Wide-Range Columnar and Lamellar Photoluminescent Liquid-Crystalline Lanthanide Complexes with Mesogenic 4-Pyridone...

A series of liquid crystals with various lanthanide ions (Eu^III , Sm^III , and Tb^III ) was designed and prepared starting from the corresponding lanthanide nitrates and N-alkylated 4-pyridone derivatives bearing mesogenic 3,4,5-tris(alkyloxy)benzyl moieties (alkyl=hexyl, octyl, decyl, dodecyl, tetradecyl, or hexadecyl). These new lanthanidomesogens were investigated for their mesogenic properties by a combination of differential scanning calorimetry, polarizing optical microscopy, and temperature-dependent powder X-ray diffraction (XRD). Their thermal stability was assessed by thermogravimetric analysis. All of these complexes show enantiotropic liquid-crystalline behavior with lamellar (SmA) phases in the case of shorter-chain complexes (C₆ and C₈ ) or hexagonal columnar phases (Col_h ) for complexes with longer alkyl chains (C₁₂ , C₁₄ , and C₁₆ ), which were assigned on the basis of their characteristic textures and XRD studies. For complexes with an intermediate number of carbon atoms in the side chains (C₁₀ ), both a lamellar phase at lower temperatures and a Col_h phase at higher temperatures were evidenced. In the solid state, all these complexes show characteristic emissions assigned to the corresponding lanthanide ion. In addition, the luminescence decay curves showed single-exponential decays with characteristic times in the millisecond range (0.75-0.90 ms for Eu^III , 0.045-0.060 ms for Sm^III , and 0.75-1.05 ms for Tb^III ).