Issue 8, 2013
From the journal:

New Journal of Chemistry

A new synthetic route towards binuclear 3d–4f complexes, using non-compartmental ligands derived from o-vanillin. Syntheses, crystal structures, magnetic and luminescent properties†‡

Masood Sarwar,a   Augustin M. Madalan,*a   Carmen Tiseanu,*b   Ghenadie Novitchi,c   Catalin Maxim,a   Gabriela Marinescu,d   Dominique Luneaue  and  Marius Andruh*a  

* Corresponding authors

a University of Bucharest, Faculty of Chemistry, Inorganic Chemistry Laboratory, Str. Dumbrava Rosie nr. 23, 020464-Bucharest, Romania
E-mail: madalin.madalan@g.unibuc.ro, marius.andruh@dnt.ro

b National Institute for Laser, Plasma and Radiation Physics, Laboratory of Solid-State Quantum Electronics, PO Box MG-36, Magurele, Romania
E-mail: tiseanuc@yahoo.com

c Laboratoire National des Champs Magnétiques Intenses, CNRS UPR-3228, 25 rue des Martyrs, 38042 Grenoble Cedex 9, France

d Ilie Murgulescu Institute of Physical Chemistry of the Romanian Academy, Coordination and Supramolecular Chemistry Laboratory, Spl. Independentei no. 202, 060021-Bucharest, Romania

e Laboratoire des Multimatériaux et Interfaces, Groupe de Crystallographie et Ingénierie Moléculaire, Université Claude Bernard Lyon 1, UMR CNRS 5615, Bâtiment Berthollet-Domaine Scientifique de la Doua, 69622 Villeurbanne Cedex, France

Abstract

Sixteen new 3d–4f binuclear complexes have been obtained using two Schiff-base ligands, Hvalampy and Hvalaepy, derived from the reaction of o-vanillin and 2-aminomethyl-pyridine or 2-(2-aminoethyl)-pyridine, respectively. Hvalaepy ligand: [Zn(valaepy)2Sm(O2NO)3]·CH3CN 1; [Ni(valaepy)2Eu(O2NO)3(H2O)]·CH3CN 2; [Ni(valaepy)2Gd(O2NO)3(H2O)]·CH3CN 3; [Ni(valaepy)2Dy(O2NO)3(H2O)]·CH3CN 4; [Ni(valaepy)2Ho(O2NO)3(H2O)]·CH3CN 5; [Cu(valaepy)2Eu(O2NO)3]·CH3CN 6; [Cu(valaepy)2Gd(O2NO)3]·CH3CN 7; Hvalampy ligand: [Zn(valampy)2Pr(O2NO)3]·CH3CN 8, [Zn(valampy)2Sm(O2NO)3]·CH3CN 9; [Zn(valampy)2Gd(O2NO)3]·CH3CN 10; [Zn(valampy)2Tb(O2NO)3]·CH3CN 11; [Zn(valampy)2Dy(O2NO)3]·CH3CN 12; [Zn(valampy)2Eu(O2NO)3]·CH3CN 13; [Ni(valampy)2La(O2NO)3(H2O)2]·2H2O 14, [Ni(valampy)2Sm(O2NO)3(H2O)2]·2H2O 15; [Ni(valampy)2Eu(O2NO)3(H2O)]·2CH3CN 16. The crystal structures of the sixteen compounds can be described as resulting from the coordination of two valaepy− (or valampy−) ligands to the 3d metal ions through two phenoxo oxygen atoms and nitrogen atoms, arising from the pyridyl and azomethynic groups. In all these compounds the 3d and 4f metal ions are bridged by the phenoxo oxygen atoms. The comparative analysis of the crystal structures shows several differences, which arise mainly from the stereochemical preference of the 3d metal ions. These ions arrange the two organic ligands in positions that favour or not the coordination of the methoxy groups to the lanthanide ions. The magnetic properties of compounds 2, 3, 4, 5, 7, 14, 15, and 16 have been investigated. The exchange interactions between NiII and GdIII in 3, and between CuII and GdIII in 7 were found to be ferromagnetic (JNiGd = 1.56 cm−1; JCuGd = 4.94 cm−1; H = −JSGdSM). For the 3d–4f binuclear complexes derived from the Hvalampy ligand (namely 8–13) the photoluminescence (PL) properties were investigated in the Vis spectral region. The results provide evidence for the relatively stronger antenna effect in 9 and 11 compared to 8, 12 and 13.

Graphical abstract: A new synthetic route towards binuclear 3d–4f complexes, using non-compartmental ligands derived from o-vanillin. Syntheses, crystal structures, magnetic and luminescent properties

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Article information

DOI
https://doi.org/10.1039/C3NJ00199G
Article type
Paper
Submitted
21 Feb 2013
Accepted
27 Mar 2013
First published
27 Mar 2013

New J. Chem., 2013,37, 2280-2292

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A new synthetic route towards binuclear 3d–4f complexes, using non-compartmental ligands derived from o-vanillin. Syntheses, crystal structures, magnetic and luminescent properties

M. Sarwar, A. M. Madalan, C. Tiseanu, G. Novitchi, C. Maxim, G. Marinescu, D. Luneau and M. Andruh, New J. Chem., 2013, 37, 2280 DOI: 10.1039/C3NJ00199G

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