Formation of mononuclear rhodium(III) sulfates: <Superscript>103</Superscript>Rh and <Superscript>17</Superscript>O NMR study

It was shown that the monomeric rhodium sulfate complexes [Rh(H₂O)₄(SO₄)]⁺, trans-[Rh(H₂O)₂(SO₄)₂]^?, cis-[Rh(H₂O)₂(SO₄)₂]^?, and [Rh(SO₄)₃]^3? were not predominant forms in aqueous solutions. The ¹⁰³Rh NMR chemical shifts of the complexes were assigned, and the conditions for their formation in solutions, concentration parameters, and acidity at which the fraction of the monomers was maximal were determined. The constants of formation of the complexes and ion pair (IP) were estimated: K _IP = 8 ± 3.5, K ₁ ≈ 8, K _2trans ≈ 1, K _2cis ≈ 1, and K ₃ ≈ 2.     

Crystal structures of <Emphasis Type="Italic">tris</Emphasis>-hexafluoro-acetylacetonates of aluminum and scandium

The structures of tris-hexafluoroacetylacetonates Al(hfa)₃ and Sc(hfa)₃·H₂O are determined by single crystal X-ray crystallography (Bruker-Nonius X8 Apex diffractometer, MoK _α radiation, T = 150(2) K). The Al(hfa)₃ complex is trigonal, a = 17.8944(11) Å, c = 12.4061(11) Å, P-3c1 space group, V = 3440.3(4) ų, Z = 6, R = 0.076. The Sc(hfa)₃·H₂O complex is monoclinic, a = 16.0926(4) Å, b = 14.7980(3) Å, c = 24.4020(5) Å, β = 125.641(1)°, P2₁/c space group, V = 4722.54(18) ų, Z = 8, R = 0.060. The structures of the complexes are formed by neutral molecules; the coordination environment of the metal atom involves six oxygen atoms of three β-diketone ligands (Al(hfa)₃) and, additionally, a water oxygen atom (Sc(hfa)₃·H₂O). The shortest Al...Al distance is 6.203(6) Å. The Sc(hfa)₃·H₂O molecules are joined in dimers by hydrogen bonds with Sc...Sc separations of 5.6992(8) Å and 5.6853(8) Å. In the crystals, the molecules are joined by van der Waals interactions, moreover, there are intermolecular contacts F...H ～ 2.5 Å in the structure of Sc(hfa)₃·H₂O.     

Crystalline cadmium dialkyl phosphorodithioate complexes: Synthesis and structural organization as probed by multinuclear <Superscript>13</Superscript>C, <Superscript>31</Superscript>P,and <Superscript>113</Superscript>Cd CP/MAS NMR and single-crystal X-ray diffraction

The cadmium O,O′-dethyl (I) and O,O′-di-sec-butyl phosphorodithioate (II) complexes have been synthesized and characterized in detail by ¹³C, ³¹P, and ¹¹³Cd CP/MAS NMR. X-ray crystallography shows that complex II has a binuclear molecular structure [Cd₂{S₂P(O-s-C₄H₉)₂}₄]. For ³¹P and ¹¹³Cd NMR signals, the chemical shift anisotropy δ_aniso and the asymmetry parameter η have been calculated. The ³¹P NMR signals are assigned to the terminal and bridging ligands in the complexes.     

Crystal structures of a family of layered coordination polymers containing divalent metal ions (Mn<Superscript>2+</Superscript>, Co<Superscript>2+</Superscript>, Ni<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript>) and the 3-amino 4-methyl benzoate ion

