Synthesis, Structure, Magnetic and Photoluminescent Properties of Lanthanide(III) Complexes with a Ligand Based on 1,10-Phenanthroline and (+)−3-Carene

• Published in: Journal of structural chemistry 2019-08, Vol.60 (8), p.1314-1326
• Main Authors: Bryleva, Yu. A., Glinskaya, L. A., Agafontsev, A. M., Rakhmanova, M. I., Bogomyakov, A. S., Sukhikh, T. S., Gorbunova, E. A., Tkachev, A. V., Larionov, S. V.
• Format: Article
• Language: English
• Subjects: Anisotropy; Atomic; Atomic/Molecular Structure and Spectra; Chelation; Chemistry; Chemistry and Materials Science; Coordination compounds; Crystal structure; Crystallography; Dependence; Dysprosium; Inorganic Chemistry; Ligands; Luminescence; Magnetic properties; Molecular; Optical activity; Optical and Plasma Physics; Photoluminescence; Physical Chemistry; Polyhedra; Samarium; Solid State Physics
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1134/S0022476619080110

Ionic complexes of the composition [LnL 2 (NO 3 ) 2 ] 2 [Ln(NO 3 ) 5 ]3Me 2 CO (Ln = Sm ( 1 ), Eu ( 2 ), Tb ( 3 ), Dy ( 4 )) with an optically active ligand L containing 1,10-phenanthroline and (+)−3-carene moieties are synthesized. According to the X-ray crystallographic data, the crystal structure of compound 2 is composed of complex [EuL 2 (NO 3 ) 2 ] + cations (N 6 O 4 polyhedron) and complex [Eu(NO 3 ) 5 ] 2− anions (O 10 polyhedron), and also Me 2 CO molecules. The L and NO 3 ligands perform both tridentate and bidentate chelating functions respectively. Complexes 1–4 are isostructural and crystallize in the non-centrosymmetric space group P 1; their magnetic properties are studied in the temperature range 2–300 K. The μ eff values for 1–4 at 300 K are 3.14 μ B , 6.08 μ B , 16.76 μ B , and 18.30 μ B respectively and are typical of Ln 3+ ions. For complex 3 significant anisotropy results in a nonlinear field dependence of the magnetization at 2 K. Complexes 1–4 exhibit metal-centered orange (Sm 3+ ), red (Eu 3+ ), green (Tb 3+ ), and yellow (Dy 3+ ) luminescence in the solid state at room temperature. Luminescence quantum yield decreases for solid samples in the order 2 > 1 > 3 ≈ 4.