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1

Synthesis, Crystal Structure and DNA Binding Studies of Bis(piperidinium)bis-(N,N,N',N'-tetramethylethylenediammonium) Decavanadate(V) Tetrahydrate

Jiang M., Li Y. -T., Wu Z. -Y., Yan C. -W.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 11

1849-1858

EN

A new decavanadate compound consisting of one decavanadate polyanion [V10O28]6–, two protonated piperidinium cations [C5H12N]+, two doubly protonated N,N,N',N'- tetramethylethylenediammonium cat ions [C6N2H18]2+ and four lattice water molecules, namely, [(C5H12N)2][(C6N2H18)2][V10O28]×4H2O, has been synthesized and characterized by spectroscopic (IR, UV-vis and ESR) studies and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n and Z = 2, with a = 11.1267(18) capital A, ring, b = 16.854(3) capital A, ring, c = 12.973(2) capital A, ring and beta = 95.426(2)°. The cat ions, an ions and lattice water molecules are assembled by hydrogen bonds, forming a three-dimensional supramolecular architecture. The DNA-binding property of the compound was preliminarily investigated by using fluorescence spectrum, and the results indicating that the interaction mode between the compound and herring sperm DNA (HS-DNA) might be groove binding with the quenching constant of 1.20×104. To the best of our knowledge, this is the first report about the DNA-binding study of decavanadate compounds.

2

Synthesis and magnetic Studies of mi-Iodanilato-Bridged Iron(III)-Iron(III) Binuclear Complexes

Li Y., Yan C. -W., Guan H. -S.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 8

935-942

EN

Four new _-iodanilato-bridged binuclear iron(III) complexes have been prepared and identified: [Fe2(IA)L4](ClO4)4, where IA represents the dianion of iodanilic acid and L denotes 2,2_-bipyridine (bpy); 1,10-phenanthroline (phen), 5-chloro-1,10-phenanthroline (Cl-phen) or 5-nitro-1,10-phenanthroline (NO2-phen). Based on elemental analyses, molar conductivity, magnetic moment of room-temperature measurements, IR and electronic spectra studies, these complexes are proposed to have extended IA-bridged structures consisting of two iron(III) ions, each in a distorted octahedral environment. The complexes [Fe2(IA)(bpy)4](ClO4)4 (1) and [Fe2(IA)(phen)4](ClO4)4 (2) were further characterized by variable temperature (4.2~300 K) magnetic susceptibility measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator,_ _ _ H = 2JS S 1 2 Ĺ , giving the exchange parameter J = -6.9 cm-1 for (1) and J = -9.8 cm-1 for (2). These results are commensurate with antiferromagnetic spin-exchange interaction between the two iron(III) ions within each molecule. The influence of halogen substituents in the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is also discussed.

3

Synthesis and magnetic Properties of mi-2-Nitroterephthalato-Bridged Binuclear Lanthanide(III) Complexes

Li Y., Zhang J., Yan C. -W.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 7

797-804

EN

Nine new binuclear lanthanide(III) complexes described by the overall formula [Ln2(NTPHA)(Me2bpy)4(ClO4)2](ClO4)2 (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er), where Me2bpy stands for 4,4_-dimethyl-2,2_-bipyridine, and NTPHA represents the 2-nitroterephthalate dianions, have been synthesized and characterized by elemental analyses, IR, ESR and electronic spectra, and molar conductance measurements. It is proposed that these complexes present NTPHA-bridged structures consisting of two lanthanide(III) ions. The variable-temperature magnetic susceptibilities (4~300 K) of complex [Gd2(NTPHA)(Me2bpy)4(ClO4)2](ClO4)2 were measured and studied, demonstrating a very weak antiferromagnetic spin-exchange interaction between Gd(III)-Gd(III) ions within the complex. Based on the spin Hamiltonian operator,_ _ _ H = 2JS S 1 Ĺ 2, the exchange parameter (J) was evaluated as -0.12 cm-1.

