Self-assembled multibilayers of europium alkanoates: structure, photophysics, and mesomorphic behavior

A series of europium alkanoates (C(n-1)H(2n-1)CO(2))(3)Eu, (n = 14, 16, 18, 20) have been synthesized and characterized in detail. X-ray diffraction and Fourier transform infrared spectroscopic measurements confirm the multibilayer structure of these homologues. In such bilayers, the europium ionic layers are well separated by the highly ordered alkyl chains which are in an all-trans conformation and perpendicular to both sides of the europium ionic layers. There is a mixed-coordination type of chelating bidentate and bridging bidentate between the carboxylate groups and the europium ions. All samples exhibit characteristic emission of europium, though the luminescent intensity has been partly quenched by the carboxylate groups. Differential scanning calorimetry (DSC) shows multiple melting points for these homologues, and temperature-dependent X-ray diffraction measurements also confirm the existence of the mesophase on heating. This mesophase is not truly liquid crystalline, but is similar to the smectic A phase of organic rodlike molecules. Meanwhile, it seems that with increasing atomic number of lanthanide ions, longer alkyl chains will be required to form such a mesophase for the corresponding lanthanide alkanoates.