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1.
二甲双胍盐酸盐、硝酸盐及与Zn2+, Cu2+, Ni2+三种金属离子配合物的结构特点、电荷分布和二甲双胍配合物对四氧嘧啶糖尿病小鼠血糖影响的研究表明:Zn2+配合物表现为较为少见的单齿配位,而Cu2+, Ni2+配合物表现为双齿配位.进一步电荷分布计算发现,与端基N原子相比,二甲双胍的桥基N原子具有较高的负电荷.三种金属离子配合物对四氧嘧啶糖尿病小鼠血糖的影响研究显示,桥基N配位掩蔽后,二甲双胍的降血糖功能丧失.说明桥基N对二甲双胍的降血糖作用具有重要意义. 相似文献
2.
V. A. Dobysh N. V. Koktysh V. A. Tarasevich V. E. Agabekov V. N. Makatun L. I. Antonovskaya N. A. Belyasova 《Russian Journal of General Chemistry》2012,82(11):1764-1769
The reaction products of polyhexamethyleneguanidine hydrochloride with the Cu2+, Zn2+, and Ni2+ ions, which are the polyligand coordination compounds formed by polyguanidine and hydroxyl ligands, were studied using IR, UV, and ESR spectroscopy. The influence of the nature of the chelating agent on the structure of the complexes formed was revealed. Antibacterial properties of the synthesized complexes were assessed. 相似文献
3.
Tetraaza complexes with M(2+) were produced in the gas phase by Electrospray (ESI) of solutions containing salts of M(2+)dinitrates and a tetraaza compound such as cyclam. The complex CyclM(2+) formed in solution and transferred to the gas phase via ESI was introduced into a reaction chamber containing known partial pressures of a ligand L. Equilibria between CyclM(2+) and L establish CyclML(n)(2+) = CyclML(n-1)(2+) + L and the equilibrium constants K(n,n-1) are determined with a mass spectrometer. Determinations at different temperatures lead to not only the DeltaG(0)(n,n-1) values but also the DeltaH(0)(n,n-1) and DeltaS(0)(n,n-1) values. Data for n = 1, 2, and 3 were obtained for L = H(2)O and CH(3)OH. The DeltaG(0)(1,0), DeltaH(0)(1,0) as well as DeltaG(0)(2,1), DeltaH(0)(2,1) values, when M(2+) = Mn(2+) and Zn(2+), were larger than those for Ni(2+) and Cu(2+). The ligand field theory and the Irvine-Williams series predict a reverse order, i.e., stronger bonding with Ni(2+) and Cu(2+) for simple ligand reactions with M(2+). An examination of the differences of the reactions in solution and gas phase provides a rationale for the observed reverse order for the CyclM(2+) + L reactions. Differences between gas phase and solution are found also when M(2+) = Cu(2+), but the tetraaza macrocycle is changed from, 12-ane to 14-ane to 15-ane. The strongest bonding in solution is with the 14-ane while in the gas phase it is with the 15-ane. Bond free energies, DeltaG(0)(1,0), for CyclCu(2+) with L = H(2)O, CH(3)OH, NH(3), C(2)H(5)OH, C(3)H(7)OH, (C(2)H(5))(2)O, and CH(3)COCH(3), are found to increase in the above order. The order and magnitude of the DeltaG(0)(1,0) values is close to DeltaG(0)(1,0) values observed with potassium K(+) and the same ligands. These results show that the cyclam in CyclCu(2+) leads to an extensive shielding of the +2 charge of Cu(2+). Ligands with gas phase basicities that are relatively high, lead to deprotonation of CyclM(2+). The deprotonation varies with the nature of M(2+) and provides information on the extent of electron transfer from the N atoms of the cyclam, to the M(2+) ions. 相似文献
4.
Mahmood Payehghadr Akram Zamani Ali Reza Salehi Sadaghiani Mehdi Taghdiri 《Journal of inclusion phenomena and macrocyclic chemistry》2008,62(3-4):255-261
The complexation reaction between 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane ligand (Kryptofix5) and Zn2+, Ni2+, Co2+, Pb2+ and Cu2+ ions were studied conductometrically in acetonitrile solution. The formation constants of the resulting 1:1 complexes were calculated from the computer fitting of the molar conductance and absorbance measurements in various mole ratios. The enthalpy and entropy changes of the complexation reactions were derived from titration conductometry in acetonitrile at various temperatures. At 25 °C, the stability of the resulting complexes varied in the order Pb2+ > Zn2+ > Cu2+> Co2+> Ni2+. 相似文献
5.
