title: Spectroscopic studies of lanthanide complexes of varying nuclearity based on a compartmentalised ligand.
abstract: The synthesis, characterization and solid-state luminescence spectroscopy of mononuclear (f), heterodinuclear (d-f) and heterotrinuclear (d-f-d) coordination compounds with the compartmental ligand N,N'-bis(3-hydroxyl salicylidene)benzene-1,2-diamine (H2L) are reported. The trivalent lanthanide ions Nd(III), Sm(III), Eu(III), Gd(III), Tb(III) and Dy(III) as single metal centres or in combination with either Zn(II) or Ni(II) were coordinated. Compounds are characterised by elemental analyses, IR, 1D and 2D solution (1)H and (13)C NMR spectroscopy, measurements of magnetic moments and solid state UV-Vis-NIR reflectance, luminescence and Raman spectroscopy techniques. Crystal structures of the dinuclear compounds [SmZn(O2NO)3(L)(OH2)]·EtOH and [DyZn(O2NO)2(Cl)(L)(EtOH)]·3EtOH and the trinuclear compound [TbZn2(L)2(Cl)2(OH2)](NO3)·EtOH are presented, where samarium(iii) displays a coordination number of ten, with a bicapped cubic geometry, while for the dysprosium compound a nine-coordinated environment with a tricapped trigonal prismatic geometry is shown. Their crystals belong to the triclinic system and the P1[combining macron] space group. The coordination number for terbium(iii) in the trinuclear complex is nine, with a tricapped trigonal prismatic geometry, and its crystal belongs to the monoclinic system, space group C2/c. For these three compounds, the zinc ion stabilises a penta-coordinated environment with square pyramid geometry. All mononuclear and dinuclear compounds are neutral, whereas the trinuclear complexes are ionic. The results of DFT theoretical calculations for the ligand (H2L) are used to assign the ligand singlet and triplet excited state energy levels. Luminescence studies of the neodymium compounds indicate that the ligand is a sensitizer for NIR emitters.
authors.affiliation: Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, Coyoacán, D. F. 04510, México. blum@unam.mx.
authors.forename: Daniela
authors.initials: D
authors.lastname: Olea-Román
authors.forename: Nicolas
authors.initials: N
authors.lastname: Bélanger-Desmarais
authors.forename: Marcos
authors.initials: M
authors.lastname: Flores-Álamo
authors.forename: Claudia
authors.initials: C
authors.lastname: Bazán
authors.forename: Félix
authors.initials: F
authors.lastname: Thouin
authors.forename: Christian
authors.initials: C
authors.lastname: Reber
authors.forename: Silvia E
authors.initials: SE
authors.lastname: Castillo-Blum