Synthesis,structural analysis,and thermal and spectroscopic studies of methylmalonate-containing zinc(II) complexes |
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| Authors: | Mariadel Déniz Jorge Pasán Oscar Fabelo Laura Cañadillas-Delgado Pablo Lorenzo-Luis Fernando Lahoz David López Consuelo Yuste Miguel Julve Catalina Ruiz-Pérez |
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| Institution: | 1. 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;2. Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, 50009 Zaragoza, Spain;3. Institut Laue-Langevin, 6, rue Jules-Horowitz, BP 156, 38042 Grenoble cedex 9, France;4. Departamento de Química Inorgánica, Facultad de Química, Universidad de La Laguna, Avenida Astrofísico Francisco Sánchez s/n, 38204 La Laguna (Tenerife), Spain;5. 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;6. Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMol), Facultat de Química, Universitat de València, Polígono La Coma s/n, 46980 Paterna (València), Spain |
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| Abstract: | The synthesis, crystal structure, thermal analysis and spectroscopic studies of five zinc(II) complexes of formulae Zn(Memal)(H2O)]n (1) and Zn2(L)(Memal)2(H2O)2]n (2-5) H2Memal = 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 μ3-κ2O:κO’: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 μ3-κO:κO′: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. |
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| Keywords: | Carboxylate ligands Zinc Coordination modes Fluorescence spectroscopy Crystal engineering |
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