The coordination behavior and reactivity of the phenol-substituted bis(pyrazolyl)methane ligands, (3,5-(t)Bu(2)-2-phenol)bis(3,5-Me(2)-pyrazol-1-yl)methane (L1-H) and 2-phenol-bis(3,5-Me(2)-pyrazol-1-yl)methane (L2-H) have been investigated in the metal complexes (L1-H)CoCl(2) (1), (L1-H)ZnCl(2) (2), (L3)CuCl(2) (3), (L2)(2)Co(2)Cl(2) (4) (L2-H)ZnCl(2) (5), and (L2-H)CuCl(2)·H(2)O (6). The mononuclear tetrahedral cobalt complex 1 was isolated and fully characterized by X-ray single crystal diffraction and (1)H NMR spectroscopy and relaxometry. The neutral L1-H is κ(2)-coordinated to the metal center whereas the not coordinated hydroxy-phenyl group is involved in extended intermolecular hydrogen bonds. Aerobic oxidation of L1-H was observed in the reaction of this ligand with CuCl(2) to yield the para-quinone derivative L3 (L3 = 2-(t)Bu-6-(bis(3,5-Me(2)-pyrazol-1-yl)methyl)cyclohexa-2,5-diene-1,4-dione). Upon oxidation L3 resulted κ(2)-coordinated to the tetrahedral Cu(II) metal center, affording 3. The reaction of L2-H with CoCl(2)·6H(2)O produced the elimination of 1 equiv of hydrochloric acid and the formation of the binuclear complex 4 in which one cobalt is in an octahedral environment featuring two κ(3)-coordinated deprotonated ligands whereas the second cobalt center is detected in tetrahedral coordination geometry, bound to the octahedral cobalt via two phenoxo bridging moieties. Interestingly L2-H, (3-(t)Bu-2-phenol)bis(3,5-Me(2)-pyrazol-1-yl)methane (L4-H), or (5-(t)Bu-2-phenol)bis(3,5-Me(2)-pyrazol-1-yl)methane (L5-H) were not oxidized in the reaction with CuCl(2). The reaction of the ligand L2-H with ZnCl(2) and CuCl(2)·2H(2)O yielded the κ(2)-coordinated tetrahedral complex 5 and the square planar complex 6, respectively. The application of the cobalt complex 1 as molecular dosimeter for H(2)S was explored and compared to that of the zinc analogue 2. Density functional theory (DFT) calculations and NMR experiments to assess the possible mechanisms of H(2)S detection by both 1 and 2 are also described. 相似文献
6.
Plush SE Lincoln SF Wainwright KP 《Dalton transactions (Cambridge, England : 2003)》2004,(9):1410-1417
The pK(a)s and Zn2+, Cd2+ and Cu2+ complexation constants (K) for 1,4,7-tris[(2'S)-acetamido-2'-(methyl-3'-phenylpropionate)]-1,4,7-triazacyclononane, 1, 1,4,7-tris[(2'S)-acetamido-2'-(1'-carboxy-3'-phenylpropane)]-1,4,7-triazacyclononane, H(3)2, 1,4,7-tris[(2'S)-acetamido-2'-(methyl-3'-(1H-3-indolyl)propionate)]-1,4,7-triazacyclononane, 3, and 1,4,7,10-tetrakis[(2'S)-acetamido-2'-(methyl-3'-phenylpropionate)]-1,4,7,10-tetraazacyclododecane, 4, 1,4,7,10-tetrakis[(2'S)-acetamido-2'-(1'-carboxy-3'-phenylpropane)]-1,4,7,10-tetraazacyclododecane, H(4)5, in 20 : 80 v/v water-methanol solution are reported. The pK(a)s within the potentiometric detection range for H(3)1(3+) = 8.69 and 3.59, for H(6)2(3+) = 9.06, 6.13, 4.93 and 4.52, H(3)3(3+) = 8.79 and 3.67, H(4)4(4+) = 8.50, 5.62 and 3.77 and for H(8)5(4+) = 9.89, 7.06, 5.53, 5.46, 4.44 and 4.26 where each tertiary amine nitrogen is protonated. The complexes of 1: [Zn(1)]2+(9.00), [Cd(1)]2+ (6.49), [Cd(H1)]3+ (4.54) and [Cu(1)]2+ (10.01) are characterized by the log(K/dm3 mol(-1)) values shown in parentheses. Analogous complexes are formed by 3 and 4: [Zn(3)]2+ (10.19), [Cd(3)]2+ (8.54), [Cu(3)]2+ (10.77), [Zn(4)]2+ (11.41) [Cd(4)]2+ (9.16), [Cd(H4)]3+ (6.16) and [Cu(4)]2+ (11.71). The tricarboxylic acid H(3)2 generates a greater variety of complexes as exemplified by: [Zn(2)-] (10.68) [Zn(H2)] (6.60) [Zn(H(2)2)+] (5.15), [Cd(2)](-) (4.99), [Cd(H2)] (4.64), [Cd(H2(2))]+ (3.99), [Cd(H(3)2)]2+ (3.55), [Cu(2)](-) (12.55) [Cu(H2)] (7.66), [Cu(H(2)2)]+ (5.54) and [Cu(2)2](4-) (3.23). The complexes of H(4)5 were insufficiently soluble to study in this way. The 1H and 13C NMR spectra of the ligands are consistent with formation of a predominant Zn2+ and Cd2+ Delta or Lambda diastereomer. The preparations of the new pendant arm macrocycles H(3)2, 3, 4 and H(4)5 are reported. 相似文献
7.