4

Synthesis and Magnetic Characterization of mi-Oxamido-bridged Cu(II)-M(III) (M=Fe and Cr) Heterobinuclear Complexes

Li Y., Yan C. -W., Guan H. -S.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 10

1235-1244

EN

Two new _-oxamido-bridged heterobinuclear complexes have been synthesized and identified as [Cu(dmoxae)Cr(Ph2phen)2](ClO4)3 (1) and [Cu(dmoxae)Fe(Ph2phen)2](ClO4)3 (2), where dmoxae denotes N,N_-bis[2-(dimethylamino)ethyl]oxamido dianion and Ph2phen represents 4,7-diphenyl-1,10-phenanthroline. Based on elemental analyses, IR, ESR and electronic spectra studies, and molar conductivity measurements, the complexes are proposed to have an extended oxamido-bridged structure consisting of planar copper(II) and octahedral chromium(III) or iron(III) ions. The two heterobinuclear complexes were further characterized by variable-temperature magnetic susceptibility (4.2~300 K) measurements and the magnetic data have been also used to deduce the indicated heterobinuclear structure. The results derived from least-squares fit of the experimental data have confirmed that the adjacent copper(II) and chromium(III) ions through the oxamido-bridge in complex (1) are ferromagnetically coupled with the exchange integral J(Cu-Cr) = +13.6 cm-1, while an intramolecular antiferromagnetic coupling is detected between the copper(II) and iron(III) ions through the oxamido-bridge in complex (2) with the exchange integral J(Cu-Fe) = -17.5 cm-1, on the basis of the spin Hamiltonian operator, _ _ _ H JS S Cu M = Ĺ 2 (M = Cr3+ and Fe3+). The influence of electronic-structural variation of the metal ions on the nature of spin-exchange interaction between the paramagnetic centers is also discussed.

5

Synthesis and Magnetic Analysis of mi-Oxamido-Bridged Copper(II)-Iron(II) Heterodinuclear Complexes

Li Y., Yan C. -W., Guan H. -S.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 2

137-145

EN

Five new copper(II)-iron(II) heterodinuclear complexes bridged by the dianion of N,N_-bis[3-(dimethylamino)propyl]oxamido (dmoxpn) and end-capped with 2,2_-bipyridine (bpy); 1,10-phenanthroline (phen); 5-nitro-1,10-phenanthroline (NO2-phen); 5-chloro-1,10-phenanthroline (Cl-phen) or 5-bromo-1,10-phenanthroline (Br-phen); namely [Cu(dmoxpn)FeL2](ClO4)2 (L = bpy, phen, NO2-phen, Cl-phen, Br-phen), have been synthesized and characterized. Based on elemental analyses, magnetic moments (at room temperature), molar conductivity measurements, and spectroscopic studies, extended oxamido-bridged structures consisting of a copper(II) ion and an iron(II) ion, which have a square-planar environment and an octahedral environment, respectively, are proposed for these complexes. The [Cu(dmoxpn)Fe(bpy)2](ClO4)2 (1) and [Cu(dmoxpn)Fe(phen)2](ClO4)2 (2) complexes have been further characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(II) ion,_ _ _ _ H = 2JS S DS 1 2 Z1 2 Ĺ , giving the exchange integrals J = -15.9 cm-1 for (1) and J = -17.5 cm-1 for (2). These results indicated that the spin coupling between the adjacent copper(II) and iron(II) ions through oxamido-bridge in both complexes (1) and (2) is antiferromagnetic. The influence of methyl (-CH3) substituents in the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is also discussed.

6

Synthesis and Ferromagnetic Interaction in μ-Oxamido-Bridged Copper(II)-Oxovanadium(IV) Heterodinuclear Complexes

Li Y., Yan C. -W., Guan H. -S.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 8

943-959

EN

Three new copper(II)-oxovanadium(IV) heterodinuclear complexes bridged by dianions of N,N_-oxamidobis(propionato)cuprate, [Cu(obp)] and end-capped with 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 5-chloro-1,10-phenanthroline (Cl-phen), have been synthesized and characterized; namely [Cu(obp)VO(phen)] (1), [Cu(obp)VO(NO2-phen)] (2) and [Cu(obp)VO(Cl-phen)] (3). The three complexes have not yet been isolated in crystalline form suitable for X-ray structure analysis, but based on elemental analyses, IR and electronic spectra studies, magnetic moments at room-temperature and molar conductivity measurements, these complexes are proposed to have an extended oxamido-bridged structure consisting of planar copper(II) and square-pyramidal oxovanadium(IV) ions. The heterodinuclear complexes (1) and (2) were further characterized by variable-temperature magnetic susceptibility (4.2~300 K) measurements and the magnetic data have been also used to deduce the indicated heterodinuclear structure. The results derived from least-squares fit of the experimental data have confirmed that the operation of a ferromagnetic interaction between the adjacent oxovanadium(IV) and copper(II) ions through the oxamido-bridge within each molecule. Based on spin Hamiltonian, _ _ _ H = 2JS S 1 2 Ĺ , the exchange integral (J) was evaluated as J = +11.68 cm-1 for (1) and J = +10.27 cm-1 for (2). The influence of the symmetry of the magnetic orbitals on the nature of the magnetic interaction between the paramagnetic centers is also discussed.

