期刊
NEW JOURNAL OF CHEMISTRY
卷 45, 期 4, 页码 2276-2284出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0nj05277a
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资金
- Russian Science Foundation [18-13-00246]
- Russian Foundation for Basic Research [17-03-00252]
- Siberian Branch of the Russian Academy of Sciences Siberian Supercomputer Center
- Russian Science Foundation [18-13-00246] Funding Source: Russian Science Foundation
Chiral lanthanide(iii) complexes containing optically active 1H-pyrazolo[3,4-b]pyridine derivative fused with a natural monoterpene (-)-alpha-pinene moiety have been synthesized and shown to exhibit metal-centered luminescence in both solution and solid state. Among the complexes, complex 3 has the highest luminescence quantum yield, indicating efficient energy transfer from the ligands to the lanthanide center. DFT and TD-DFT studies were conducted to investigate the geometry, electronic structure, and absorption properties of the complexes.
Chiral lanthanide(iii) complexes, [LnL(2)(NO3)(3)]center dot MeCN (Ln = Sm (1), Eu (2), Tb (3)), containing an optically active 1H-pyrazolo[3,4-b]pyridine derivative fused with a natural monoterpene (-)-alpha-pinene moiety (L) have been synthesized and structurally characterized. The mononuclear complexes 1-3 are isostructural and crystallize in the non-centrosymmetric space group P2(1)2(1)2. The lanthanide ions are ten-coordinated with three bidentate chelating nitrate ions and two bidentate N,N-donor ligands L. Complexes 1-3 show metal-centered luminescence at room temperature in solution and in the solid state. The solid-state and solution-phase luminescence quantum yields increase in the order 1 < 2 < 3. Complex 3 possesses a very high luminescence quantum yield both in acetonitrile solution (phi(f) = 0.736) and in the solid state (phi(f) = 0.890), indicating efficient energy transfer from two ligands L to the Ln center. The luminescence quantum yields of complexes 1 and 2 in the acetonitrile solutions are almost two and four times higher, respectively, than those in the solid state. DFT and TD-DFT studies were carried out to explore geometry and electronic structure of L and to gain insight into its absorption properties.
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