The formation and dissociation kinetics of the pentaco-ordinated Cu2+, Ni2+, Co2+ and Zn2+ complexes with 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (4-MeCyclam-14) was studied by pH-stat techniques and spectrophotometrically. The rates of the reactions between 4-MeCyclam-14 and each of the four metal ions, although slower than normal complexations by a factor of 103?104, closely follow the order Cu2+ > Zn2+ > Co2+ > Ni2+, found for the rate of water exchange. This implies that beside water exchange an other constant factor plays an important role in the rate determing step. The dissociation of the pentaco-ordinated 4-MeCyclam-14 complexes is acid catalyzed. The limiting rate for acid dissociation is not reached even in 2.5M HNO3 in the case of Ni(4-MeCyclam-14)2+. From the formation and dissociation rates stability constants have been calculated, which do not show any macrocyclic effect. 相似文献
8.
Ibtissam Elaaraj Safae ER. Raouan Asmae Nakkabi Bouchra Es-sounni Ibnsouda Koraichi Noureddine El moualij Mohammed Fahim 《印度化学会志》2022,99(5):100404
New metal complexes of (Zn(II), Co(II), Ni(II) and Cu(II)) based on the ligand 2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzo[d]imidazole] were synthesized, whose structures were determined with the different spectroscopic techniques 1H NMR,13C NMR, FT-IR, UV–Visible and by mass spectrometry. The thermal analysis was performed by TG-DTA. The antioxidant activity of the ligand and its complexes was evaluated by DPPH (2,2-diphenyl-1-picrylhydrazyl) method, in comparison with the synthetic antioxidant, ascorbic acid. The results obtained showed that the antioxidant activity of the ligand and its complexes is moderate and that the copper complex has a high activity that exceeds that of ascorbic acid. Antimicrobial activity of the ligand and its metal complexes was studied against two Gram-positive bacteria: Bacillus subtilis ILP1428B, Staphylococcus aureus CIP543154 and two Gram-negative bacteria: Pseudomonas aeruginosa ATCC27653, Escherichia coli CIP5412 (American Type Culture Collection)the activity data show that the metal complexes are more potent than the free ligand. 相似文献
9.
Aliakbar Dehno Khalaji Mahsa Nikookar Debasis Das 《Journal of Thermal Analysis and Calorimetry》2014,115(1):409-417
Asymmetric bidentate Schiff base ligand (HL) and its cobalt(III), nickel(II), and copper(II) complexes have been synthesized (where L = 2-[(4-methoxy-2-nitrophenyl)iminomethyl]phenol). The ligand and its metal complexes have been characterized by elemental analyses (CHN) and FTIR spectroscopy. Thermogravimetric analyses of the compounds reveal their thermal stabilities along with their thermal decomposition pattern. In addition, the complexes have been used for the preparation of corresponding metal oxide nanoparticles by controlled aerobic thermal decomposed at 500 °C. The FTIR pattern of the obtained solids receals the formation of the metal oxides nanoparticles. 相似文献
10.
A decamer duplex model of Domain II of the hammerhead ribozyme was synthesized with [8-13C-1,7,NH2-15N3]-guanosine at the known metal binding site, G10.1 and, for comparison, [2-13C-1,7,NH2-15N3]-guanosine at G16.2. The 15N NMR chemical shifts of the labeled N7s monitored during addition of Mg2+, Cd2+, and Zn2+ showed the same preference for binding at G10.1 over G16.2 for each metal. These results demonstrate that 15N labeling can be used to evaluate the binding of different metals, including Mg2+, to a given nitrogen, as well as to compare the binding potential of different sites. 相似文献
11.
