Département de chimie moléculaire

The effects of a direct connection between ferrocene and porphyrin units were thoroughly studied by electrochem. and spectroscopic methods. These data not only reveal that substitution of the porphyrin macrocycle by one, two, three or four ferrocenyl groups strongly affects the electronic properties of the porphyrin and ferrocenyl moieties, also the metallocene centers are connected through the porphyrin-based electronic network. The dynamic properties of selected ferrocene-porphyrin conjugates were studied by VT NMR and metadynamic calcns. 1,3-Dithiolanyl protecting groups were introduced on the upper rings of the ferrocene fragments to allow a straightforward and easy access to redox active picket-fence porphyrins. X-ray diffraction analyses of the Zn(II) 5-[1'-[2-(1,3-dithiolanyl)]ferrocenyl]-10,15,20-tri(p-tolyl)porphyrin and 5,15-bis[1'-[2-(1,3-dithiolanyl)]ferrocenyl]-10,20-bis(p-tolyl)porphyrin complexes reveal the existence of S-Zn bonds involved in supramol. arrays. The solid state anal. of the trans-5,15-di-(1'-(formyl)ferrocenyl)-10,20-di-(p-tolyl)-porphyrinatozinc(II) complex, obtained by deprotection of the dithiolane substituted analog, is conversely found in the crystal lattice as a monomer exhibiting a hexacoordinated Zn metal center. [on SciFinder(R)]