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Excited State Structure Correlates with Efficient Photoconversion in Unidirectional Motors.

Palas Roy1, Andy S Sardjan2, Arjen Cnossen2

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Understanding ultrafast photochemical isomerization is key for designing molecular motors. This study links molecular structure, dark state lifetime, and vibrational spectra to photoisomerization efficiency, guiding the development of improved motor designs.

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Area of Science:

  • Photochemistry
  • Molecular machines
  • Ultrafast spectroscopy

Background:

  • Unidirectional photomolecular motors rely on ultrafast photochemical isomerization.
  • An intermediate dark excited state mediates this reaction through a conical intersection (CI) with the ground state.
  • The relationship between molecular structure and photoisomerization efficiency remains unclear.

Purpose of the Study:

  • To investigate the correlation between molecular structure and photoisomerization efficiency in molecular motors.
  • To capture vibrational spectra of the dark state using femtosecond stimulated Raman spectroscopy.
  • To establish guidelines for designing more efficient molecular motor derivatives.

Main Methods:

  • Femtosecond stimulated Raman spectroscopy (FSRS) was employed.
  • Vibrational spectra of the dark state were recorded for molecular motors with varying substituents.
  • Photoisomerization quantum yield and dark state lifetime were measured.

Main Results:

  • A direct correlation was found between isomerization quantum yield, dark state lifetime, and excited state vibrational spectrum.
  • Electron-withdrawing substituents induced activity in lower frequency modes, linked to pyramidalization distortion at the ethylenic axle within 100 fs.
  • Electron-donating substituents did not promote this distortion, maintaining double bond character at the axle.

Conclusions:

  • The dark state structure significantly influences photoconversion performance.
  • Substituent effects on molecular structure, particularly ethylenic axle distortion, are critical for motor efficiency.
  • These findings provide a basis for rational design of enhanced photomolecular motors.