The syntheses and crystal structures of the layered coordination polymers M(C₈H₈NO₂)₂ [M = Mn (1), Co (2), Ni (3) and Zn (4)] are described. These isostructural compounds contain centrosymmetric trans-MN₂O₄ octahedra as parts of infinite sheets; the ligand bonds to three adjacent metal ions in μ³-N,O,O′ mode from both its carboxylate O atoms and its amine N atom. In each case, weak intra-sheet N–H?O and C–H?O hydrogen bonds may help to consolidate the structure. Crystal data: 1, C₁₆H₁₆MnN₂O₄, M _r = 355.25, monoclinic, P2₁/c (No. 14), a = 10.6534(2) Å, b = 4.3990(1) Å, c = 15.5733(5) Å, β = 95.1827(10)°, V = 726.85(3) ų, Z = 2, R(F) = 0.026, wR(F ²) = 0.067. 2, C₁₆H₁₆CoN₂O₄, M _r = 359.24, monoclinic, P2₁/c (No. 14), a = 10.6131(10) Å, b = 4.3374(4) Å, c = 15.3556(17) Å, β = 95.473(4)°, V = 703.65(12) ų, Z = 2, R(F) = 0.041, wR(F ²) = 0.091. 3, C₁₆H₁₆N₂NiO₄, M _r = 359.02, monoclinic, P2₁/c (No. 14), a = 10.6374(4) Å, b = 4.2964(2) Å, c = 15.2827(8) Å, β = 95.9744(14)°, V = 694.66(6) ų, Z = 2, R(F) = 0.028, wR(F ²) = 0.070. 4, C₁₆H₁₆N₂O₄Zn, M _r = 365.68, monoclinic, P2₁/c (No. 14), a = 10.6385(5) Å, b = 4.2967(3) Å, c = 15.2844(8) Å, β = 95.941(3)°, V = 694.89(7) ų, Z = 2, R(F) = 0.038, wR(F ²) = 0.107.     

A new high-spin iron(III) bis(aqua) complex with the <Emphasis Type="Italic">meso</Emphasis>-tetra(para-chlorophenyl)porphyrin: X-ray crystallography,Hirshfeld surface analysis,magnetic, EPR and electrochemical properties

Chemical preparation of the bis(aqua) iron(III) metalloporphyrin [Fe^III(TClPP)(H₂O)₂](SO₃CF₃)·2(Pnz)·3/4(C₆H₁₂)·2H₂O (TClPP?=?TClPP?=?5,10,15,20-tetra(para-chlorophenyl)porphyrinato and Pnz?=?phenazine) coordination complex (I) was made. The crystal structure of (I) was determined by X-ray single-crystal diffraction and elucidated by Hirshfeld surface approach. Magnetic, spectroscopic and electrochemical properties were also reported and discussed. The mean equatorial distance (Fe–Np) between the iron(III) atom and porphyrin nitrogen atoms is appropriate to a high-spin (S?=?5/2) iron(III) complex. The high-spin state is also confirmed by both magnetic and electron paramagnetic resonance (EPR) spectroscopy data. The repetitive building unit of the crystal structure provides [Fe^III(TClPP)(H₂O)₂]⁺ ion complexes, two non-coordinated Pnz molecules and two water molecules which are interconnected by O–H···O/N/Cl, C–H···O/F/Cl hydrogen bonds, and by C–X···π, C–H···π and π–π stacking intermolecular contacts, forming a 3D supramolecular network. The role and nature of these intermolecular interactions were quantitatively analysed by 3D Hirshfeld surface analysis and associated 2D fingerprint plots. Cyclic voltammetry measurements indicate a one-electron reversible reduction wave with an E_1/2 (Fe(III)/Fe(II) half-potential value of ?0.24 V, which confirms the high-spin S?=?5/2 state of the studied complex.     

Crystal Structure of <Emphasis Type="Italic">DL</Emphasis>-Valinium Tetrafluoroantimonate(III) Monohydrate

The crystal structure of an antimony(III) fluoride complex of the composition (C₅H₁₂NO₂)SbF₄·H₂O (I) involving a cation of α-amino isovaleric acid (DL-valine, Val) is determined. Crystals are monoclinic: a = 12.2024(2) Å, b = 6.1636(1) Å, c = 15.5167(3) Å, Z = 4, space group P2₁/c. The structure is formed of DL-valinium (C₅H₁₂NO₂)⁺ cations, complex [SbF₄]_n^n? anions having a polymeric chain structure, and crystallization water molecules. The [SbF₄]_n^n? complex anions consist of trigonal SbF4E bipyramids joined together by asymmetric bridging Sb–F(3)···Sb bonds. The structural units are organized into a threedimensional framework via N–H···F, N–H···O, and O–H···F hydrogen bonds.     

Crystal structure and triboluminescence of centrosymmetric complex [Eu(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>(HMPA)<Subscript>3</Subscript>]

By single crystal X-ray analysis, the atomic structure of the crystals of [Eu(NO₃)₃(HMPA)₃] complex (HMPA is hexamethylphosphorotriamide) possessing intense triboluminescence is determined. Symmetry of centrosymmetrical crystals is monoclinic: a = 13.785(1) Å, b = 19.746(2) Å, c = 14.723(1) Å, β= 102.143(2)°, P2₁/n space group, Z = 4, d _x = 1.484 g/cm³. The crystal structure is represented by separate C₁₈H₅₄EuN₁₂O₁₂P₃ complexes linked by van der Waals interactions with pronounced cleavage planes. The coordination polyhedron of Eu(III) atom reflects the state of distorted square antiprism. The possible causes of spectral differences in the Stark structure of photo- and triboluminescence are discussed.     

