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<p>We developed a new method to measure the time-resolved CD (TR-CD) spectra of the photo-excited triplet states of chiral supramolecules of bis(zinc octaethylporphyrin) and (<i>R</i>)- and (<i>S</i>)-diaminocyclohexane in the wide wavelength region (UV and visible) even overlapping with the intense steady-state CD signals. Such measurements are possible by developing a high-sensitive TR-CD equipment assembled in our laboratory. The observed TR-CD spectra of the triplet states of chiral supramolecules show mono-signate CD signals corresponding to each transient absorption band in the 300–500-nm region. Combination of the TR-CD spectral pattern with the dynamic behavior of the CD signals in the excited triplet states affords information for the electron distribution change of the triplet state from that of the ground state. In addition, the zero-field splitting parameters obtained from the time-resolved EPR spectra of the photo-excited supramolecules suggest that the electron spin density distributes on one side of two porphyrin rings of the chiral bis-porphyrin supramolecules in the triplet states, which is further confirmed by the DFT calculations.</p> Graphical Abstract <p></p>

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Time-resolved spectroscopic study on chiral supramolecules consist of bis(zinc octaethylporphyrin) and (R)- and (S)-diaminocyclohexanes using; transient absorption, CD,and EPR spectroscopies

  • 期刊论文

  • 发表日期：

    2026年1月23日

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  • Makoto Murakami,
  • Ken Imai,
  • Takahito Ida,
  • Yasuyuki Araki,
  • Takehiko Wada,
  • Seigo Yamauchi,
  • Yasuhiro Kobori,
  • Osamu Ito

摘要

We developed a new method to measure the time-resolved CD (TR-CD) spectra of the photo-excited triplet states of chiral supramolecules of bis(zinc octaethylporphyrin) and (R)- and (S)-diaminocyclohexane in the wide wavelength region (UV and visible) even overlapping with the intense steady-state CD signals. Such measurements are possible by developing a high-sensitive TR-CD equipment assembled in our laboratory. The observed TR-CD spectra of the triplet states of chiral supramolecules show mono-signate CD signals corresponding to each transient absorption band in the 300–500-nm region. Combination of the TR-CD spectral pattern with the dynamic behavior of the CD signals in the excited triplet states affords information for the electron distribution change of the triplet state from that of the ground state. In addition, the zero-field splitting parameters obtained from the time-resolved EPR spectra of the photo-excited supramolecules suggest that the electron spin density distributes on one side of two porphyrin rings of the chiral bis-porphyrin supramolecules in the triplet states, which is further confirmed by the DFT calculations.

Graphical Abstract