Syntheses,Structures,Luminescence And Magnetism Of 3d And 3d–4f Complexes Constructed From Salamo–type Bisoxime

Salen(N,N?-disalicylideneethylenediamine) and its analogues owing to their flexible chelate function can form a variety of metal complexes. As these metal complexes have potential application in spectral properties and magnetic properties, which became one of heat points of coordination chemistry. Their synthesis, structure characterization, luminescent properties and molecular magnetism, especially Salen–type 3d–4f heterometallic complexes,had been studied. In order to investigate the syntheses and crystal structures of the Salen–type3d and 3d–4f heterometallic complexes, together with the magnetism and luminescence properties. In this article, twelve homotrinuclear Co(II) and Ni(II) complexes have been obtained by reaction of three tetradentate Salen–type bisoxime(H2L1, H2L2 and H2L3) with transition metal, and three series of thirty-six 3d–4f heterometallic complexes have been designed and synthesized by self–assembly reactions of hexadentate Salen–type bisoxime(H2L4) with transition and lanthanide metals. All the complexes have been characterized by elemental analyses, IR spectra, UV–Vis spectra and structurally characterized by X–ray single crystal diffraction. Furthermore, luminescence properties and molecular magnetism of some complexes have been studied.1. Through tetradentate Salamo–type ligand H2L1:4,4?-dichloro-2,2?-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol reaction with Co(II)acetate and Ni(II) acetate obtain three homotrinuclear complexes{[CoL1(OAc)(DMSO)]2Co}·2DMSO(1), {[NiL1(OAc)(MeOH)]2Ni}(2),{[NiL1(OAc)(DMSO)]2Ni}·2DMSO(3). Tetradentate Salamo–type ligand H2L2:4-nitro-4?-chloro-2,2?-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol reaction with Co(II) acetate and Ni(II) acetate obtain six homotrinuclear complexes {[Co L2(OAc)R]2Co}(R = MeOH(4), Py(5), DMF(6))(Py = pyridine), {[NiL2(OAc)(R)]2Ni}(R = MeOH(7)·MeOH, DMF(8), 2DMSO(9)). Finally, tetradentate Salamo–type ligand H2L3:5-methoxy-4?-chloro-2,2?-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol reaction with Co(II) acetate and Ni(II) acetate obtain three homotrinuclear complexes{[CoL3(OAc)(MeOH)]2Co}(10), {[CoL3(OAc)Py]2Co}(11) and{[NiL3(OAc)(MeOH)]2Ni}·MeOH(12). The magnetic measurements are performed on the complexes 2, 5, 10 and 11.2. Five 3d–4f heterometallic Co(II)–Ln(III) complexes, a discrete heterodinuclear complex [L4CoLa(py)(NO3)3(CH3OH)](13), a heterotetranuclear dimer[(L4)2Co2La2(4,4'-bipy)(NO3)6(CH3OH)2](14)(4,4'-bipy = 4,4'-bipyridine) and three discrete heterodinuclear complexes [L4CoLn(OAc)(NO3)2(CH3OH)](Ln = Gd(15), Tb(16), Dy(17))self–assemble by hexadentate 3-MeOsalamo ligand H2L4:1,2-bis(3-methoxysalicylideneaminooxy)ethane with Co(II) acetate, Ln(III) nitrate(Ln = La,Ga, Tb, Dy) and Py(13)(or 4,4'-bipy(14)). The magnetic measurements are performed on the complexes 15, 16 and 17.3. Through the self–assembly of hexadentate 3-MeOsalamo ligand H2L4 with Ni(II)acetate, Ln(III) nitrate(Ln = La, Ce, Gd, Tb and Dy) and Py, 4,4'-bipy or H2bdc(H2bdc =terephthalic acid), ten new 3d–4f Ni(II)–Ln(III) heterometallic complexes: two discrete heterodinuclear complexes [LNiLa(Py)(OAc)(NO3)2(CH3OH)]·CH3OH(18) and[LNiDy(Py)(OAc)(NO3)2](19), two 1D coordination polymers1?[L4NiLa(4,4'-bipy)(NO3)3(CH3OH)](20) and 1?[L4NiTb(4,4'-bipy)(NO3)3](21), one discrete heterodinuclear complex [L4Ni Dy(4,4'-bipy)(OAc)(NO3)2](22), three heterotetranuclear dimers [(L4)2Ni2Ln2(bdc)(NO3)4(DMF)2(CH3OH)2](Ln = La(23), Ce(24), Gd(25)) and two heterotetranuclear dimers [(L4)2Ni2Ln2(bdc)(NO3)4(DMF)2](Ln = Tb(26), Dy(27)) have been obtained, respectively. The magnetic measurements are performed on the complexes of Gd(III), Tb(III) and Dy(III).4. One discrete 3d–4f heterotrinuclear complexes [(L4Zn)2La(OAc)2]·ClO4·2CHCl3(28),one unusual 3d–4f polynuclear species [(L4Zn)2Ce(OAc)2]·[Ce(NO3)6]·Py(29) and six discrete 3d–4f heterobinuclear complexes [L4ZnLn(Py)(NO3)3](Ln = Nd(30), Sm(31), Tb(34)), [L4ZnLn(OAc)(NO3)2](Ln = Eu(32), Gd(33), Dy(35)) have been successfully prepared by the reaction of hexadentate 3-MeOsalamo ligand H2L4 with Zn(II) acetate, Ln(III)ions(Ln = La, Ce, Nd, Sm, Eu, Gd, Tb and Dy) and Py. Through the self–assembly of hexadentate 3-MeOsalamo ligand H2L4 with Zn(II) acetate, Ln(III) nitrate(Ln = La, Ce, Pr,Nd, Sm, Eu, Gd and Tb) and 4,4'-bipy or H2 bdc, three new families of thirteen 3d–4f heteromultinuclear Zn(II)–Ln(III) complexes: two heterotetranuclear dimers[(L4)2Zn2Ln2(4,4'-bipy)(NO3)6(CH3OH)2](Ln = La(36·2CH3OH), Ce(37)), six heterotetranuclear dimers [(L4)2Zn2Ln2(4,4'-bipy)(NO3)6](Ln = Pr(38), Nd(39), Sm(40), Eu(41), Gd(42), Tb(43)), three heterohexanuclear complexes[(L4)4Zn4Ln2(bdc)2]·(NO3)2·2CHCl3(Ln = Ce(44), Pr(45), Sm(46·2CH3CH2OH)) and two2 D coordination polymers 2?[L4ZnLn(bdc)1.5](Ln = Eu(47), Gd(48·2CHCl3)) have been obtained, respectively. Furthermore, the luminescence properties of the Zn(II)–Ln(III)complexes have been studied.