TY - JOUR
T1 - Theoretical investigation of the second-order nonlinear optical properties of helical pyridine-pyrimidine oligomers
AU - Botek, Edith
AU - Castet, Frédéric
AU - Champagne, Benoît
PY - 2006/11/24
Y1 - 2006/11/24
N2 - The structure and second-order nonlinear optical properties of a series of helical pyridine-pyrimidine oligqmers recently synthesized by Barboiu and Lehn have been investigated theoretically by combining molecular mechanics and quantum chemistry approaches. In the absence of substituents, the hyper-Rayleigh scattering response (βHRS) and the projection of the first hyperpolarizability on the dipole moment (β) exhibit periodic variations with chain length, but these non-linear optical responses remain small. The first hyperpolarizabilities can, however, be enhanced by adding sub-stituents. The greatest enhancement is obtained by substituting the pyrimidine groups by donor groups. Moreover, regular distributions of the donor groups around the helices enable thedesign of supramolecular structures exhibiting dipolar, octupolar or Λ-shaped nonlinear optical characters, evident from the values of the depolarization ratios in hyper-Rayleigh scattering. Therefore this theoretical investigation demonstrates the potential of helical structures for the organization of chromophores in such a way that they exhibit large and specific second-order nonlinear optical responses.
AB - The structure and second-order nonlinear optical properties of a series of helical pyridine-pyrimidine oligqmers recently synthesized by Barboiu and Lehn have been investigated theoretically by combining molecular mechanics and quantum chemistry approaches. In the absence of substituents, the hyper-Rayleigh scattering response (βHRS) and the projection of the first hyperpolarizability on the dipole moment (β) exhibit periodic variations with chain length, but these non-linear optical responses remain small. The first hyperpolarizabilities can, however, be enhanced by adding sub-stituents. The greatest enhancement is obtained by substituting the pyrimidine groups by donor groups. Moreover, regular distributions of the donor groups around the helices enable thedesign of supramolecular structures exhibiting dipolar, octupolar or Λ-shaped nonlinear optical characters, evident from the values of the depolarization ratios in hyper-Rayleigh scattering. Therefore this theoretical investigation demonstrates the potential of helical structures for the organization of chromophores in such a way that they exhibit large and specific second-order nonlinear optical responses.
KW - Helical structures
KW - Nitrogen heterocycles
KW - Nonlinear optics
KW - Substituent effects
UR - http://www.scopus.com/inward/record.url?scp=33845223895&partnerID=8YFLogxK
U2 - 10.1002/chem.200600551
DO - 10.1002/chem.200600551
M3 - Article
AN - SCOPUS:33845223895
SN - 0947-6539
VL - 12
SP - 8687
EP - 8695
JO - Chemistry: A European Journal
JF - Chemistry: A European Journal
IS - 34
ER -