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1.
Six novel μ-oxamido trinuclear complexes, namely Cu2(oxap)2Ln(ClO4)3 (Ln: La, Pr, Nd, Gd, Yb, Ho), where oxap is N,N′-bis(2-aminopropyl)oxamido, have been synthesized. The complex Cu2(oxap)2Gd(ClO4)3 was characterized with variable temperature magnetic susceptibility (4—300 K). The exchange integrals J (Cu—Gd) and J′ (Cu–Cu) were found to be 0.83 cm?1 and ?1.62 cm?1, indicating that very weakly ferromagnetic spin-exchange interaction operates between Cu(II) and Gd (III) ions.  相似文献   

2.
Summary Seven novel -oxamido hetero-metal binuclear complexes have been prepared and characterized, namely [Cu(oxae)-Ln(NO2-phen)2 (ClO4)](ClO4)2, where oxae denotes the N,N-bis(2-aminoethyl)oxamido dianion, NO2-phen denotes 5-nitro-1,10-phenanthroline and Ln is Nd, Eu, Gd, Tb, Dy, Ho or Er. The magnetic susceptibility of [Cu(oxae)Gd(NO2-phen)2(ClO4)](ClO4)2 was measured over a 4–300 K temperature range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator = -2J 1·2, giving the exchange integral for GdIII J (Cu-Gd) = -1.52cm-1. This indicated a weak antiferromagnetic interaction between the CuII and CdIII ions.Visiting scholar: Qufu Normal University.Visiting scholar: Tianjin Second Medical College.  相似文献   

3.
Kong  Xiang-He  Yan  Cui-Wei  Li  Yan-Tuan  Liao  Dai-Zheng 《中国化学》1999,17(6):609-617
Seven new μ-isophthalato dinuclear lanthanide(III) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln=La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1,10-phenanthroline (Me2-phen), IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [ Gd2 (IPHTA) (Me2-phen)4 ( ClO4 )2 ] ((ClO4 )2 complex were measured in the temperature range of 4–300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = -2JS1. J2. giving the exchange parameter J = -0.19 cm?1. This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(III)-Gd(III) im within the complex.  相似文献   

4.
Six novel μ-oxamido heterobinuclear complexes, namely Cu(oxae)Ln(Me2bpy)2-(ClO4)3 (Ln? La, Nd, Gd, Tb, Ho, Er), where oxae denotes N, N'-bis(2-aminoethyl)oxamido dianion, Me2bpy is 4,4'-dimethyl-2,2'-bipyridyl, have been synthesized and characterised by elemental analyses, IR, conductivity measurements and electronic spectra. The temperature dependence of the magnetic susceptibility of Cu(oxae)Gd(Me2bpy)2(ClO4)3 has been measured over the range 4–300 K. The least-squares fit of the experimental susceptibilities yielded J = 1.87 cm?1. The observed Gd(III)-Cu(II) coupling is ferromagnetic. One plausible mechanism that can cause a ferromagnetic coupling between Gd(III) and Cu(II) is discussed in terms of spin-polarization.  相似文献   

5.
Twelve oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes Ln[Cu(PMoxd)]4(ClO4)3 · 5H2O (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and PMoxd = the N,N′-Bi(α-pyridylmethyl)-oxamide dianion) and 12 oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes with the formula of Ln[Cu(PEoxd)]4(ClO4)3 · 5H2O (PEoxd = the N,N′-Bi(α-pyridylethyl)-oxamide dianion) were synthesized and characterized. The magnetic properties of Gd[Cu(PMoxd)]4(ClO4)3 · 5H2O (7) and Gd[Cu(PEoxd)]4(ClO4)3 · 2H2O (19) show that there are ferromagnetic interactions between Gd(III) and Cu(II) in the complexes with J Cu–Gd = 1.38 cm?1 and J Cu–Gd = 1.00 cm?1, respectively. Fluorescent quenching phenomena for Eu[Cu(PMoxd)]4(ClO4)3 · 5H2O (6) and Tb[Cu(PMoxd)]4(ClO4)3 · 5H2O (8) were also observed.  相似文献   

