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Journal of the Mexican Chemical Society
Print version ISSN 1870-249X
J. Mex. Chem. Soc vol.54 n.3 Ciudad de México Jul./Sep. 2010
Article
Synthesis, Solid and Solution Studies of Paraquat Dichloride Calixarene Complexes. Molecular Modelling
Irma GarcíaSosa and Flor de María Ramírez*
Instituto Nacional de Investigaciones Nucleares, Departamento de Química, Carretera MéxicoToluca S/N. La Marquesa, Ocoyoacac. C.P. 52750, México. Phone: (+) 53297200. FAX: (+) 53297301.*Responsible author: flor.ramirez@inin.gob.mx.
Received November 25, 2009
Accepted April 28, 2010
Abstract
The interaction of the herbicide paraquat dichloride (PQ, substrate) with ptertbutylcalix[6, 8]arenes (L, receptor) was investigated in both the solution and solid states. The isolated paraquat calixarene complexes were characterised by UVvisible, 1H NMR, ESIMS, Luminescence and IR spectroscopies and elemental analysis. The stoichiometry of complexes 1 and 2 was 1:1 (1 herbicide:1 calixarene) and both revealed a biexponential luminescence decay with lifetimes depending on the size and the conformational particularity of the calixarenes. Molecular modelling suggested that both calixarenes interact with the herbicide through cationπ interaction. PQ is included in the ptertbutylcalix[8]arene cavity, a situation favoured by its pinched conformation in polar solvent while it is partially included in the ptertbutylcalix[6]arene cavity because of its inout cone conformation. The theoretical results, in particular using MOPAC procedures, were in agreement with the experimental findings.
Keywords: Parent calixarenes; Pesticides; Phosphorescence; Augmented Molecular Mechanics Calculations; CONFLEX.
Resumen
Se investigó la interacción del herbicida dicloruro de paraquat (PQ, substrato) con el pterbutilocalix[6,S]areno (L, receptor) en el estado sólido y solución. Se aislaron los complejos calixarénicos de paraquat y se caracterizaron por espectroscopias de UVvisible, IR, RMN de hidrógeno, masasESI, Luminiscencia, IR y análisis elemental. La estequiometría de los complejos 1 y 2 fue 1:1 (1PQ:1calixarene) y el decaimiento de luminiscencia en ambos casos fue biexponencial con tiempos de vidas dependientes del tamaño y la conformación del calixareno. El modelado molecular sugirió que ambos calixarenos interaccionan con el herbicida mediante interacción del tipo catiónπ. PQ se incluye en la cavidad del pterbutilocalix[8]areno, situación que se favorece por su conformación "pinched" en un solvente polar mientras que en el pterbutilocalix[6]areno se incluye parcialmente debido a su conformación de cono "inout". Los resultados teóricos, en particular, procedimientos MOPAC, concordaron con los experimentales.
Palabras clave: Calixarenos padres, Plaguicidas, Fosforescencia, Cálculos de Mecánica Molecular Aumentado, CONFLEX.
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Acknowledgments
This study was supported by Conacyt (México), project 36689E. We thank the technicians of the Department of Chemistry of ININ for their help, Dr. Carol Pérez from UNAM for the 1H NMR measurement of the free calixarenes in CD2Cl2, and Mr. Claudio Fernández at the Library of ININ for his assistance whenever it was needed.
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