7

Antiferromagnetically Coupled Binuclear Chromium(III) Complexes Through mi-Isophthalato-Bridge

Li Y., Yan C. -W., Guan H. -S.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 8

953-959

EN

Three new _-isophthalato-bridged binuclear chromium(III) complexes were synthesized and characterized, namely [Cr2(IPHTA)(Me2bpy)4](NO3)4 (1), [Cr2(IPHTA)(Me2phen)4](NO3)4 (2) and [Cr2(IPHTA)(Cl-phen)4](NO3)4 (3), where IPHTA represents the isophthalate dianions; Me2bpy, Me2phen and Cl-phen stand for 4,4_-dimethyl-2,2_-bipyridine; 2,9-dimethyl-1,10-phenanthroline and 5-chloro- 1,10-phenanthroline, respectively. The three complexes have not yet been isolated in crystalline form suitable for X-ray structure analysis, but based on elemental analyses, molar conductance and magnetic moments of room-temperature measurements, and spectroscopic studies, extended IPHTA-bridged structures consisting of two chromium( III) ions, each in an octahedral environment are proposed for these complexes. The complexes [Cr2(IPHTA)(Me2bpy)4](NO3)4 (1) and [Cr2(IPHTA)(Me2phen)4](NO3)4 (2) were further 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 JS S = Ĺ 2 1 2, giving the exchange integrals J = -1.27 cm-1 for (1) and J = -2.19 cm-1 for (2). This result indicates the presence of weak antiferromagnetic spin-exchange interaction between the metal ions within each molecule.

8

Synthesis, Characterization and Magnetism of Fe(II)-Pd(II0-Fe(II) Heterotrinuclear Complexes Bridged by Dioximato Groups

Li Y., Yan C. -W., Zeng X.-C.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 5

645-652

EN

Three new Fe(II)-Pd(II)-Fe(II) heterotrinuclear complexes with dioximato-bridge have been synthesized and identified as [Fe2Pd(_-FD)2(Me2-bpy)4]SO4 (1), [Fe2Pd(_-FD)2(Me2-phen)4]SO4 (2) and [Fe2Pd(_-FD)2(Me-phen)4]SO4 (3); where (_-FD)2_ represents _-furildioximato; Me2-bpy, Me2-phen and Me-phen denote 4,4_-dimethyl-2,2_-bipyridine; 2,9-dimethyl-1,10-phenanthroline (Me2-phen) and 5-methyl-1,10-phenanthroline (Me-phen). Based on elemental analyses, molar conductance measurements, IR and electronic spectral studies, these complexes are proposed to have extended dioximato-bridged structures and to consist of two iron(II) ions and a palladium(II) ion, in which the central palladium(II) ion has a square-planar environment and the end capped two iron(II) ions have a distorted octahedral environment. The magnetic properties of complexes [Fe2Pd(_-FD)2(Me2-bpy)4]SO4 (1) and [Fe2Pd(_-FD)2(Me2-phen)4]SO4 (2) were investigated over the 4.2~300Krange and correspond to what is expected for an antiferromagnetic Fe(II)-Fe(II) pair with SFe(II) = 2 and SPd(II) = 0 (Pd2+ is a diamagnetic in a square-planar environment) local spins. The exchange integral (J) was evaluated as J = _2.89 for (1) and J = _3.16 for (2) based on the spin Hamiltonian operator, _ _ _ H = JS S 1 2 _ _ 2 .

9

Synthesis, Characterization and Magnetic Studies of ž-Oxamido-Bridged Cu(II)-MN(II) Heterobinuclear Complexes

Li Y., Yan C. -W., Yin X.-C.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 1