6.
Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO3)2, Cu(ClO4)2, Zn(ClO4)2, Ni(NO3)2 and PdCl2 gives complexes with stoichiometry [Cu(L)2(H2O)2](NO3)2, [Cu(L)2(H2O)2](ClO4)2, [Zn(L)2(H2O)2] (ClO4)2, [Ni(L)2(H2O)Cl](NO3) and PdLCl2. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)2(H2O)2](NO3)2, [Cu(L)2(H2O)2](ClO4)2, and [Zn(L)2(H2O)2](ClO4)2 were determined by X-ray crystallography. The cation complexes [M(L)2(H2O)2] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.  相似文献   

7.
Three new μ‐oxamido‐bridged heterodinuclear copper (II)‐chromium (III) complexes formulated [Cu(Me2oxpn)Cr‐(L)2](NO3)3, where Me2oxpn denotes N,N'‐bis(3‐amino‐2, 2‐dimethylpropyl)oxamido dianion and L represents 5‐methyl‐1,10‐phenanthroline (Mephen), 4,7‐diphenyl‐1,10‐phenanthroline (Ph2phen) or 2,2′‐bipyridine (bpy), have been synthesized and characterized by elemental analyses, IR and electronic spectral studies, magnetic moments of room‐temperature and molar conductivity measurements. It is proposed that these complexes have oxamido‐bridged structures consisting of planar copper (II) and octahedral chromium (III) ions. The variable temperature magnetic susceptibilities (4.2–300 K) of complexes [Cu(Me2oxpn)Cr(Ph2phen)2](NO3)3 (1) and [Cu(Me2oxpn)Cr(Mephen)2] (NO3)3 (2) were further measured and studied, demonstrating the ferromagnetic interaction between the adjacent chromium (III) and copper (II) ions through the oxamido‐bridge in both complexes 1 and 2. Based on the spin Hamiltonian, ? = ‐ 2J?1 · ?2, the exchange integrals J were evaluated as + 21.5 an?1 for 1 and + 22.8 cm?1 for 2.  相似文献   

8.
Summary Reaction of Cu(OAc)2, 4-(1H)-pyridone (LH) and Dy or Gd nitrate in MeOH resulted in the formation of the heterometallic complexes [Cu2LnL2(LH)2(NO3)(OH)4· xH2O], Ln = Dy (1) or Gd (2). Reaction of Cu(OH)2 with 4-(1H)-pyridone and Dy(NO3)3 in DMF resulted in the formation of the heterometallic compound [Cu2DyL2(LH)2(NO3)2(OH)3·DMF] (3). The Cu complexes [Cu(OAc)L]2 and [CuL2·DMF] x have also been prepared from the reaction of 4-(1H)-pyridone with Cu2+ in MeOH and DMF, respectively. All the complexes were characterized by elemental analyses, and i.r. and X-band e.s.r. spectroscopies.  相似文献   

9.
Summary Four new trinuclear copper(II) complexes bridged by o-phenylenebis(oxamato) (opba) and end-capped with 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen), 2,2-bipyridyl (bipy) or 4,4-dimethyl-2,2-bipyridyl (Me2bipy), {[Cu(opba)][Cu(L)]2}(ClO4)2 (L = phen, NO2-phen, bipy or Me2bipy), have been synthesized and characterized. Based on i.r., elemental analyses, conductivity measurements and electronic spectra, oxamato-bridged structures consisting of three copper(II) ions in which each copper(II) ion has a square-planar environment are proposed. The temperature-dependent magnetic susceptibility of {[Cu(opba)][Cu(phen)]2} (ClO4)2 has been studied in the 4.2–300 K range, giving the exchange integral J = -134.4cm–1. The result revealed the operation of an antiferromagnetic spin-exchange interaction between the adjacent copper ions.  相似文献   

