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Chirogenesis and Pfeiffer Effect in Optically Inactive Eu III and Tb III Tris(β-diketonate) Upon Intermolecular Chirality Transfer From Poly- and Monosaccharide Alkyl Esters and α-Pinene: Emerging Circularly Polarized Luminescence (CPL) and Circular Dichroism (CD)

Authors
  • Fujiki, Michiya1
  • Wang, Laibing1
  • Ogata, Nanami1
  • Asanoma, Fumio1
  • Okubo, Asuka1
  • Okazaki, Shun1
  • Kamite, Hiroki1
  • Jalilah, Abd Jalil1, 2, 3
  • 1 Division of Materials Science, Graduate School of Science and Technology, Nara Institute of Science and Technology, Ikoma , (Japan)
  • 2 School of Materials Engineering, Universiti Malaysia Perlis, Jejawi , (Malaysia)
  • 3 Centre of Excellence Frontier Materials Research, Universiti Malaysia Perlis, Kangar , (Malaysia)
Type
Published Article
Journal
Frontiers in Chemistry
Publisher
Frontiers Media S.A.
Publication Date
Aug 11, 2020
Volume
8
Identifiers
DOI: 10.3389/fchem.2020.00685
PMID: 32903703
PMCID: PMC7438854
Source
PubMed Central
Keywords
License
Unknown

Abstract

We report emerging circularly polarized luminescence (CPL) at 4 f- 4 f transitions when lanthanide (EuIII and TbIII) tris(β-diketonate) embedded to cellulose triacetate ( CTA ), cellulose acetate butyrate ( CABu ), D -/ L -glucose pentamethyl esters ( D - / L -Glu ), and D -/ L -arabinose tetramethyl esters ( D - / L -Ara ) are in film states. Herein, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate (fod) and 2,2,6,6-tetramethyl-3,5-heptanedione (dpm) were chosen as the β-diketonates. The g lum value of Eu(fod)3 in CABu are +0.0671 at 593 nm (5 D 0 → 7 F1) and −0.0059 at 613 nm (5 D 0 → 7 F2), respectively, while those in CTA are +0.0463 and −0.0040 at these transitions, respectively. The g lum value of Tb(fod)3 in CABu are −0.0029 at 490 nm (5 D 4 → 7 F6), +0.0078 at 540 nm (5 D 4 → 7 F5), and −0.0018 at 552 nm (5 D 4 → 7 F5), respectively, while those in CTA are −0.0053, +0.0037, and −0.0059 at these transitions, respectively. D - / L -Glu and D - / L -Ara induced weaker g lum values at 4 f- 4 f transitions of Eu(fod)3, Tb(fod)3, and Tb(dpm)3. For comparison, Tb(dpm)3 in α-pinene showed clear CPL characteristics, though Eu(dpm)3 did not. A surplus charge neutralization hypothesis was applied to the origin of attractive intermolecular interactions between the ligands and saccharides. This idea was supported from the concomitant opposite tendency in upfield 19F-NMR and downfield 1H-NMR chemical shifts of Eu(fod)3 and the opposite Mulliken charges between F -C bonds (fod) and H -C bonds ( CTA and D - / L -Glu ). An analysis of CPL excitation (CPLE) and CPL spectra suggests that (+)- and (–)-sign CPL signals of EuIII and TbIII at different 4 f- 4 f transitions in the visible region are the same with the (+)-and (–)-sign exhibited by CPLE bands at high energy levels of EuIII and TbIII in the near-UV region.

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