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Peer-reviewedCC BY-NCChemical science

Biasing the dynamic Δ/Λ equilibrium of a helical and luminescent Tb(iii) complex on chiral amine-functionalized silica surfaces.

  • Sora Shirai1
  • Satoshi Muratsugu1
  • Keiko Hibi1
  • Naoki Yokoyama2
  • Hisaki Matsui2
  • Takafumi Shiraogawa3
  • Masahiro Ehara3
  • Hidetaka Nakai2
  • Mizuki Tada1
  1. 1Department of Chemistry, Graduate School of Science/Integrated Research Consortium on Chemical Science/Research Center for Materials Science, Nagoya University Furo-cho, Chikusa Nagoya Aichi 464-8602 Japan [email protected] [email protected].
  2. 2Department of Energy and Materials, Faculty of Science and Engineering/Graduate School of Science and Engineering, Kindai University 3-4-1 Kowakae Higashiosaka City Osaka 577-8502 Japan [email protected].
  3. 3Institute for Molecular Science, Research Center for Computational Science, Graduate University for Advanced Studies Myodaiji Okazaki 444-8585 Aichi Japan.
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Abstract

The pre-existing dynamic Δ/Λ equilibrium of a racemic luminescent terbium (Tb) complex with a tetrakis-ortho-phenylphenoxide-functionalized 1,4,7,10-tetraazacyclododecane (cyclen) ligand (1Tb) was biased by binding to a newly prepared, chiral (R)- or (S)-1-phenylethylamine (PEA)-functionalized SiO2 surface ((R)- or (S)-LNH2/SiO2). The circular dichroism (CD) and circularly polarized luminescence (CPL) activities of 1Tb were induced on the SiO2 surface, indicating that the population ratio of the Δ and Λ helical conformations of 1Tb was deviated from unity on (R)- or (S)-LNH2/SiO2. The induced chiroptical responses were more pronounced at lower surface densities of 1Tb, suggesting an important role of the local chiral surface environment. Density functional theory (DFT) and time-dependent-DFT calculations suggested that the CD originated from the π-π* transition of the ortho-phenylphenoxide moiety of 1Tb bound to (R)- or (S)-PEA. Comparison of the simulated and experimental CD spectra suggested preferential population of the Δ form of 1Tb on (R)-LNH2/SiO2 and of the Λ form on (S)-LNH2/SiO2.

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Cite

BibTeXRIS
BibTeX
@article{shirai2026biasing,
  title = {{Biasing the dynamic Δ/Λ equilibrium of a helical and luminescent Tb(iii) complex on chiral amine-functionalized silica surfaces.}},
  author = {Sora Shirai and Satoshi Muratsugu and Keiko Hibi and Naoki Yokoyama and Hisaki Matsui and Takafumi Shiraogawa and Masahiro Ehara and Hidetaka Nakai and Mizuki Tada},
  journal = {Chemical science},
  year = {2026},
  month = oct,
  doi = {10.1039/d6sc04846c},
  url = {https://europepmc.org/article/MED/42953111},
  note = {CC BY-NC},
}
RIS
TY  - JOUR
TI  - Biasing the dynamic Δ/Λ equilibrium of a helical and luminescent Tb(iii) complex on chiral amine-functionalized silica surfaces.
AU  - Sora Shirai
AU  - Satoshi Muratsugu
AU  - Keiko Hibi
AU  - Naoki Yokoyama
AU  - Hisaki Matsui
AU  - Takafumi Shiraogawa
AU  - Masahiro Ehara
AU  - Hidetaka Nakai
AU  - Mizuki Tada
PY  - 2026
DA  - 2026/10/28
JO  - Chemical science
DO  - 10.1039/d6sc04846c
UR  - https://europepmc.org/article/MED/42953111
AB  - The pre-existing dynamic Δ/Λ equilibrium of a racemic luminescent terbium (Tb) complex with a tetrakis-ortho-phenylphenoxide-functionalized 1,4,7,10-tetraazacyclododecane (cyclen) ligand (1Tb) was biased by binding to a newly prepared, chiral (R)- or (S)-1-phenylethylamine (PEA)-functionalized SiO2 surface ((R)- or (S)-LNH2/SiO2). The circular dichroism (CD) and circularly polarized luminescence (CPL) activities of 1Tb were induced on the SiO2 surface, indicating that the population ratio of the Δ and Λ helical conformations of 1Tb was deviated from unity on (R)- or (S)-LNH2/SiO2. The induced chiroptical responses were more pronounced at lower surface densities of 1Tb, suggesting an important role of the local chiral surface environment. Density functional theory (DFT) and time-dependent-DFT calculations suggested that the CD originated from the π-π* transition of the ortho-phenylphenoxide moiety of 1Tb bound to (R)- or (S)-PEA. Comparison of the simulated and experimental CD spectra suggested preferential population of the Δ form of 1Tb on (R)-LNH2/SiO2 and of the Λ form on (S)-LNH2/SiO2.
SN  - 2041-6520
SN  - 2041-6539
ER  -