10.
Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-l,10-phenanthroline(NO2-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)23H2O has been studied in the 4–300 K range, giving the exchange integral J—109 cm?1. The HMT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.  相似文献   

11.
The two complexes, [Ln(Ala)2(Im)(H2O)](ClO4)3 (Ln=Pr, Gd), were synthesized and characterized. Using a solution-reaction isoperibol calorimeter, standard enthalpies of reaction of two reactions: LnCl3⋅6H2O(s)+2Ala(s)+Im(s)+3NaClO4(s)=[Ln(Ala)2(Im)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(l) (Ln=Pr, Gd), at T=298.15 K, were determined to be (39.26±0.10) and (5.33±0.12) kJ mol–1 , respectively. Standard enthalpies of formation of the two complexes at T=298.15 K, ΔfHΘm {[Ln(Ala)2(Im)(H2O)](ClO4)3(s)} (Ln=Pr, Gd), were calculated as –(2424.2±3.3) and –(2443.4±3.3) kJ mol–1 , respectively.  相似文献   

12.
Five chloroanilato-bridged manganese(II) binuclear complexes, [Mn2(CA)L4](ClO4)2, where L = 4,4′-dimethyl-2,2′-bipyridine (Me2-bpy), 5-methyl-1,10-phenanthroline (Me-phen), 5-chloro-1,10-phenanthroline (Cl-phen), 5-nitro-1,10-phenanthroline (NO2-phen) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen), and CA represents the dianion of chloroanilic acid, have been synthesized and characterized by elemental analyses, molar conductivity and room temperature magnetic moment measurements, and by spectroscopy. It is proposed that these complexes have CA-bridged structures and consist of two manganese(II) ions in a distorted-octahedral environment. The complexes [Mn2(CA)(Me2-bpy)4](ClO4)2 (1) and [Mn2(CA)(Me-phen)4](ClO4)2 (2) were characterized by variable temperature magnetic susceptibility measurements (4–300 K) and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator, Ĥ = −2 1 Ŝ 2, giving the exchange integral J = −1.98 cm−1 for (1) and J = −2.41 cm−1 for (2). This result indicates that there is a weak antiferromagnetic spin-exchange interaction between the two MnII ions within each molecule. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

13.
Newly designed hetero-dinuclear 3d–4f complex [Cu(L)La (NO3)2(μ-NO3)(H2O)]·EtOH ( 1 ), hetero-tetranuclear 3d–4f complex [Cu(L)Ce (NO3)2(μ-NO3)(OAc)2]2·MeOH ( 2 ) and hetero-multinuclear 3d–4f complexes [{Cu(L)Ln (NO3)3}2][Cu(L)Ln (NO3)3]2 (Ln = Pr ( 3 ) and Nd = ( 4 )) have been self-assembled from the reaction of Cu (OAc)2·H2O, Ln (NO3)3·6H2O (Ln = La, Ce, Pr and Nd) with an unsymmetric salamo-like bisoxime ligand H2L (6-Methoxy-6′-ethoxy-2,2′-[ethylenedioxybis (nitrilomethylidyne)]diphenol) based on a Schiff base condensation of 2-[O-(1-ethoxyamide)]oxime-6-methoxyphenol and 3-ethoxysalicylaldehyde. The structures of complexes 1 – 4 were characterized by elemental analyses, PXRD analyses, IR, UV–Vis spectra, and single-crystal X-ray analyses. In addition, the supramolecular interactions and fluorescence properties of complexes 1 – 4 are discussed in detail. Moreover, the antioxidant activities of the complexes 1 – 4 were determined by superoxide radical-scavenging method in vitro, which indicates that the complexes 1 – 4 all show potential antioxidant properties.  相似文献   