13-21

EN

Four new ž-oxamido-bridged copper(II)-manganese(II) heterobinuclear complexes described by the overall formula [Cu(dmoxpn)MnL2](ClO4)2, where dmoxpn denotes N,N_-bis[3-(dimethylamino)propyl)]oxamido dianion, L represents 2,2_-bipyridine (bpy); 4,4_-dimethyl-2,2_-bipyridine (Me2-bpy); 5-chloro-1,10-phenanthroline (Cl-phen) or 5-bromo-1,10-phenanthroline (Br-phen), have been synthesized and characterized. Based on elemental analyses, IR and electronic spectra studies and molar conductivity measurements, these complexes are proposed to have oxamido-bridged structures and to consist of the copper(II) ion in a planar environment and the manganese(II) ion in an octahedral environment. The electronic reflectance spectrum indicates the presence of exchange- coupling interaction between bridging copper(II) and manganese(II) ions. The [Cu(dmoxpn)Mn(bpy)2](ClO4)2 complex has been further characterized by variable temperature susceptibility (4.2-300 K) and the observed data were least-square fitted to the susceptibility equation derived from the spin Hamiltonian, _H = -2J _ S1_ S2, giving the exchange integral J = -27.8 cm-1. The results are commensurate with antiferromagnetic interaction between the adjacent manganese(II) and copper(II) ions through the oxamido-bridge within the complex. The influence of structural variation of the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is also discussed.

10

Synthesis, Characterization and magnetic Properties of mi-2-Nitroterephthalato Binuclear Iron(II) Complexes

Li Y., Yan C. -W.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 6

765-771

EN

Four new binuclear iron(II) complexes bridged by 2-nitroterephthalato groups (NTPHA) and ended with 4,4_-dimethyl-2,2_-bipyridine (Me2-bpy), 2,9-dimethyl-1,10-phenanthroline (Me2-phen), 5-chloro-1,10-phenanthroline (Cl-phen) or 5-bromo-1,10-phenanthroline (Br-phen), namely [Fe2(NTPHA)L4](ClO4)2 (L=Me2-bpy,Me2-phen, Cl-phen, Br-phen), have been synthesized and characterized. Based on elemental analyses, magnetic moments (at room temperature), molar conductance measurements, and spectroscopic studies, extended NTPHA-bridged structures consisting of two iron(II) ions, each in a distorted octahedral environment are proposed for these complexes. The variable temperature magnetic susceptibilities of complexes [Fe2(NTPHA)(Me2-bpy)4](ClO4)2 (1) and [Fe2(NTPHA)(Me2-phen)4](ClO4)2 (2) were measured over the range 4.2~300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, _ _ _ H JS S _ _ _ 2 1 2, giving the exchange integrals J = -1.02 cm-1 for (1) and J = -1.96 cm-1 for (2). These results indicate the presence of a very weakly antiferromagnetic spin-exchange interaction between the iron(II) ions within each molecule. The influence of nitro substituent in the bridging ligand on magnetic interaction between the metal ions of this kind of complexes is also discussed.

11

Synthesis and Magnetism of Copper(II)-Lanthanoid(III) Heterobinuclear Complexes with N,N'

Li Y.-T., Yan C. -W., Wang G.-M.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 5

653-662

EN

Eleven novel ž-oxamido-bridged copper(II)-lanthanoid(III) heterobinuclear complexes described by the overall formula Cu(obp)Ln(Ph2-phen)2ClO4 (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb), where obp denotes N,N_-oxamidobis(propionato) and Ph2-phen represents 4,7-diphenyl-1,10-phenanthroline (Ph2-phen), have been synthesized and characterized by elemental analyses, spectroscopic (IR, UV, ESR) studies, and molar conductivity measurements. The temperature dependence of the magnetic susceptibility of complex Cu(obp)Gd(Ph2-phen)2ClO4 has been measured over the range 4.2~300 K and the magnetic properties were studied in detail, demonstrating the presence of a very weak ferromagnetic interaction between the adjacent Gd(III) and Cu(II) ions through the oxamido-bridge. Based on the spin Hamiltonian operator, _ _ _ H = 2JS S 1 2 _ _ , the exchange integral (J) was evaluated as +2.98 cm-1. A plausible mechanism for the ferromagnetic coupling between Gd(III) and Cu(II) is discussed in terms of spin-polarization.

12

Synthesis and Magnetic Studies of Binuclear Iron(II) Complexes Bridged by Tetracarboxylato Groups

