Coordination chemistry in the solid: evidence for coordination modes within hybrid materials different from those in solution.

Two routes of incorporation of europium(III) salts into cyclam-containing hybrid materials have been explored, to elucidate the coordination mode of EuIII in cyclam-containing hybrid materials in a study of the arrangement of cyclam moieties during the solgel process. They were 1) complexation of europium salts by N-tetrasubstituted 1,4,8,11-tetraazacyclotetradecane (cyclam) derivatives bearing four hydrolysable Si(OEt)3 groups, followed by hydrolysis and polycondensation of these complexes; and 2) hydrolysis and polycondensation of N-tetrasubstituted silylated cyclam derivatives, then incorporation of europium salts directly into the hybrid materials. The coordination mode of europium salts within solids is not the same as in solution. In solution, the complexation of EuIII with cyclam is not possible; it requires cyclam derivatives containing N-chelating substituents such as amido groups in an appropriate geometry. In contrast, the incorporation of EuIII into hybrid materials is always possible, whatever the nature of the arms of the cyclam moieties. Thus, EuIII uptake is one EuIII/two macrocycles with cyclam moieties containing N-alkyl substituents. This constitutes the first example of 4N + 4N lanthanide coordination.