14.
6-Aminocoumarin reacts with pyridine-2-carboxaldehyde and has synthesized N-[(2-pyridyl)methyliden]-6-coumarin (L). The ligand, L, reacts with [Cu(MeCN)4]ClO4/AgNO3 to synthesize Cu(I) and Ag(I) complexes of formulae, [Cu(L)2]ClO4 and [Ag(L)2]NO3, respectively. While similar reaction in the presence of PPh3 has isolated [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3. All these compounds are characterized by FTIR, UV-Vis and 1H NMR spectroscopic data. In case of [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3, the structures have been confirmed by X-ray crystallography. The structure of the complexes are distorted tetrahedral in which L coordinates in a N,N′ bidentate fashion and other two coordination sites are occupied by PPh3. The ligand and the complexes are fluorescent and the fluorescence quantum yields of [Cu(L)(PPh3)2]ClO4 and [Ag(L)(PPh3)2]NO3 are higher than [Cu(L)2]ClO4 and [Ag(L)2]NO3. Cu(I) complexes show Cu(II)/Cu(I) quasireversible redox couple while Ag(I) complexes exhibit deposition of Ag(0) on the electrode surface during cyclic voltammetric experiments. gaussian 03 computations of representative complexes have been used to determine the composition and energy of molecular levels. An attempt has been made to explain solution spectra and redox properties of the complexes.  相似文献   

15.
Six new μ-phthalato binuclear oxovanadium(IV) complexes, namely [(VO)2(PHTH)-(L)2]SO4 (L denotes 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me2 bpy); 5-nitro-1,10-phenanthroline (NO2-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 5-methyl-1,10-phenanthroline (CH3-phen), where PHTH is the phthalate dianion), have been synthesized and characterized by elemental analyses, IR, electronic spectra, magnetic moments at room temperature and molar conductivity measurements. The temperature dependence of the magnetic susceptibility of complexes [(VO)2(PHTH)(phen)2]SO4 (1) and [(VO)2(PHTH)(CH3-phen)2]SO4 (2) was measured in 4—300 K range and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, ?=?2J?1·?2, giving the exchange integrals J=?12.8 cm?1 for 1 and J=?7.9 cm?l for 2. This indicates an antiferromagnetic spin-exchange interaction between the metal ions within each molecule.  相似文献   

16.
Seven new μ‐oxamido copper(II)‐lanthanide(III) heterobimetalic complexes described by the formula Cu(obbz) Ln‐(Ph‐phen)2NO3(Ln = La, Nd, Eu, Gd, Tb, Ho, Er), where obbz denotes the oxamidobis(benzoato) and Ph‐phen represents 5‐phenyl‐1, 10‐phenanthroline, have been synthesized and characterized by the elemental analyses, spectroscopic (IR, UV, ESR) studies, magnetic moments (at room temperature) and molar conductivity measurement. The temperature dependence of the magnetic susceptibility of Cu(obbz)Gd(Ph‐phen)2NO3 complex has been measured over the range 4.2–300 K. The least‐squares fit of the experimental susceptibilities based on the spin Hamiltonian operator, ? = ?2 J?1·?2, yielded J= +1.28 cm?1, a weak ferromagnetic coupling, A plausible mechanism for a ferromagnetic coupling between Gd(III)‐Cu(II) is discussed in terms of spin‐polarization.  相似文献   

17.
Four binuclear Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) complexes bridged by oxamidate (oxd) group have been synthesized, namely Co2(byp)2(oxd)(ClO4)2 (1), Co2(Me2bpy)2(oxd)(ClO4)2.H2O (2), Ni2(bpy)2(oxd)(ClO4)2.2H2O (3) and Cu2(Me2bpy)2(oxd)(NO3)2 (4). (bpy=2,2'-bipyridyl, Me2-bpy=4,4'-dimethylbipyridyl, oxd=oxamidate) The complexes are characterized by IR, UV spectra, EPR and variable-temperature magnetic susceptibility (4-300 K). The susceptibility data for. complexes 1 and 3 were least-squares fit to the susceptibility equation derived from the spin Hamiltonian H=-2J . S1 . S2. The exchange integral, J, was found to be equal to -3.62 cm-1 in 1 and -1.82 cm-1 in 3. This indicates a weak antiferromagnetic spin exchange interaction between the metal ions.  相似文献   