Synthesis and crystal structure of a supramolecular adduct of the aqua nitrato complex of gadolinium [Gd(NO<Subscript>3</Subscript>)(H<Subscript>2</Subscript>O)<Subscript>7</Subscript>]<Superscript>2+</Superscript> with macrocyclic cavitand cucurbit[6]uril

A supramolecular adduct of gadolinium aqua nitrato complex and cucurbit[6]uril { [Gd(NO₃)(H₂O)₇](C₅H₅N)@(C₃₆H₃₆N₂₄O₁₂)}(NO₃)₂·10H₂O is obtained by slow diffusion of methanol into an aqueous solution containing gadolinium nitrate, pyridine, and cucurbit[6]uril. According to single crystal X-ray diffraction data, water molecules coordinated to metal atom make hydrogen bonds to polarized carbonyl groups of the macrocycle. The heptaaquanitratogadolinium(III) [Gd(NO₃)(H₂O)₇]²⁺ cation is structurally characterized for the first time. Crystal system is triclinic, space group \(P\overline 1 \), a = 12.3137(4) Å, b = 14.2334(5) Å, c = 19.5629(6) Å; α = 80.850(1)°, β = 86.879(1)°, γ = 68.855(1)°; V = 3157.15(18) ų, Z = 2. Oriented hydrogen-bonded chains of alternating cucurbit[6]uril molecules and gadolinium aqua cations form in the crystal structure.     

Hydrothermal Synthesis,Crystal Structures,and Fluorescence Properties of Ni(II)–Ln(III) Complexes (Ln = Sm,Pr, Eu)

Three novel 3d–4f heterometal complexes [Ln(NiL)₃(Btca)(NO₃)] · xH₂O (Ln = Sm(III) (I), Pr(III) (II), Eu(III) (III) (H₂L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H₂Btca = benzotriazole-5-carboxylic acid) were solvothermally synthesized and characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1555557 (I), 1555555 (II), 1555556 (III)). They crystallized in the monoclinic space group P2₁/n for I (x = 1.5) and C2/c for (II) and (III) (x = 1), respectively. In these complexes, the central Ln(III) and external nickel ions are bridged by macrocyclic oxamide groups. The metal center of Ln(III) resides in a distorted bicapped square antiprism surrounding with six oxygen atoms of three oxamide groups, two oxygen atoms of Btca^2– ion and two oxygen atoms of NO₃^-. Furthermore, there are C–H···O and/or C–H···N hydrogen bond interactions among nitrate, benzotriazole-5-carboxylate, macrocyclic oxamide and water to form three-dimensional superamolecular architecture. The fluorescence properties of the compounds I and II are also discussed.     

Electrochemical properties of <Emphasis Type="Italic">n</Emphasis>-sulfonatothiacalyx[4]arene complexes with Fe<Superscript>3+</Superscript> and [Co(dipy)<Subscript>3</Subscript>]<Superscript>3+</Superscript> ions

The electrochemical properties of n-sulfonatothiacalyx[4]arene (H₄XNa₄) complexes with [Co(dipy)₃]³⁺ and Fe³⁺ ions were studied by means of cyclic voltammetry in aqueous solution at pH 2.5. The observed single-electron reduction of [Co(dipy)₃]³⁺ bound extraspherically to the upper rim and Fe³⁺ ion bound intraspherically to the lower rim of n-sulfonatothiacalyx[4]arene in binary [Co(dipy)₃]³⁺ · H₃X^5?, H₃X^5? · Fe³⁺, and ternary [Co(dipy)₃]³⁺ · H₃X^5? · Fe³⁺ heterometal complexes was more difficult than in the free state. The reversible single-electron transfer to the metal ion results in lower binding energy ([Co(dipy)₃]³⁺, ΔΔG ₀ = 3.9 kJ/mol) or in full fast dissociation of the complex (Fe³⁺). The ternary complex in the solution forms the aggregates, in which inner encapsulated Fe(III) and Co(III) ions are not reduced on the electrode. Their quantitative reduction takes place by the relay mechanism of intra- and intermolecular electron transfer through electrochemically generated [Co(dipy)₃]²⁺ outer ions.     