《Chemical physics letters》1986,132(2):200-204
A method for measuring the kinetic-energy spectrum of high-Rydberg fragments from collisions of keV molecular ions with rare-gas atoms is described. The kinetic-energy spectra of high-Rydberg fragments from the collisions between D2+, H2+, N2+ and C2+ ions having 8 keV kinetic energy and thermal He and Xe are reported. Two single-collision processes for the generation of high-Rydberg fragments have been identified. 相似文献
12.
Two bis(N,N-dialkylamide) derivatives of DTPA [(carboxymethyl)iminobis (ethylenenitrilo) tetraacetic acid], DTPA-BDMA = the bis(N,N-dimethylamide) and DTPA-BDEA = the bis(N,N-diethylamide) were synthesized. Their protonation constants were determined by potentiometric titration in 0.10 M Me4NNO3 and by NMR pH titration at 25.0 ± 0.1 °C. Stability and selectivity constants were measured to evaluate the possibility of using the corresponding gadolinium(III) complexes for magnetic resonance imaging contrast agents. The stability constants of gadolinium(III), copper(II), zinc(II), and calcium(II) complexes with DTPA-BDMA and DTPA-BDEA were investigated quantitatively by potentiometry. The stability constant for gadolinium(III) complexes is larger than those for Ca(II), Zn(II), and Cu(II) complexes. The selectivity constants and modified selectivity constants of the amides for Gd3+ over endogenously available metal ions were calculated. Effectiveness of these two ligands in binding divalent and trivalent metal ions in biological media is assessed by comparing pM values at physiological pH 7.4. Spin-lattice relaxivity values R1 for Gd(III) complexes were also determined. The observed relaxivity values were found to decrease with increasing pH in the acid range below pH 4 and relaxivity values became invariant with respect to pH changes over the range of 4–10. 17O NMR shifts showed that the [Dy(DTPA-BDMA)] and [Dy(DTPA-BDEA)] complexes had one inner-sphere water molecule. Water proton spin-lattice relaxation rates for the [Gd(DTPA-BDMA)] and [Gd(DTPA-BDEA)] complexes were also consistent with one inner-sphere gadolinium(III) coordination position. 相似文献
13.
A calix[4]arene conjugate bearing salicylyl imine having dibenzyl moiety (L) has been synthesized and characterized, and its ability to recognize three most important essential elements of human system, viz., iron, copper, and zinc, has been addressed by colorimetry and fluorescence techniques. L acts as a sensor for Cu(2+) and Fe(2+) by exhibiting visual color change and for Zn(2+) based on fluorescence spectroscopy. L shows a minimum detection limit of 3.96 ± 0.42 and 4.51 ± 0.53 ppm and 45 ± 4 ppb, respectively, toward Fe(2+), Cu(2+), and Zn(2+). The in situ prepared [ZnL] exhibits phosphate sensing among 14 anions studied with a detection limit of 247 ± 25 ppb. The complexes of Zn(2+), Cu(2+), and Fe(2+) of L have been synthesized and characterized by different techniques. The crystalline nature of the zinc and copper complexes and the noncrystalline nature of simple L and its iron complex have been demonstrated by powder XRD. The structures of Cu(2+) and Zn(2+) complexes have been established by single crystal XRD wherein these were found to be 1:1 monomeric and 2:2 dimeric, respectively, using N(2)O(2) as binding core. The geometries exhibited by the Zn(2+) and the Cu(2+) complexes were found to be distorted tetrahedral and distorted square planar, respectively. The iron complex of L exists in 1:1 stoichiometry as evident from the mass spectrometry and elemental analysis. 相似文献
14.
微波衍生-离子对高效液相-磺化四苯基卟啉光度法同时测定痕量镍、铜、锰和锌 总被引:2,自引:0,他引:2
用磺化四苯基卟啉 (TPPS4 )作柱前衍生试剂 ,在微波作用下进行衍生反应 ,研究了衍生和分离Ni2 + ,Mn2 + ,Zn2 + 和Cu2 + 的最佳条件。在 75 0W的微波作用下衍生反应 3min ,在C18柱上采用乙腈 水 (体积比为 2 2 5∶77 5 )体系作流动相 ,四乙基溴化铵 (TEABr)作离子对试剂 ,在 415nm处检测 ,建立了微波衍生 离子对高效液相快速分离、光度检测Ni2 + ,Mn2 + ,Zn2 + 和Cu2 + 的新方法。络合物和反应试剂在 15min内出峰完毕。Zn2 + ,Cu2 + ,Ni2 + 和Mn2 + 的检测限分别为 0 0 5 μg/L ,0 0 1μg/L ,0 10 μg/L和 0 40 μg/L。 相似文献
15.
