Non-Linear Optical Activity of Chiral Bipyrimidine-Based Thin Films

Nicolas P., Abdallah S., Dok A., de Coene Y., Jeannin O., Bellec N., ...More

Chemistry - An Asian Journal, vol.19, no.9, 2024 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 19 Issue: 9
  • Publication Date: 2024
  • Doi Number: 10.1002/asia.202400112
  • Journal Name: Chemistry - An Asian Journal
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Applied Science & Technology Source, Chemical Abstracts Core, Chimica, Compendex, EMBASE, MEDLINE
  • Keywords: Bipyrimidine, Chirality, Molecular organisation, Nonlinear Optic, Thin Films
  • Yıldız Technical University Affiliated: Yes


An original series of bipyrimidine-based chromophores featuring alkoxystyryl donor groups bearing short chiral (S)-2-methylbutyl chains in positions 4, 3,4 and 3,5, connected to electron-accepting 2,2-bipyrimidine rings, has been developed. Their linear and non-linear optical properties were studied using a variety of techniques, including one- and two-photon absorption spectroscopy, fluorescence measurements, as well as Hyper-Rayleigh scattering to determine the first hyperpolarizabilities. Their electronic and geometrical properties were rationalized by TD-DFT calculations. The thermal properties of the compounds were also investigated by a combination of polarized light optical microscopy, differential scanning calorimetry measurements and small-angle X-ray scattering experiments. The derivatives were found not to have mesomorphic properties, but to exhibit melting temperatures or cold crystallization behavior that enabled the isolation of well-organized thin films. The nonlinear optical properties of amorphous or crystalline thin films were studied by wide-field second harmonic generation and multiphoton fluorescence imaging, confirming that non-centrosymmetric crystal organization enables strong second and third harmonic generation. This new series confirms that our strategy of functionalizing 3D organic octupoles with short chiral chains to generate non-centrosymmetric organized thin films enables the development of highly second order nonlinear optical active materials without the use of corona-poling or tedious deposition techniques.