title: Pentanuclear 3d-4f Heterometal Complexes of M(II)3Ln(III)2 (M = Ni, Cu, Zn and Ln = Nd, Gd, Tb) Combinations: Syntheses, Structures, Magnetism, and Photoluminescence Properties.
abstract: A new family of pentanuclear 3d-4f heterometal complexes of general composition [Ln(III)2(M(II)L)3(μ3-O)3H](ClO4)·xH2O (1-5) [Ln = Nd, M = Zn, 1; Nd, Ni, 2; Nd, Cu, 3; Gd, Cu, 4; Tb, Cu, 5] have been synthesized in moderate yields (50-60%) following a self-assembly reaction involving the hexadentate phenol-based ligand, viz., N,N-bis(2-hydroxy-3-methoxy-5-methylbenzyl)-N('),N(')-diethylethylenediamine (H2L). Single-crystal X-ray diffraction analyses have been used to characterize these complexes. The compounds are all isostructural, having a 3-fold axis of symmetry that passes through the 4f metal centers. The [M(II)L] units in these complexes are acting as bis-bidentate metalloligands and, together with μ3-oxido bridging ligands, complete the slightly distorted monocapped square antiprismatic nine-coordination environment around the 4f metal centers. The cationic complexes also contain a H(+) ion that occupies the central position at the 3-fold axis. Magnetic properties of the copper(II) complexes (3-5) show a changeover from antiferromagnetic in 3 to ferromagnetic 3d-4f interactions in 4 and 5. For the isotropic Cu(II)-Gd(III) compound 4, the simulation of magnetic data provides very weak Cu-Gd (J1 = 0.57 cm(-1)) and Gd-Gd exchange constants (J2 = 0.14 cm(-1)). Compound 4 is the only member of this triad, showing a tail of an out-of-phase signal in the ac susceptibility measurement. A large-spin ground state (S = 17/2) and a negative value of D (-0.12 cm(-1)) result in a very small barrier (8 cm(-1)) for this compound. Among the three Nd(III)2M(II)3 (M = Zn(II), Ni(II), and Cu(II)) complexes, only the Zn(II) analogue (1) displays an NIR luminescence due to the (4)F(3/2) → (4)I(11/2) transition in Nd(III) when excited at 290 nm. The rest of the compounds do not show such Nd(III)/Tb(III)-based emission. The paramagnetic Cu(II) and Ni(II) ions quench the fluorescence in 2-5 and thereby lower the population of the triplet state.
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science , Kolkata 700 032, India.
authors.forename: Manoranjan
authors.initials: M
authors.lastname: Maity
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science , Kolkata 700 032, India.
authors.forename: Mithun Chandra
authors.initials: MC
authors.lastname: Majee
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science , Kolkata 700 032, India.
authors.forename: Sanchita
authors.initials: S
authors.lastname: Kundu
authors.affiliation: Department of Chemistry, Presidency University , 86/1 College Street, Kolkata 700 073, India.
authors.forename: Swarna Kamal
authors.initials: SK
authors.lastname: Samanta
authors.affiliation: Departament de Quimica Inorgànica i Institut de Nanociència i Nanotecnologia, Universitat de Barcelona , Diagonal 645, 08028 Barcelona, Spain.
authors.forename: E Carolina
authors.initials: EC
authors.lastname: Sañudo
authors.affiliation: Department of Chemistry, Presidency University , 86/1 College Street, Kolkata 700 073, India.
authors.forename: Sanjib
authors.initials: S
authors.lastname: Ghosh
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science , Kolkata 700 032, India.
authors.forename: Muktimoy
authors.initials: M
authors.lastname: Chaudhury