Coordination Chemistry of the Magic Inorganic Building Block {Fe<Superscript>II</Superscript>[Mo<Subscript>6</Subscript>P<Subscript>4</Subscript>O<Subscript>31</Subscript>]<Subscript>2</Subscript>}: Hydrothermal Synthesis and Crystal Structure of a New Reduced Ferrous Molybdophosphate

A new reduced ferrous molybdophosphate composite solid of the formula, [(C₁₀H₁₄N₂)H]₄[Fe^II ₁₀Mo^V ₂₄(H₂PO₄)₄(HPO₄)₁₂(PO₄)₄(H₂O)₁₆(OH)₁₆O₄₄]·12H₂O, has been synthesized from a reaction mixture of MoO₃, FeSO₄·7H₂O, C₂H₂O₄·2H₂O, nicotine, H₃PO₄, and H₂O under hydrothermal conditions. The crystal data: monoclinic, space group C2/m, a = 24.4349(124), b = 12.9935(66), c = 14.7281(74) Å, β = 104.87(1) Å, V = 4520(4) Å³, Z = 2, R ₁  = 0.0874, wR ₂  = 0.2179. The structure is built from the building blocks of the formula, {Fe^II[Mo₆P₄O₃₁]₂}, consisting of a network of MO₆ (M = Fe, Mo) octahedral and PO₄ tetrahedral linked through their vertices. The connectivity of the building blocks with two pairs of face-sharing dinuclear Fe(II) clusters of the formula of [Fe^II ₂(H₂O)₄O₅] on which a phosphate group is hanging gives rise to one-dimensional chains with eight-membered apertures. The remarkable hydrogen bonded interactions between the chains form a unique and interesting framework with three-dimensional intersecting tunnels where the protonated nicotine molecules as structuring templates and crystallization water molecules are situated.     

Structural features of monomeric octahedral <Emphasis Type="Italic">d</Emphasis><Superscript>2</Superscript>-rhenium(V) monooxo complexes with oxygen atoms of bidentate-chelating neutral and acidic ligands (O,P)

The structural features of 38 mononuclear d ²-Re(V) octahedral monooxo complexes (I–XXXVIII) with oxygen atoms of bidentate-chelating (O, P) ligands (L ⁿ ) are considered. The atoms O(L ⁿ ) are mostly in trans positions to O(oxo) ligands. In three compounds of general formula [ReO(L_mono)(L ⁿ )₂] (XXXVI–XXXVIII), the O atoms of two L ⁿ ligands occupy both trans and cis positions to oxo ligands. In one complex, namely, in [ReO(L ⁿ )(L _tri ¹¹ )], n = 3 (XXXV), the atom O(L³) is in the cis position to the oxo ligand; the trans position to O(oxo) is occupied by the atom O(L _tri ¹¹ ).     

Homo- and heteronuclear iron complexes {Fe<Subscript>2</Subscript>MO} with salicylic acid: Synthesis,structures, and physicochemical properties

A reaction of iron nitrate with magnesium salicylate and reactions of iron and cobalt chlorides with ammonium salicylate in the presence of water, methanol, DMAA, and DMF gave the trinuclear heterometallic complexes: [hexa-μ-salicylato-μ₃-oxo-0.4-dimethylacetamide-2.6-aquadiiron(III)magnesium(II)] tetra(dimethylacetamide), [Fe₂MgO(SalH)₆(DMAA)_0.4(H₂O)_2.6]·4DMAA (I); [hexa-μ]-salicylato-μ₃-oxo(dimethanol)aquadiiron(III)cobalt(II)] dimethylformamide · 2.5-hydrate, [Fe₂CoO(SalH)₆(CH₃OH)₂(H₂O)] · DMF · 2.5H₂O (II); and [hexa-μ-salicylato-μ₃-oxotriaquatriiron(III)] chloride dimethylacetamide monohydrate, [Fe₃O(SalH)₆(H₂O)₃]Cl · DMAA · H₂O (III). The X-ray study revealed that the molecular structures of complexes I and II are [Fe₂ ^IIIM^II(μ₃-O)(RCOO)₆L₃] · nSolv. The IR and Mössbauer spectra of complexes I–III were examined; their magnetochemical and thermal properties were studied. The parameters of the Mössbauer spectra (δ_Na ⁺ = 0.69 ± 0.03 mm/s, ΔE _Q = 0.76–1.08 mm/s, 300 K) suggest the high-spin state of the Fe³⁺ ions in complexes I–III (S = 5/2). The paramagnetic Fe³⁺ ions are involved in antiferromagnetic exchange interactions with the parameter J = ?44 cm^?1, g = 2.05 (for I). Complexes I–III are thermally unstable.     