Four d10 transition-metal coordination complexes 1–4 (1: [Ag2(TPT)2(TPTH)2]; 2: [Cu6(TPT)6]·2DMF; 3: [Cd(TPT)2(TPTH)]·CH3CH2OH, 4: [Zn(TPT)2]n) have been constructed from a newly designed heterocyclic thioamide ligand, TPTH (TPTH = 4-(thiophen-2-yl)-pyrimidine-2-thiol). All complexes have been structurally elucidated by single crystal X-ray diffraction analyses. Except for 4, which shows a one-dimensional (1-D) chain structure, 1–3 are all discrete coordination complexes featuring dinuclear, hexanuclear and mononuclear entities, respectively. Their photophysical properties have been evaluated in the solid state at room temperature by UV–vis diffuse reflectance and luminescence spectra. Among them, 2 exhibits a strong red luminescence (λem = 699 nm) with a remarkable red-shift of the maximum emission compared to that of the TPTH ligand (λem = 536 nm). The red emission observed with 2 is ascribed to a LMCT (ligand-to-metal charge transfer) transition which agrees with the DFT calculations. 相似文献
16.
Coordination complexes of modified hydrazine are prepared with Ni(II), Cu(II), and Zn(II) metal ions. The ligand is synthesized by removing the methoxy moiety of methyl anthranilate with nitrogen of hydrazine hydrate, creating new coordination site. The coordination complexes are synthesized by reacting the ABH ligand with dehydrated M(II) [Cu2+, Zn2+ and Ni2+] bromide in an inert environment. The structures of the coordination complexes are elucidated basing on the physical measurements including elemental analysis, NMR, IR, UV–Vis spectra, magnetic and conductance measurements. These results reflect the M(ABH)Br2 composition of the corresponding complexes. Thermal studies show the Irving William trend for the stability of complexes. Antibacterial activities and antifungal studies are also carried out in order to investigate the biological activity upon complexation. 相似文献
17.
Knobloch B Mucha A Operschall BP Sigel H Jeżowska-Bojczuk M Kozłowski H Sigel RK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(19):5393-5403
With a view on protein–nucleic acid interactions in the presence of metal ions we studied the “simple” mixed‐ligand model systems containing histamine (Ha), the metal ions Ni2+, Cu2+, or Zn2+ (M2+), and the nucleotides adenosine 5′‐triphosphate (ATP4?) or uridine 5′‐triphosphate (UTP4?), which will both be referred to as nucleoside 5′‐triphosphate (NTP4?) . The stability constants of the ternary M(NTP)(Ha)2? complexes were determined in aqueous solution by potentiometric pH titrations. We show for both ternary‐complex types, M(ATP)(Ha)2? and M(UTP)(Ha)2?, that intramolecular stacking between the nucleobase and the imidazole residue occurs and that the stacking intensity is approximately the same for a given M2+ in both types of complexes: The formation degree of the intramolecular stacks is estimated to be 20 to 50 %. Consequently, in protein–nucleic acid interactions imidazole–nucleobase stacks may well be of relevance. Furthermore, the well‐known formation of macrochelates in binary M2+ complexes of purine nucleotides, that is, the phosphate‐coordinated M2+ interacts with N7, is confirmed for the M(ATP)2? complexes. It is concluded that upon formation of the mixed‐ligand complexes the M2+? N7 bond is broken and the energy needed for this process corresponds to the stability differences determined for the M(UTP)(Ha)2? and M(ATP)(Ha)2? complexes. It is, therefore, possible to calculate from these stability differences of the ternary complexes the formation degrees of the binary macrochelates: The closed forms amount to (65±10) %, (75±8) %, and (31±14) % for Ni(ATP)2?, Cu(ATP)2?, and Zn(ATP)2?, respectively, and these percentages agree excellently with previous results obtained by different methods, confirming thus the internal validity of the data and the arguments used in the evaluation processes. Based on the overall results it is suggested that M(ATP)2? species, when bound to an enzyme, may exist in a closed macrochelated form only, if no enzyme groups coordinate directly to the metal ion. 相似文献
18.
