Bernátková M1,2, Andrioletti B1, Rose E1, Král V2
1Laboratoire de Synthèse Organique et Organométallique UMR 7611 Université P. et M. Curie, Paris, France, 2Department of Analytical Chemistry, ICT Prague, Czech Republic
During the last decade, the development of novel specific receptors has been the main interest of supramolecular and analytical chemist. Chemical hybrids of porphyrins and calixpyrroles, called calix[n]phyrins, are oligopyrrolic macrocycles that contain at least one sp3 hybridized meso-like bridging carbon atom. While porphyrins are well known cation coordinating ligands, the calixpyrroles have recently emerged as simple-to-make anion receptors. It is thus of interest to prepare and study calix[4]phyrins to ascertain whether they would react with cations, anions, or both. Here, we wish to report the unexpected reactivity of electron deficient aryl aldehydes with 5,5-dimethyldipyrromethane under acid catalysis in propionitrile that conveniently affords functionalized porphomethenes at the expense of the expected parent calix[4]phyrins in good yield. As part of our efforts on the development of easy-to-prepare oligopyrrolic macrocycles, we intended to design a new series of easily tunable calixphyrine-type systems. The functionalized calix[4]phyrins open the possibilities for constructing multifunctional receptors. This application will be demonstrated on the preparation of the first chiral calixphyrin dimer. Also, the preparation of water soluble calixphyrins considered for use in photodynamic therapy will be presented. The first electrochemical results will be reported. [Financial support from the Ministry of Education of the Czech Republic Grant No. MSM 223400008, the Grant EU QLRT-2000-02360, Grant Agency of the Czech Republic No. 309/02/1193 and from French government is gratefully acknowledged].