Complexation of the Fe(III) and Fe(II) sulphates with diphenyl-4-amine barium sulphonate (DAS) Synthesis,thermogravimetric and spectroscopic studies

Reactions in aqueous-alcoholic solution between diphenyl-4-amine barium sulphonate (Ba-DAS—anionic surfactant) and the hydrated sulphates of Fe(III) and Fe(II) ions and their use to ovtain iron oxides are described here. The formation of Fe(II) complexes was reached by using an excess of Ba-DAS, in absence of light under inert atmosphere. The complexes achieved Fe₂[(C₁₂H₁₀NO₃S)₄]·9H₂O and Fe₃[(C₁₂H₁₀NO₃S)₆]·12H₂O were characterized by TG/DTG and IR, UV-VIS and ⁵⁷Fe-Mössbauer analyses.     

Synthesis and characterization of three ionic pairs of Fe(II) and Co(II) complexes with tridentate salicylideneglycine

Three new transition metal complexes, [Fe^II(H₂O)₆][(C₉H₇NO₃)₂Fe^II] · H₂O (1), H[K(H₂O)₃][(C₉H₇NO₃)₂Co^II] · H₂O (2), and [Co^II(H₂O)₆][(C₉H₇NO₃)₂Co^II] · H₂O (3), with salicylideneglycine have been synthesized and characterized by elemental analysis, IR spectra, UV-Vis spectroscopy, and X-ray crystallography. The structure analyses indicate that the tridentate salicylideneglycine binds through aliphatic nitrogen, phenoxy, and carboxylic oxygen in the anion. There are many inter- and intra-molecular hydrogen bonds among lattice water, the anion, and the cation to form a 3-D network. The thermogravimetric analyses and the quantum chemistry calculations of compounds 1, 2, and 3 are also discussed.     

Heterobinuclear and Heterotrinuclear complexes of Oxorhenium(V) with Cu(II), Ni(II), Fe(III), UO2(VI) and Th(IV) in the solid state

New heteronuclear complexes containing oxorhenium(V), Cu(II), Ni(II), Fe(III), UO₂(VI) and Th(IV) ions were prepared by the reaction of the complex ligand, [ReO(H₄L)Cl]Cl₂, where H₄L = 8,17-dimethyl-6,15-dioxo-5,7,14,16-tetrahydrodibenzo[a,h][14]annulene-2,11-dicarboxylic acid, with the previous transition and actinide salts. Three heteronuclear Cu(II) complexes were isolated depending on the ratio of [ReO(H₄L)Cl]Cl₂?:?Cu(II) ion. When the ratios were 1?:?0.5, 1?:?1 and 1?:?2, the heteronuclear complexes {[ReO(H₃L)Cl]₂CuCl₂(OH₂)₂}SO₄ · H₂O (I), [ReO(H₃L)Cl₂Cu(OH₂)₂(SO₄)] (II) and {ReO(H₂L)Cl[Cu(OH₂)₃ SO₄]₂} (III) were obtained, respectively. Heteronuclear complexes of the other metal cations were obtained by mixing [ReO(H₄L)Cl]Cl₂ with the metal salt in the ratio 1?:?1 to obtain the heteronuclear complexes [ReO(H₃L)Cl₂Ni(OH₂)₂](NO₃)₂ (IV), [ReO(H₃L)Cl₃Fe(OH₂)₃](NO₃)₂ (V), [ReO(H₃L)ClUO₂(NO₃)₂ (OH₂)]Cl (VI) and [ReO(H₃L)Cl₃Th(NO₃)₂(OH₂)]NO₃ · 2H₂O (VII). The complex ligand coordinates with the heterometal ion via the carboxylate group, and the infrared bands ν_as COO and ν_s COO indicate that the carboxylate acts as a unidentate ligand to the heterometal cations. Cu(II) and Fe(III) cations in the heteronuclear complexes have octahedral geometry, while Ni(II) is square planar. Thermal studies explored the possibility of obtaining new heteronuclear complexes pyrolytically in the solid state from the corresponding mother complexes. The structures of the complexes were elucidated by conductance, IR and electronic spectra, magnetic moments, ¹H NMR and TG-DSC measurements as well as by mass spectroscopy.     