Application of an experimental design to optimize a segregation method of <Superscript>129</Superscript>I and <Superscript>14</Superscript>C

In this work, the optimization of a segregation method of ¹²⁹I and ¹⁴C, two long-living radionuclides, main constituents of nuclear radioactive waste, has been developed. To be able to carry out this project, a fractional factorial experimental design was applied using 5 factors and 2 levels by factor (2^5–2). Only 8 experiments were necessary to identify the variables affecting the process, and very good recoveries of both radionuclides were obtained: (94?±?2)% for ¹²⁹I, and (99?±?1)% for ¹⁴C. The segregation of ¹²⁹I was influenced by flow (Q), volume of H₂SO₄ (V_H+), and carriers (CR), while V_H+ and time (t) played a major role in the segregation of ¹⁴C.     

Complexes of some tervalent metals with <Emphasis Type="Italic">N</Emphasis>-alkyl(benzyl)nitrozohydroxylamine derivatives

Twenty two new complexes of some tervalent metals (aluminum, chromium, iron, and lanthanides) with nitrozohydroxylamine N-alkyl(benzyl) derivatives ML₃^m · nH₂O, (m = 1?5) were synthesized and isolated in a crystalline state. The crystal and molecular structures of the iron(III) complex with N-(2-fluorobenzyl)-N-nitrozohydroxylamine were determined by X-ray diffraction. An octahedral coordination of the central ion and a bidentate chelating coordination of the organic ligand were established. The spectral criteria of coordination of nitrozohydroxylamine alkyl(benzyl) derivatives were determined, and the complexation processes in solutions were studied.     

Photochemical properties of mixed-ligand complexes europium carboxylates

The photochemical behavior of mixed-ligand complexes of europium carboxylates with nitrogen-and phosphorus-containing neutral ligands of island and dimer types, Eu(L)₃ · xD · nH₂O and [Eu(L)₃ · xD]₂ · nH₂O (L is the trifluoroacetate, toluate, or cinnamate anion), was studied. During UV irradiation of the complexes of europium carboxylates with 1,10-phenanthroline and 2,2′-dipyridyl, a luminescence buildup was observed. EPR measurements demonstrated that the observed buildup of luminescence from europium occurs in parallel with the increase of the concentration of radical anions formed from neutral ligands.     

Crystal and molecular structures and luminescence properties of [Eu(Cin)<Subscript>3</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> complex

The crystal structure of europium cinnamate of the composition [Eu(Cin)₃] _n (Cin is cinnamic acid anion C₉H₇O ₂ ^? ) was determined by X-ray crystallography (a = 22.626(1) Å, c = 7.7330(7) Å, space group R3/c, Z = 3, ρ_calc = 1.448 g/cm³). The coordination polyhedron of Eu atoms is a distorted trigonal prism with three centered square faces. The structure is built of infinite polymeric chains [Eu(Cin)₃] _n running along the c axis and linked by van der Waals and π stacking interactions. Luminescent characteristics of the compound were determined.     

Thermodynamic Study on the Protonation and Na<Superscript>+</Superscript>, Ca<Superscript>2+</Superscript>, Mg<Superscript>2+</Superscript>-Complexation of a Biodegradable Chelant (HEIDA) at Different Ionic Strengths and Temperatures

