Ln(iii) complexes with a chiral 1H-pyrazolo[3,4-b]pyridine derivative fused with a (−)-α-pinene moiety: synthesis, crystal structure, and photophysical studies in solution and in the solid state

Yuliya A. Bryleva, Yuliya P. Ustimenko, Victor F. Plyusnin, Alexsandr V. Mikheilis, Aleksandr A. Shubin, Ludmila A. Glinskaya, Vladislav Yu Komarov, Alexander M. Agafontsev, Alexey V. Tkachev

Research output: Contribution to journalArticlepeer-review

Abstract

Chiral lanthanide(iii) complexes, [LnL2(NO3)3]·MeCN (Ln = Sm (1), Eu (2), Tb (3)), containing an optically active 1H-pyrazolo[3,4-b]pyridine derivative fused with a natural monoterpene (−)-α-pinene moiety (L) have been synthesized and structurally characterized. The mononuclear complexes1-3are isostructural and crystallize in the non-centrosymmetric space groupP21212. The lanthanide ions are ten-coordinated with three bidentate chelating nitrate ions and two bidentate N,N-donor ligands L. Complexes1-3show 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 order1<2<3. Complex3possesses a very high luminescence quantum yield both in acetonitrile solution (φf= 0.736) and in the solid state (φf= 0.890), indicating efficient energy transfer from two ligands L to the Ln center. The luminescence quantum yields of complexes1and2in 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.

Original languageEnglish
Pages (from-to)2276-2284
Number of pages9
JournalNew Journal of Chemistry
Volume45
Issue number4
DOIs
Publication statusPublished - 28 Jan 2021

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