18.
By using the neutral bidentate nitrogen-containing ligands; bis(3,5-dimethyl-1-pyrazolyl)methane (L0″), bis(3,5-diisopropyl-1-pyrazolyl)methane (L1″), bis(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)methane (L3″), and bis(3,5-ditertiary-butyl-1-pyrazolyl)methane (L4″), the copper(II) nitrato complexes [Cu(L0″)2(NO3)]NO3 (1NO3), [Cu(L0″)(NO3)2] (2), [Cu(L1″)(NO3)2] (3), [Cu(L3″)(NO3)2] (4), and [Cu(L4″)(NO3)2] (5), chloro complexes [Cu(L0″)2Cl]2(CuCl4) (6CuCl4), [Cu(L0″)2Cl]2(Cu2Cl6) (6Cu2Cl6), [Cu(L1″)Cl2] (7), and [Cu(L3″)Cl2] (8), nitrito complexes [Cu(L0″)(ONO)2] (9) and [Cu(L1″)(ONO)2] (10), and the complexes with perchlorate ions [Cu(L0″)2(CH3OH)](ClO4)2 (11ClO4) and [Cu(L1″)2(H2O)](ClO4)2 (12ClO4) were systematically synthesized and fully characterized by X-ray crystallography and by IR, far-IR, UV–Vis absorption, and ESR spectroscopy. In comparison with the obtained complexes with four bis(pyrazolyl)methanes having different bulkiness at pyrazolyl rings, the second coordination sphere effects on the ligands are discussed in detail. Moreover, the structures and physicochemical properties of these obtained complexes are compared with those of the related complexes with the neutral tridentate tris(pyrazolyl)methane ligand.  相似文献   

19.
Four μ-2-chloroterephthalato binuclear iron(Ⅱ) complexes, namely [Fe2 (CTPHA) L4]-(ClO4)2, where L stands for 4,4'-dimethyl-2,2'-bipyridine (Me2-bpy); 2,9-dimethyl-l, 10-phenanthro-line (Me2-phen); 5-chloro-l, 10-phenanthroline (Cl-phen); 4, 7-diphenyl-l, 10-phenanthroline (Ph2-phen), respectively, and CTPHA represents 2-chlorolerephthalate dianion, have been synthesized and characterized. Based on the elemental analyses, molar conductance measurements and spectroscopic studies, extended CTPHA-bridged structures consisting of two iron(Ⅱ) ions, each in a distorted octahedral environment, are proposed for these complexes. [Fe2 CTPHA)-(Me2-bpy)4] (ClO2 (1) and [Fe2(CT-PHA)·(Me2-phen)4](ClO4)2 (2) complexes were characterized by variable temperature magnetic susceptibility (4-300 K) measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2 , giving the exchange integrals J = - 1.28 cm-1 for 1 and J = - 1.85 cm-1 for 2. These r  相似文献   

20.
Summary Four novel trinuclear copper(II) complexes have been synthesized, namely {[Cu(pbaOH)][Cu(L)]2}(ClO4)2, where pbaOH = 2-hydroxy-1,3-propanediylbis(oxamato) and L is 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen), 2,2-bipyridyl (bipy) or 4,4-dimethyl-2,2-bipyridyl (Me2bipy). Based on i.r. and electronic spectra, elemental analyses, and conductivity measurements oxamato-bridged structures consisting of three copper(II) ions, in which each copper(II) ion has a square-planar environment, are proposed. The temperature-dependent magnetic susceptibility of {[Cu-(pbaOH)][Cu(phen)]2}(ClO4) 2 has been studied in the 4.2–300 K range, giving the exchange integral J=- 111.9cm–1. The result revealed the operation of an antiferromagnetic spin-exchange interaction between adjacent copper ions.  相似文献   

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