Li Y., Yan C. -W.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 12

1681-1687

EN

Four novel binuclear iron(II) complexes, namely [Fe2(PMTA)L4], where L denotes 4,4_-dimethyl-2,2_-bipyridine (Me2-bpy); 1,10-phenanthroline (phen); 5-chloro-1,10- phenanthroline (Cl-phen) or 5-bromo-1,10-phenanthroline (Br-phen), respectively, and PMTA stands for the tetraanion of pyromellitic acid, have been synthesized and characterized. Based on elemental analyses, magnetic moments at room-temperature and molar conductivity measurements, and spectroscopic (electronic and IR spectra) studies, extended PMTA-bridged structures consisting of two iron(II) ions, each in a distorted octahedral environment, are proposed for these complexes. The variable temperature magnetic susceptibilities (4_300 K) of the complexes [Fe2(PMTA)(Me2-bpy)4] (1) and [Fe2(PMTA)(phen)4] (2) were measured and the magnetic analysis was carried out by least-square method to the observed data with the susceptibility equation derived from the spin Hamiltonian operator, _ _ _ H 2JS S 1 2 _ _ _ , giving the exchange integrals J = _1.09 cm_1 for (1) and J = ___18 cm_1 for (2). The results indicate that there is a very weak antiferromagnetic spin-exchange interaction between the Fe(II) ions within each molecule.

13

Synthesis and Magnetic Properties of mi-Oxalato-Bridged Cu(II)-Fe(III)-Cu(II) Heterotrinuclear Complexes

Wang H. D., Li Y. -T., Yan C. -W., Zeng X.-C.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 5

637-644

EN

Three new _-oxalato-bridged copper(II)-iron(III)-copper(II) heterotrinuclear complexes described by the overall formula [Cu2Fe(ox)3L2]ClO4, where ox represents the oxalato dianions and L stands for 5-phenyl-1,10-phenanthroline (Ph-phen), 4,7-diphenyl- 1,10-phenanthroline (Ph2-phen) or 5-chloro-1,10-phenanthroline (Cl-phen), have been synthesized and characterized by elemental analyses, molar conductivity and magnetic moment (at room-temperature) measurements, IR and electronic spectral studies. It is proposed that these complexes have extended ox-bridged structures, consisting of two copper(II) and an iron(III) ions, in which the central iron(III) ion has an octahedral environment and the end capped two copper(II) ions have a square-planar environment. The variable-temperature susceptibilities of [Cu2Fe(ox)3(Ph-phen)2]ClO4 complex were measured and studied in the 4.2~300 K range. The least-squares fit of the experimental susceptibility based on the spin Hamiltonian operator, _ _ _ H = JS S 1 2 _ _ 2 , yielded J = -9.89 cm-1. The magnetic coupling parameter is consistent with an antiferromagnetic exchange interaction between the copper(II) and iron(III) ions through the oxalato-bridge in the complex.

14

Syntesis and Ferromagnetic Interaction in Oxalato-Bridged Copper(II)-Chromium(III)-Copper(II) Heterotrinuclear Complexes

Li Y., Yan C. -W., Guan S. -H.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 12

1655-1663

15

Synthesis and Magnetic Properties of Heterobinuclear Copper(II)-Manganese(II) Complexes with N, N'-Bis[2-(dimethylamino)ethyl]oxamide as Ligand

Li Y., Yan C. -W., Miao S. -H.

Polish Journal of Chemistry

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2001

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Vol. 75, nr 2

223-230

EN

Four new copper(II)-manganese(II) heterobinuclear complexes bridged by N,N - bis[2-(dimethylamino)ethyl)]oxamido dianion (dmoxae) and end-capped with 2,2 -bipyridine (bpy); 4,4 -dimethyl-2,2 -bipyridine (Me2-bpy); 5-chloro-1,10-phenanthroline (Cl-phen) or 5-bromo-1,10-phenanthroline (Br-phen), respectively, namely, [Cu(dmoxae)MnL2](ClO4)2 (L = bpy, Me2-bpy, Cl-phen, Br-phen), have been synthesized and characterized by elemental analyses, IR and electronic spectra studies and molar conductivity measurements. The electronic reflectance spectrum indicates the presence of exchange-coupling interaction between bridging copper(II) and manganese(II) ions. The cryomagnetic measurements (4.2-300 K) of [Cu(dmoxae)Mn(bpy)2](ClO4)2 complex demonstrated the operation of an antiferromagnetic interaction between the adjacent manganese(II) and copper(II) ions through the oxamido-bridge within the complex. On the basis of spin Hamiltonian, H = 2JS S 1 2 , the magnetic analysis was carried out for the complex and the spin-coupling constant (J) was evaluated as -36.9 cm-1. The influence of methyl substituents in amine groups of the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is also discussed.

16

Synthesis and ferromagnetic oxamido-bridged heterodinuclear copper(II)-chromium(III) complexes

Yan C.-W., Li Y.-T.

Polish Journal of Chemistry

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1998

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Vol. 72, nr 5

844-851

EN

Four new my-oxamido heterodinuclear complexes [Cu(oxap)Cr(L)2](NO3)3, where oxap denotes the N