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Comptes Rendus Chimie
Volume 15, n° 10
pages 911-923 (octobre 2012)
Doi : 10.1016/j.crci.2012.04.007
Received : 5 Mars 2012 ;  accepted : 20 April 2012
Synthesis, structural analysis, and thermal and spectroscopic studies of methylmalonate-containing zinc(II) complexes

Mariadel Déniz a, Jorge Pasán a, , Oscar Fabelo a, b, c, Laura Cañadillas-Delgado a, b, c, 1, Pablo Lorenzo-Luis d, Fernando Lahoz e, David López e, Consuelo Yuste f, Miguel Julve f, Catalina Ruiz-Pérez a,
a Laboratorio de Rayos X y Materiales Moleculares, Departamento de Física Fundamental II, Facultad de Física, Universidad de La Laguna, Avenida Astrofísico Francisco Sánchez s/n, 38204 La Laguna (Tenerife), Spain 
b Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, 50009 Zaragoza, Spain 
c Institut Laue-Langevin, 6, rue Jules-Horowitz, BP 156, 38042 Grenoble cedex 9, France 
d Departamento de Química Inorgánica, Facultad de Química, Universidad de La Laguna, Avenida Astrofísico Francisco Sánchez s/n, 38204 La Laguna (Tenerife), Spain 
e Departamento de Física Fundamental y Experimental, Electrónica y Sistemas, Facultad de Física, Universidad de La Laguna, Avenida Astrofísico Francisco Sánchez s/n, 38204 La Laguna (Tenerife), Spain 
f Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMol), Facultat de Química, Universitat de València, Polígono La Coma s/n, 46980 Paterna (València), Spain 

Corresponding authors.

The synthesis, crystal structure, thermal analysis and spectroscopic studies of five zinc(II) complexes of formulae [Zn(Memal)(H2 O)]n (1) and [Zn2 (L)(Memal)2 (H2 O)2 ]n (2-5) [H2 Memal=methylmalonic acid, and L=4,4′-bipyridine (4,4′-bpy) (2), 1,2-bis(4-pyridyl)ethylene (bpe) (3), 1,2-bis(4-pyridyl)ethane (bpa) (4) and 4,4′-azobispyridine (azpy) (5)] are presented here. The crystal structure of 1 is a three-dimensional arrangement of zinc(II) cations interconnected by methylmalonate groups adopting the μ32OO ’:κO”: κO”’ coordination mode to afford a rare (10,3)-d utp-network. The structures of the compounds 2-5 are also three-dimensional and they consist of corrugated square layers of methylmalonate-bridged zinc(II) ions which are pillared by bis-monodentate 4,4′-bpy (2), bpe (3), bpa (4) and azpy (5) ligands. The Memal ligand in 2-5 adopts the μ3OO ′:κO ′′: κO ′′′ coordination mode. Each zinc(II) ion in 1-5 is six-coordinated with five (1)/four (2-5) methylmalonate-oxygen atoms, a water molecule (1-5) and a nitrogen atom from a L ligand (2-5) building distorted octahedral environments. The rod-like L co-ligands in 2-5 appear as useful tools to control the interlayer metal-metal separation, which covers the range 8.4311(5) Å (2) – 9.644(3) Å (5). The influence of the co-ligand on the fluorescence properties of this series of compounds has been analyzed and discussed by steady-state and time resolved spectroscopy on all five compounds in the solid state.

The full text of this article is available in PDF format.

Keywords : Carboxylate ligands, Zinc, Coordination modes, Fluorescence spectroscopy, Crystal engineering

1  Present address: Centro Universitario para la Defensa, Academia General Militar, Ctra de Huesca s/n, 50090 Zaragoza, Spain.
2  DIAMOND 2.1d, Crystal Impact GbR, CRYSTAL IMPACT, K. Brandenburg & H. Putz GbR, Postfach 1251, 53002 Bonn, Germany, 2000.

© 2012  Académie des sciences@@#104156@@
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