Three new mononuclear complexes [Co(2-Acpy)2(H2O)2](NO3)2 (1), [Ni(2-Acpy)2(H2O)2](NO3)2 (2) and [Cd(2-Acpy)2(NO3)2] (3) (2-Acpy = 2-acetylpyridine) have been synthesized and characterized by elemental analysis, IR and UV–Vis spectroscopy. The structures of 1 and 3 were accomplished by single crystal X-ray diffraction. Crystallographic investigation of 1 reveals monomeric, dicationic units in which the cobalt(II) ion is six-coordinate. The coordination sphere is formed by two N, O bidentate acetylpyridine ligands and two water molecules. The crystal structure of 3 consists of monomeric units in which the cadmium is eight-coordinate. Both the organic ligand and nitrate groups are bidentate chelators. The supramolecular solid-state architecture is sustained by π–π interactions.

Lanthanum chromites doped with divalent transition metals

Abstract Heteropolynuclear complex compounds isolated in Cr 2 O 3 · x H 2 O–La(NO 3 ) 3 –M(NO 3 ) 2 –A–NH 3 , (A=CH 3 COO − ,C 2 O 4 2− ; M=Cu, Ni) systems were used as precursors for LaCr 1− x M x O 3 . The perovskite structure of doped lanthanum chromites was determined by XRD analysis. The unit cell volumes, specific surface areas and magnetic properties were investigated. The proposed methods offer new, simple, less expensive procedures for obtaining doped lanthanum chromites.

Nonconventional methods for obtaining hexaferrites

Small particles of PbFe12O19 have been synthesized. X-ray diffraction, thermal analysis and magnetic investigations have been conducted in order to obtain information on the mechanism of lead hexaferrite formation.