Jump to main content
Jump to site search

Issue 36, 2011
Previous Article Next Article

Chain-like and dinuclear coordination polymers in lanthanide (Nd, Eu) oxochloride complexes with 2,2′:6′,2′′-terpyridine: synthesis, XRD structure and magnetic properties

Author affiliations

Abstract

The solvothermal reactions (at 180 °C for 48 h) of a mixture of lanthanide chlorides (Nd, Eu) with the tridendate heterocyclic nitrogen ligand, 2,2′:6′,2′′-terpyridine (terpy), in ethanol medium give rise to the formation of crystalline mixed chloro-hydroxo-aquo complex Ln2Cl5(OH)(H2O)(terpy). Its crystal structure consists of the connection of eight- and nine-fold coordinated lanthanide centers linked to each other viaμ2,3-chloro and μ3-hydroxo species to form a tetranuclear unit, which are then further connected through chloro edges to generate infinite ribbons. Only one lanthanide cation in every two is chelated by terpy. Similar molar composition of the starting reactants led to the crystallization at room temperature of a second type of complex LnCl3(H2O)(terpy) (Ln = Nd, Eu). It is built up from the molecular assembly of dinuclear species containing two eight-fold coordinated lanthanide centers chelated by terpy and linked through a μ2-Cl edge. Luminescence spectra have been collected for the europium-based compound and indicates a strong red signal with the expected bands from the F–D transitions. The magnetic properties of the four compounds were investigated. Their behaviors correspond to that of the rare-earth ions present in the structure. The magnetic susceptibility of the neodymium-based compounds agrees with that of the Nd(III) ion with an 4I9/2 ground state split by crystal field. Concerning the Eu(III) derivatives, the term 7F is split by spin–orbit coupling, the first excited states being thermally populated. Accordingly, the thermal dependence of the magnetic susceptibility was nicely reproduced by using appropriate analytical relations. The refined values of the spin–orbit coupling are consistent with the energies of the electronic levels deduced from the photoluminescence spectra. Unexpectedly, the magnetic susceptibility exhibits a hysteretic behavior in the range 45–75 K.

Graphical abstract: Chain-like and dinuclear coordination polymers in lanthanide (Nd, Eu) oxochloride complexes with 2,2′:6′,2′′-terpyridine: synthesis, XRD structure and magnetic properties

Back to tab navigation

Supplementary files

Publication details

The article was received on 22 Mar 2011, accepted on 13 Jun 2011 and first published on 05 Aug 2011


Article type: Paper
DOI: 10.1039/C1DT10485C
Citation: Dalton Trans., 2011,40, 9136-9144
  •   Request permissions

    Chain-like and dinuclear coordination polymers in lanthanide (Nd, Eu) oxochloride complexes with 2,2′:6′,2′′-terpyridine: synthesis, XRD structure and magnetic properties

    J. Lhoste, A. Pérez-Campos, N. Henry, T. Loiseau, P. Rabu and F. Abraham, Dalton Trans., 2011, 40, 9136
    DOI: 10.1039/C1DT10485C

Search articles by author

Spotlight

Advertisements