通过铜(II)、铁(III)和铁(II)与2,2'-联咪唑协同作用构筑的超分子及其结构的研究

在水和乙醇溶剂中, 通过Cu(II), Fe(III)和Fe(II)与2,2-联咪唑协同作用, 构筑了四种新的超分子配合物[Cu(H₂biim)(gly)(H₂O)]Cl•H₂O (1), [Cu(H₂biim)(C₃H₂O₄)(H₂O)]•1.5H₂O (2), [Fe₂(μ-O)(H₂biim)₄(H₂O)₂](NO₃)₄•C₂H₅OH (3)和[Fe(H₂biim)₃]SO₄ (4) (H₂biim＝2,2-联咪唑; gly^－＝甘氨酸根; C₃H₂O＝丙二酸根). 并通过元素分析, 红外光谱和X射线单晶衍射对其组成、结构和谱学性质进行研究. H₂biim配体, 丙二酸根和甘氨酸根三种配体都采用了双齿螯合方式与金属离子配位. 配合物1～4中, 通过H₂biim配体的N—H键与阴离子、水分子和溶剂分子形成多种氢键, 如R(7), R(9)和R(4)等, 以及H₂biim配体之间的π-π堆积, 阳离子不对称单元构筑了多维结构的超分子配合物.     

REPARATION AND CHARACTERIZATION OF NEW SUPROFEN COMPLEXES OF Fe(III), Co(II) AND Ni(II)

Abstract

The preparation and properties of new complexes containing the biometals Fe(III), Co(II) and Ni(II) coordinated to the anti-inflammatory drug Suprofen are reported. The elemental analyses, together with the magnetic and thermal behavior and electronic, IR and Raman spectra, indicated the following stoichiometries for the latter two complexes: [M(Sup)₂(H₂O)₄]. For the Fe(III) complex, the generation of a dinuclear species may be proposed on the basis of ⁵⁷Fe Mössbauer measurements.     

New iron(III) nitrate hydrates: Fe(NO3)3·xH2O with x = 4, 5 and 6

Crystals of the title compounds were grown from their hydrous melts or solutions. The crystal structure of iron(III) trinitrate hexahydrate {hexaaquairon(III) trinitrate, [Fe(H₂O)₆](NO₃)₃} is built up from [Fe(H₂O)₆]²⁺ octahedra and nitrate anions connected via hydrogen bonds. In iron(III) trinitrate pentahydrate {pentaaquanitratoiron(III) dinitrate, [Fe(NO₃)(H₂O)₅](NO₃)₂}, one water molecule in the coordination octahedron of the Fe^III atom is substituted by an O atom of a nitrate group. Iron(III) trinitrate tetrahydrate {triaquadinitratoiron(III) nitrate monohydrate, [Fe(NO₃)₂(H₂O)₃]NO₃·H₂O} represents the first example of a simple iron(III) nitrate with pentagonal–bipyramidal coordination geometry, where two bidentate nitrate anions and one water molecule form a pentagonal plane.     

Kinetics of thermal decomposition of iron(III) dicarboxylate complexes

Summary Tris(dicarboxylate) complexes of iron(III) with oxalate, maleate, malonate and phthalate viz. K₃[Fe(C₂O₄)₃]×3H₂O (1), K₃[Fe(OOCCH₂COO)₃]×3H₂O (2), K₃[Fe(OOCCH=CHCOO)₃]×3H₂O (3), K₃[Fe(OOC-1,2-(C₆H₄)-COO)₃]×3H₂O (4) have been synthesized and characterized using a combination of physicochemical techniques. The thermal decomposition behaviour of these complexes have been investigated under dynamic air atmosphere upto 800 K. All these complexes undergo a three-step dehydration/decomposition process for which the kinetic parameters have been calculated using Freeman-Carrol model as well as using different mechanistic models of the solid-state reactions. The trisoxalato and trismalonato ferrate(III) complexes undergo rapid dehydration at lower temperature below 470 K. At moderately higher temperatures (i.e. >600 and 500 K, respectively) they formed bis chelate iron(III) complexes. The trismalonato and trismaleato complexes dehydrate with almost equal ease but the latter is much less stable to decomposition and yields FeCO₃ below 760 K. The cis-dicarboxylate complexes particularly with maleate(2-) and phthalate(2-) ligands are highly prone to the loss of cyclic anhydrides at moderately raised temperatures. The thermal decomposition of the tris(dicarboxylato)iron(II) to iron oxide was not observed in the investigated temperature range up to 800 K. The dehydration processes generally followed the first or second order mechanism while the third decomposition steps followed either three-dimensional diffusion or contracting volume mechanism.     

