Jian-Chun Ma

Nine self-assembled nickel(II)–lanthanide(III) heterometallic complexes constructed from a Salamo-type bisoxime and bearing a N- or O-donor auxiliary ligand: syntheses, structures and magnetic properties

Through the self-assembly of a Salamo-type ligand H2L (H2L = 1,2-bis(3-methoxysalicylideneaminooxy)ethane) with Ni(OAc)2·4H2O, Ln(NO3)3·6H2O (Ln(III) = La(III), Gd(III), Tb(III) and Dy(III)) and Py (Py = pyridine) or 4,4′-bipy (4,4′-bipy = 4,4′-bipyridine) or H2bdc (H2bdc = terephthalic acid), nine new Ni(II)–Ln(III) heterometallic complexes [Ni(L)La(OAc)(NO3)2(Py)(CH3OH)]·CH3OH (1), [Ni(L)Dy(OAc)(NO3)2(Py)] (2), 1∞[Ni(L)La(NO3)3(4,4′-bipy)(CH3OH)] (3), 1∞[Ni(L)Tb(NO3)3(4,4′-bipy)] (4), [Ni(L)Dy(OAc)(NO3)2(4,4′-bipy)] (5), [{Ni(L)Ln(NO3)2(DMF)(CH3OH)}2(bdc)] (Ln = La (6) and Gd (7)) and [{Ni(L)Ln(NO3)2(DMF)}2(bdc)] (Ln = Tb (8) and Dy (9)) were obtained, respectively. The acetato ligand bridges the Ni(II) and Ln(III) (Ln = La (1) and Dy (2)) atoms in a μ2 fashion and the Py coordinates to the apical position by a nitrogen atom in the heterobimetallic complexes 1 and 2. Complexes 3 and 4 are 1D coordination polymers constructed from heterobimetallic [Ni(L)Ln] (Ln = La (3) and Tb (4)) units which are connected by the exo-dentate ligand 4,4′-bipy bearing nitrogen-donor atoms, but complex 5 is a heterobimetallic Ni(II)–Dy(III) complex which is prepared under the same reaction conditions as complexes 3 and 4. Four heterotetranuclear dimers were constructed from heterobimetallic [Ni(L)Ln] (Ln = La (6), Gd (7)), Tb (8) and Dy (9) units which are connected by the exo-dentate H2bdc ligand with oxygen-donor atoms. Magnetic measurements were performed on the Gd(III), Tb(III) and Dy(III) complexes.

An unexpected dinuclear Cu(II) complex with a bis(Salamo) chelating ligand: synthesis, crystal structure, and photophysical properties

Abstract An unexpected dinuclear Cu(II) complex, [Cu2(L2)2], has been synthesized via complexation of Cu(II) acetate monohydrate with a bis(Salamo) ligand H2L1. Catalysis of Cu(II) ions results in unexpected cleavage of two N–O bonds in H2L1, giving a dialkoxo-bridged dinuclear Cu(II) complex. Each Cu(II) complex possesses a Cu–O–Cu–O four-membered ring instead of the usual bis(Salamo) [Cu2L1] complex with H2L1. The H2L1 molecule is stabilized by intramolecular O1–H1⋯N1 hydrogen bonds and π⋯π stacking interactions linking adjacent molecules into a 1-D infinite zigzag chain. In the structure of the Cu(II) complex, intermolecular hydrogen bonds have stabilized the Cu(II) complex to form a self-assembling infinite 1-D linear chain. Furthermore, the H2L1 ligand shows intense photoluminescence with two emissions at ca. 370 and 464 nm upon excitation at 310 nm. The Cu(II) complex shows photoluminescence with maximum emission at ca. 423 nm upon excitation at 370 nm.

Four 3d–4f heteromultinuclear zinc(II)–lanthanide(III) complexes constructed from a distinct hexadentate N2O2-type ligand: syntheses, structures and luminescence properties

Abstract Four 3d–4f heteronuclear complexes, [(ZnL)2La(OAc)2]·ClO4·2CHCl3 (1), [(ZnL)2La(OAc)2]·CF3SO3·H2O (2), [ZnNd(L)(Py)(NO3)3] (3), and [ZnGd(L)(OAc)(NO3)2] (4) (Py = pyridine; H2L = 6,6′-dimethoxy-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol), have been prepared by one-pot reaction of H2L with zinc(II) acetate, lanthanide(III) ions and Py. Although the heterobinuclear complexes 1–4 are prepared in the same reaction condition, the Py does not coordinate to Zn(II) of 1, 2, and 4. Instead, the bridging μ-acetato ligand is present. The coordination of the Py in 3 leads to smaller distortion of square pyramidal coordination site of Zn(II), the higher coplanarity between the planes of ZnO(phenoxo)2 and LnO(phenoxo)2, and the longer Zn⋯Ln distance compared with 4. The luminescence properties of 1–4 have been discussed. The ligand (L2−) can sensitize NIR luminescence of Nd(III) ions.

Hetero-trinuclear Zn(II)-M(II) (M = Sr, Ba) complexes based on a mononuclear Zn(II) complex metallohost: syntheses, structures and fluorescence properties

Abstract A new mononuclear Zn(II) complex, [ZnL(HOAc)] (1) (H2L = 6,6′-diethoxy-2,2′-[1,2-ethylenedioxybis(nitrilomethylidyne)]diphenol), was synthesized by reaction of H2L and Zn(II) acetate under solvothermal conditions. Complex 1 acts as a metallohost possessing a pentadentate O5 donor. Complex 1 molecules bonded to one Sr(II) or Ba(II) form two new hetero-trinuclear complexes, [(ZnL)2M(OAc)2] (M = Sr (2), Ba (3)). In 2 and 3, Zn(II) ions are 5-coordinate, but the Sr(II) or Ba(II) ion is 10-coordinate by four μ-phenolic oxygens from two L2− units, four oxygens from four ethoxy groups and two oxygens from two μ-acetato ligands. Furthermore, 1–3 exhibit blue emissions with the maximum emission wavelengths λmax = 477, 500, and 471 nm when excited at 360 nm.