A potentiometric method has been used for the determination of the protonation constants of N-(2-hydroxyethyl)iminodiacetic acid (HEIDA or L) at various temperatures 283.15?≤?T/K?≤?383.15 and different ionic strengths of NaCl_(aq), 0.12?≤?I/mol·kg^?1?≤?4.84. Ionic strength dependence parameters were calculated using a Debye–Hückel type equation, Specific Ion Interaction Theory and Pitzer equations. Protonation constants at infinite dilution calculated by the SIT model are \( \log_{10} \left( {{}^{T}K_{1}^{\text{H}} } \right) = 8.998 \pm 0.008 \) (amino group), \( \log_{10} \left( {{}^{T}K_{2}^{\text{H}} } \right) = 2.515 \pm 0.009 \) and \( \log_{10} \left( {{}^{T}K_{3}^{\text{H}} } \right) = 1.06 \pm 0.002 \) (carboxylic groups). The formation constants of HEIDA complexes with sodium, calcium and magnesium were determined. In the first case, the formation of a weak complex species, NaL, was found and the stability constant value at infinite dilution is log₁₀K_NaL?=?0.78?±?0.23. For Ca²⁺ and Mg²⁺, the CaL, CaHL, CaL₂ and MgL species were found, respectively. The calculated stability constants for the calcium complexes at T?=?298.15 K and I?=?0.150 mol·dm^?3 are: log₁₀β_CaL?=?4.92?±?0.01, log₁₀β_CaHL?=?11.11?±?0.02 and \( \log_{10} \beta_{\text{Ca{L}}_{2}} \)?=?7.84?±?0.03, while for the magnesium complex (at I?=?0.176 mol·dm^?3): log₁₀β_MgL?=?2.928?±?0.006. Protonation thermodynamic functions have also been calculated and interpreted.     

Solution Thermodynamics of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis><Superscript>/</Superscript>-Ethylenebis-(salicylideneiminato)-diaquochromium(III) Chloride in Aqueous Dimethylsulphoxide

The densities, viscosities and refractive indices of N,N ^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride, [Cr(salen)(H₂O)₂]Cl, in aqueous dimethylsulfoxide (DMSO) with different mass fractions (w ₂ = 0.20, 0.40, 0.60, 0.80 and 1.00) of DMSO were determined at 298.15, 308.15 and 318.15 K under atmospheric pressure. From measured densities, viscosities and refractive indices the apparent molar volumes (V _φ ), standard partial molar volume (V _φ ⁰ ), the slope (S _V ^* ), standard isobaric partial molar expansibility (φ _E ⁰ ) and its temperature dependence (?φ _E ⁰ /?T) _p , the viscosity B-coefficient, its temperature dependence (?B/?T), solvation number (S _n ) and apparent molar refractivity (R _D ^φ ), etc., were calculated and discussed on the basis of ion–ion and ion–solvent interactions. These results revealed that the solutions are characterized by ion–solvent interactions rather than by ion–ion interactions and the complex behaves as a long range structure maker. Thermodynamics of viscous flow was discussed in terms of transition state theory.     

Determination of the stability constant and thermodynamic parameters between Tl<Superscript>+</Superscript>, Ag<Superscript>+</Superscript> and Pb<Superscript>2+</Superscript> cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand

The complexation reaction between Tl⁺, Ag⁺ and Pb²⁺ cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand in acetonitrile (ACN)–H₂O and methanol (MeOH)–H₂O binary solutions has been studied at different temperatures using conductometric method. The conductometric data show that the stoichiometry of the complexes is 1: 1 [M: L] and the stability constant of complexes changes with the binary solutions identity. Also, the structure of the resulting 1: 1 complexes was optimized using the LanL2dz basis set at the B3LYP level of theory using GAUSSIAN03 software. The results show that the change of logK_f for (DFMP.Pb)²⁺ and (DFMP.Ag)⁺ complexes with the mole ratio of acetonitrile and for (DFMP.Ag)⁺ and (DFMP.Tl)⁺ complexes with the mole ratio of methanol have a linear behavior, while the change of logK_f of (DFMP.Tl)⁺complex in ACN–H₂O binary solutions (with a minimum in X_ACN = 0.5) and (DFMP.Ag)⁺ complex in MeOH–H₂O binary solutions (with a minimum in X_MeOH = 0.75) show a non-linear behavior. The selectivity order of DFMP ligand for these cations in mol % CAN = 25 and 75 obtain Tl⁺ > Pb²⁺ > Ag⁺ but in mol % CAN = 50, the selectivity order observe Pb²⁺ > Tl⁺ > Ag⁺. Also, this selectivity sequence of DFMP in MeOH–H₂O (mol % MeOH = 75 and 100) and (mol % MeOH = 50) is obtained Pb²⁺ > Ag⁺ and Tl⁺ > Ag⁺ > Pb²⁺ respectively. The values of thermodynamic parameters show that these values are influenced by the nature and the composition of binary solution. In all cases, the resulting complexes are enthalpy stabilized and entropy destabilized. The TΔS_C^° versus ΔH_C^° plot of all obtained thermodynamic data shows a fairly good linear correlation which indicates the existence of enthalpy-entropy compensation in the complexation reactions.