Comparison of density functionals for the study of the high spin low spin gap in Fe(III) spin crossover complexes

A detailed investigation of the accuracy of different quantum mechanical methods for the study of iron(III) spin crossover complexes is presented. The energy spin state gap between the high and low spin states; ΔE (HS‐LS) of nine iron(III) quinolylsalicylaldiminate complexes were calculated with nine different DFT functionals, then compared. DFT functionals: B3LYP, B3LYP‐D3, B3LYP*, BH&HLYP, BP86, OLYP, OPBE, M06L, and TPSSh were tested with six basis sets: 3‐21G*, dgdzvp, 6‐31G**, cc‐pVDZ, Def2TZVP, and cc‐pVTZ. The cations from the X‐ray crystal structures of [Fe(qsal‐OMe)₂]Cl·MeCN·H₂O, [Fe(qsal‐OMe)₂]Cl·2MeOH·0.5H₂O, [Fe(qsal‐OMe)₂]BF₄·MeOH, [Fe(qsal‐OMe)₂]NCS·CH₂Cl₂, [Fe(qsal‐F)₂]NCS, [Fe(qsal‐Cl)₂]NCS·MeOH, [Fe(qsal‐Br)₂]NCS·MeOH, [Fe(qsal‐I)₂]OTf·MeOH, and [Fe(qsal)₂]NCS?CH₂Cl₂ were used as starting structures. The results show that B3LYP, B3LYP‐D3, OLYP, and OPBE with a 6‐31G**, Def2TZVP, and cc‐pVTZ basis set give reasonable results of ΔE (HS‐LS) compared with the experimental data. The enthalpy of [Fe(qsal‐I)₂]⁺ calculated with an OLYP functional and cc‐pVTZ basis set (1.48 kcal/mol) most closely matches the experimental data (1.34 kcal/mol). B3LYP* yields an enthalpy of 5.92 kcal/mol suggesting it may be unsuitable for these Fe(III) complexes, mirroring recent results by Kepp (Inorg . Chem ., 2016, 55 , 2717–2727).     

Synthesis and spectroscopic characterization of new metal(II) complexes with methionine sulfoxide

Methionine sulfoxide complexes of iron(II) and copper(II) were synthesized and characterized by chemical and spectroscopic techniques. Elemental and atomic absorption analyses fit the compositions K₂[Fe(metSO)₂]SO₄·H₂O and [Cu(metSO)₂]·H₂O. Electronic absorption spectra of the complexes are typical of octahedral geometries. Infrared spectroscopy suggests coordination of the ligand to the metal through the carboxylate and sulfoxide groups. An EPR spectrum of the Cu(II) complex indicates tetragonal distortion of its octahedral symmetry. ⁵⁷Fe Mössbauer parameters are also consistent with octahedral stereochemistry for the iron(II) complex. The complexes are very soluble in water.     

Solid complexes of iron(II) and iron(III) with rutin

Solid complex compounds of Fe(II) and Fe(III) ions with rutin were obtained. On the basis of the elementary analysis and thermogravimetric investigation, the following composition of the compounds was determined: (1) FeOH(C₂₇H₂₉O₁₆)·5H₂O, (2) Fe₂OH(C₂₇H₂₇O₁₆)·9H₂O, (3) Fe(OH)₂(C₂₇H₂₉O₁₆)·8H₂O, (4) [Fe₆(OH)₂(4H₂O)(C₁₅H₇O₁₂)SO₄]·10H₂O. The coordination site in a rutin molecule was established on the basis of spectroscopic data (UV–Vis and IR). It was supposed that rutin was bound to the iron ions via 4C=O and 5C—oxygen in the case of (1) and (3). Groups 5C–OH and 4C=O as well as 3′C–OH and 4′C–OH of the ligand participate in binding metals ions in the case of (2). At an excess of iron(III) ions with regard to rutin under the synthesis conditions of (4), a side reaction of ligand oxidation occurs. In this compound, the ligands’ role plays a quinone which arose after rutin oxidation and the substitution of Fe(II) and Fe(III) ions takes place in 4C=O, 5C–OH as well as 4′C–OH, 3′C–OH ligands groups. The magnetic measurements indicated that (1) and (3) are high-spin complexes.     

