Synthesis, solid state characterization, theoretical and experimental spectroscopic studies of the new lanthanide...

Area of Science:

• Coordination Chemistry
• Materials Science
• Computational Chemistry

Background:

• Lanthanide complexes are crucial in luminescence applications.
• Understanding structure-property relationships is key for designing new materials.
• Picolinate ligands offer versatile coordination modes.

Purpose of the Study:

• Synthesize and characterize novel sodium lanthanide picolinate complexes.
• Investigate their structural, photoluminescent, and energy transfer properties.
• Correlate experimental findings with theoretical calculations.

Main Methods:

• Synthesis of Na[Ln(pic)4]·2.5H2O (Ln = Tb, Eu, Gd; pic = picolinate) complexes.
• Characterization using infrared spectroscopy, X-ray diffraction (powder and single-crystal), and thermogravimetric analysis.
• Photoluminescence spectroscopy, lifetime measurements, and theoretical calculations (DFT, TD-DFT, AM1/Sparkle, INDO/S-CIS).

Main Results:

• Three isostructural lanthanide complexes were synthesized and their crystal structures determined.
• Detailed photoluminescent properties were investigated, showing efficient ligand-to-lanthanide energy transfer, especially for terbium.
• Theoretical calculations using DFT (B3LYP, LC-wPBE) provided accurate structural and luminescence property descriptions, explaining low europium emission efficiency.

Conclusions:

• The synthesized complexes exhibit interesting structural and photoluminescent characteristics.
• Ligand-to-lanthanide energy transfer is efficient, with potential for luminescence applications.
• Computational methods are valuable tools for understanding and predicting the properties of these lanthanide complexes.