Florentina Pătraşcu Mihaela Badea Maria Nicoleta Grecu Nicolae Stanică Luminiţa Măruţescu Dana Marinescu Cezar Spînu Cristian Tigae Rodica Olar 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1421-1429
New species of type MLCl2·nH2O (M:Ni, n = 6; M:Cu, n = 1.5 and M:Zn, n = 1; L: 1,8-bis(3′-ketopyridil)-1,3,6,8,10,13-hexaazacyclotetradecane, ligand resulted by 1,2-diaminoethane, nicotinamide and formaldehyde template condensation) were synthesised. The compounds were characterised by chemical analysis, ESI–MS, IR, NMR, UV–Vis-NIR and EPR spectroscopy as well as magnetic data at room temperature. The modifications in the IR and NMR spectra are in accordance with the condensation process. Electronic spectra indicate that Ni(II) adopts an octahedral stereochemistry while the surrounding of Cu(II) is square-pyramidal. The proposed stereochemistry was furthermore confirmed by magnetic moments and EPR spectrum at room temperature. The water is eliminated in one or two steps, respectively, while the oxidative degradation of the ligand and chloride decomposition occur in two steps. The final residues consist of the most stable metallic oxides as X-ray powder diffraction indicates. The newly synthesised compounds were evaluated for their antimicrobial effect against different bacterial and fungal strains. 相似文献
19.
Chillemi G D'Angelo P Pavel NV Sanna N Barone V 《Journal of the American Chemical Society》2002,124(9):1968-1976
In this paper we have developed an effective computational procedure for the structural and dynamical investigation of ions in aqueous solutions. Quantum mechanical potential energy surfaces for the interaction of a transition metal ion with a water molecule have been calculated taking into account the effect of bulk solvent by the polarizable continuum model (PCM). The effective ion-water interactions have been fitted by suitable analytical potentials, and have been utilized in molecular dynamics (MD) simulations to obtain structural and dynamical properties of the ionic aqueous solutions. This procedure has been successfully applied to the Co2+-H2O open-shell system and, for the first time, Co-oxygen and Co-hydrogen pair potential functions have been determined and employed in MD simulations. The reliability of the whole procedure has been assessed by applying it also to the Zn2+ and Ni2+ aqueous solutions, and the structural and dynamical properties of the three systems have been calculated by means of MD simulations and have been found to be in very good agreement with experimental results. The structural parameters of the first solvation shells issuing from the MD simulations provide an effective complement to extended X-ray absorption fine structure (EXAFS) experiments. 相似文献
20.
Berti E Caneschi A Daiguebonne C Dapporto P Formica M Fusi V Giorgi L Guerri A Micheloni M Paoli P Pontellini R Rossi P 《Inorganic chemistry》2003,42(2):348-357
The basicity behavior and ligational properties of the ligand 2-((bis(aminoethyl)amino)methyl)phenol (L) toward Ni(II), Cu(II), and Zn(II) ions were studied by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, l = 0.15 mol dm-3). The anionic L-H- species can be obtained in strong alkaline solution; this species behaves as tetraprotic base (log K1 = 11.06, log K2 = 9.85, log K3 = 8.46, log K4 = 2.38). L forms mono- and dinuclear complexes in aqueous solution with all the transition metal ions examined; the dinuclear species show a [M2(L-H)2]2+ stoichiometry in which the ligand/metal ratio is 2:2. The studies revealed that two mononuclear [ML-H]+ species self-assemble, giving the dinuclear complexes, which can be easily isolated from the aqueous solution due to their low solubility. This behavior is ascribed to the fact that L does not fulfill the coordination requirement of the ion in the mononuclear species and to the capacity of the phenolic oxygen, as phenolate, to bridge two metal ions. All three dinuclear species were characterized by determining their crystal structures, which showed similar coordination patterns, where all the single metal ions are substantially coordinated by three amine functions and two oxygen atoms of the phenolate moieties. The two metals in the dinuclear complexes are at short distance interacting together as shown by magnetic measurements performed with Ni(II) and Cu(II) complexes, which revealed an antiferromagnetic coupling between the two metal ions. The [Cu2(L-H)2]2+ cation shows a phase transition occurring by the temperature between 100 and 90 K; the characterization of the compounds existing at different temperatures was investigated using X-ray single-crystal diffraction, EPR, and magnetic measurements. 相似文献