Spectral characterization and antimicrobial activity of Cu(II) and Fe(III) complexes of 2-(5-Cl/NO2-1H-benzimidazol-2-yl)-4-Br/NO2-phenols

The compounds of 2-(5-chloro/nitro-1H-benzimidazol-2-yl)-4-bromo/nitrophenols (HL_X : X = 1–4) and their copper(II) nitrate and iron(III) nitrate complexes have been synthesized and characterized. The structures of the complexes were confirmed on the basis of elemental analysis, thermal gravimetric analysis, molar conductivity and magnetic moment measurements, FT-IR, mass, and UV-Vis spectroscopy techniques. The complexes show high-thermal stability with >350°C m.p. In all complexes, the ligands are bidentate via one imine nitrogen and a phenolate oxygen. Cu(II) complexes having 1 : 2 M : L ratio are classified as non-electrolytes, whereas 1 : 1 M : L ratio is observed in Fe(III) complexes except [Fe(L₃)₂(H₂O)₂](NO₃) ? 3H₂O. The antimicrobial activities of the ligands and the complexes were evaluated using the disc diffusion method in DMSO as well as minimum inhibitory concentration dilution method against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, and Proteus mirabilis. Antifungal activities were reported for Candida albicans. The complexes [Fe(L₃)₂(H₂O)₂](NO₃) ? 3H₂O and [Cu(L₃)₂] ? 2H₂O are more effective against S. epidermidis than ciprofloxacin.     

Synthesis and characterization of novel heteronuclear complexes of Ln(III)-Cu(II) with non-cyclic polyether Schiff base

Nine novel heteronuclear complexes of Ln(III)-Cu(II) with salicylidene tetraethylene glycol diamine (SALTTA) have been synthesized and characterized. They have the general formulae [L_nC_u2(SALTTA)₂(NO₃)₃](NO₃)₄·3H₂O (Ln=La, Pr, Nd, Sm) and [LnCu₃(SALTTA)₃(NO₃)₅]-(NO₃)₄·4H₂O (Ln=Gd, Tb, Er, Yb, Y). The IR spectra show that v_C=N in the Ln(III)-Cu(II) heteronuclear complexes are splitted up into two peaks with a far distance. It has been confirmed that oxygen atoms in oxyethylene of the ligand are not all coordinated to the central metal ions by both IR and NMR methods.     

Synthesis,structure and DNA cleavage of mononuclear Fe(III) complexes with 1,2,4‐triazole‐base ligand

Two new mononuclear iron(III) complexes, [Fe(HL)₂](ClO₄) · (H₂O)_1.75· CH₃CN (1) and [Fe(HL)Cl₂] · DMF (2) [H₂L = 3‐(2‐phenol)‐5‐(pyridin‐2‐yl)‐1,2,4‐triazole] have been synthesized and characterized by X‐ray single‐crystal structure analysis. The single crystal X‐ray crystallographic studies reveal that the central iron atom has a distorted octahedral environment for 1 and a distorted square pyramidal geometry for 2. The DNA cleavage activity of the iron(III) complexes was measured, indicating that the six‐coordinated iron(III) (complex 1) was cleavage inactive and only five‐coordinated complex 2 effectively promoted the cleavage of plasmid DNA in the presence and/or absence of activating agents (peroxide oxygen) at physiological pH and temperature. The mechanism of plasmid DNA cleavage was also studied by adding standard radical scavengers. Copyright © 2010 John Wiley & Sons, Ltd.     

A rare octacoordinated mononuclear iron(III) spin‐crossover compound: synthesis,crystal structure and magnetic properties

