Molecular materials made of metallic polynuclears complexes with optical and magnetic properties : Thiacalixarenes / metals of transition
The realization of molecular architectures type [Mx(μ-L)yL’z]n; (with μ-L a chelating ligand, L’ a terminal ligand, n a charge and M a metallic transition ion) are attractive because of their potential applications in many domains such as magnetism, optics and catalysis.The terminal ligand which was chosen for this work is a macrocycle, called p-tert-butylsulfonylcalix[4]arene formed by phenolic units connected between them by sulfonyle groups.Firstly, a family of tetranuclear manganese (II) complexes was obtained and characterized. These clusters presented original optical properties of luminescence, in solid state and in solution.In solution, the photo-reaction of these clusters allowed to obtain the first stable ever mononuclear complex Mn3+/p-tert-butylsulfonylcalix[4]arene. Photo-reactivity of these complexes revealed that this ligand could have a molecular dynamics under a light irradiationThen the reactions made with ions Mn2+ were transposed for ions Co2+. Reactivity of Co2+ allowed to isolate various clusters with original molecular structures. Some presented properties of “Singles Ions Magnets”Finally, studies on the modification of p-tert-butylthiacalix[4]arene enabled us to design the first general method of mono-O-alkylation of this macrocycle type.