The chemistry of transition‐metal complexes with unusually high coordination numbers has been of interest because of their application in catalytic and biological systems. Deprotonation of the ionogenic tetradentate ligand 6,6′‐bis(1H‐tetrazol‐5‐yl)‐2,2′‐bipyridine [H₂bipy(ttr)₂] in the presence of iron(III) and tetra‐n‐butylammonium bromide, [n‐Bu₄N]Br, in solution resulted in the synthesis of a rare octacoordinated anionic mononuclear complex, tetra‐n‐butylammonium bis[6,6′‐bis(tetrazol‐1‐id‐5‐yl)‐2,2′‐bipyridine]iron(III) methanol hemisolvate dihydrate, (C₁₆H₃₆N)[Fe(C₁₂H₆N₁₀)₂]·0.5CH₃OH·2H₂O or [n‐Bu₄N][Fe{bipy(ttr)₂}₂]·0.5CH₃OH·2H₂O ( 1 ), which has been structurally characterized by elemental analysis, powder X‐ray diffraction (PXRD) and single‐crystal X‐ray diffraction. In 1 , the coordination sphere of the iron(III) ion is a distorted bis‐disphenoid dodecahedron, in which the eight coordination positions are occupied by eight N atoms from two independent tetradentate [bipy(ttr)₂]^2? anionic ligands, therefore forming the anionic [Fe{bipy(ttr)₂}₂]^? unit, with the negative charge balanced by a free [n‐Bu₄N]⁺ cation. An investigation of the magnetic properties of 1 revealed a gradual incomplete spin‐crossover behaviour below 150 K.     

Thermal decomposition of hydrotalcite with hexacyanoferrate(II) and hexacyanoferrate(III) anions in the interlayer

The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. The thermal decomposition of hydrotalcites with hexacyanoferrate(II) and hexacyanoferrate(III) in the interlayer has been studied using controlled rate thermal analysis technology. X-ray diffraction shows the hydrotalcites have a d(003) spacing of 10.9 and 11.1 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. Calculations show dehydration with a total loss of 7 moles of water proving the formula of hexacyanoferrate(II) intercalated hydrotalcite is Mg₆Al₂(OH)₁₆[Fe(CN)₆]_0.5·7H₂O and 9.0 moles for the hexacyanoferrate(III) intercalated hydrotalcite with the formula of Mg₆Al₂(OH)₁₆[Fe(CN)₆]_0.66·9H₂O. CRTA technology indicates the partial collapse of the dehydrated mineral. Dehydroxylation combined with CN unit loss occurs in two isothermal stages at 377 and 390°C for the hexacyanoferrate(III) and in a single isothermal process at 374°C for the hexacyanoferrate(III) hydrotalcite.     

Molecular modeling,spectral, and biological studies of 4-formylpyridine-4 N-(2-pyridyl) thiosemicarbazone (HFPTS) and its Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Cd(II), Hg(II), and UO2(II) complexes

The present work describes the preparation and characterization of some metal ion complexes derived from 4-formylpyridine-⁴ N-(2-pyridyl)thiosemicarbazone (HFPTS). The complexes have the formula; [Cd(HFPTS)₂H₂O]Cl₂, [CoCl₂(HPTS)]·H₂O, [Cu₂Cl₄(HPTS)]·H₂O, [Fe (HPTS)₂Cl₂]Cl·3H₂O, [Hg(HPTS)Cl₂]·4H₂O, [Mn(HPTS)Cl₂]·5H₂O, [Ni(HPTS)Cl₂]·2H₂O, [UO₂(FPTS)₂(H₂O)]·3H₂O. The complexes were characterized by elemental analysis, spectral (IR, ¹H-NMR and UV–Vis), thermal and magnetic moment measurements. The neutral bidentate coordination mode is major for the most investigated complexes. A mononegative bidentate for UO₂(II), and neutral tridentate for Cu(II). The tetrahedral arrangement is proposed for most investigated complexes. The biological investigation displays the toxic activity of Hg(II) and UO₂(II) complexes, whereas the ligand displays the lowest inhibition activity toward the most investigated microorganisms.     

Structure Controlling Factors of Oxido-Bridged Dinuclear Iron(III) Complexes

Oxido bridges commonly form between iron(III) ions, but their bond angles and symmetry vary with the circumstances. A large number of oxido-bridged dinuclear iron(III) complexes have been structurally characterized. Some of them belong to the C₂ point group, possessing bent Fe–O–Fe bonds, while some others belong to the C_i symmetry, possessing the linear Fe–O–Fe bonds. The question in this study is what determines the structures and symmetry of oxido-bridged dinuclear iron(III) complexes. In order to gain further insights, three oxido-bridged dinuclear iron(III) complexes were newly prepared with 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) ligands: [Fe₂OCl₂(bpy)₄][PF₆]₂ (1), [Fe₂O(NO₃)₂(bpy)₄][PF₆]₂·0.6MeCN·0.2(2-PrOH) (2), and [Fe₂OCl₂(phen)₄][PF₆]₂·MeCN·0.5H₂O (3). The crystal structures of 1, 2, and 3 were determined by the single-crystal X-ray diffraction method, and all of them were found to have the bent Fe–O–Fe bonds. Judging from the crystal structure, some intramolecular interligand hydrogen bonds were found to play an important role in fixing the structures. Additional density functional theory (DFT) calculations were conducted, also for a related oxido-bridged dinuclear iron(III) complex with a linear Fe–O–Fe bond. We conclude that the Fe–O–Fe bridge tends to bend like a water molecule, but is often stretched by interligand steric repulsion, and that the structures are mainly controlled by the intramolecular interligand interactions.     

Novel platinum(II) and (IV) complexes of naphthaldimine schiff bases

Naphthaldimines containing N₂O₂ donor centers react with platinum(II) and (IV) chlorides to give two types of complexes depending on the valence of the platinum ion. For [Pt(II)], the ligand is neutral, [(H₂L¹)PtCl₂]·3H₂O (1) and [(H₂L³)₂Pt₂Cl₄]·5H₂O (3), or monobasic [(HL²)₂Pt₂Cl₂]·2H₂O (2) and [(HL⁴)₂Pt]·2H₂O (4). These complexes are all diamagnetic having square-planar geometry. For [Pt(IV)], the ligand is dibasic, [(L¹)Pt₂Cl₄(OH)₂]·2H₂O (5), [(L²)Pt₃Cl₁₀]·3H₂O (6), [(L³)Pt₂Cl₄(OH)₂]·C₂H₅OH (7) and [(L⁴)Pt₂Cl₆]·H₂O (8). The Pt(IV) complexes are diamagnetic and exhibit octahedral configuration around the platinum ion. The complexes were characterized by elemental analysis, UV-Vis and IR spectra, electrical conductivity and thermal analyses (DTA and TGA). The molar conductances in DMF solutions indicate that the complexes are non-ionic. The complexes were tested for their catalytic activities towards cathodic reduction of oxygen.     

Singlet quenching of tetraphenylporphyrin and its metal derivatives by iron(III) coordination compounds

The quenching of fluorescence of the free-base tetraphenylporphyrin, H₂TPP, and its metal derivatives, MgTPP and ZnTPP by diverse iron(III) complexes, [Fe(CN)₆]³⁻, Fe(acac)₃, [Fe(mnt)₂]⁻, Fe(Salen)Cl, [Fe₄S₄(SPh)₄]²⁻·, FeTPPCl and [Fe(Cp)₂]⁺ has been studied both in homogeneous medium (CH₃CN) and micellar media, SDS., CTAB and Triton X-100. The quenching efficiencies are analysed in terms of diffusional encounters and it has been possible to separate static quenching components. The quenching constants are dependent on the nature of the ligating atoms around iron(III) and also on the extent of π-conjugation of the ligands. The quenching mechanism has been investigated using steady-state irradiation experiments. Evidence for oxidative quenching by iron(III) complexes was obtained, though the spin multiplicities of the excited electronic states of iron(III) complexes permit both energy and electron transfer mechanisms for quenching of the singlet excited state of the porphyrins.     

Complexes of Co(II), Ni(II), and Cu(II) with 4-(3,4-dichlorophenyl)-1,2,4-triazole

Novel oligonuclear complexes of Co(II), Ni(II), and Cu(II) with 4-(3,4-dichlorophenyl)-1,2,4-triazole (L) of the composition [M₃L₁₀(H₂O)₂](NO₃)₆ (M = Co(II), Ni(II)), [Ni₃L₆(H₂O)₆]Hal₆ (Hal = Cl^?, Br^?), and [Cu₅L₁₆(H₂O)₂](NO₃)₁₀ · 2H₂O were synthesized and studied by magnetic susceptibility, electronic and IR spectroscopy, and powder X-ray diffraction methods. All the above complexes are X-ray amorphous. Antifer-romagnetic exchange interactions between the M²⁺ ions were discovered in the [Co₃L₁₀(H₂O)₂](NO₃)₆ and [Ni₃L₁₀(H₂O)₂](NO₃)₆ complexes, whereas ferromagnetic exchange interactions were observed in the complexes [Ni₃L₆(H₂O)₆]Cl₆, [Ni₃L₆(H₂O)₆]Br₆, and [Cu₅L₁₆(H₂O)₂](NO₃)₁₀ · 2H₂O.