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Title: Quadratic optical nonlinearities of N-methyl and N-aryl pyridinium salts
Authors: Coe, BJ ×
Harris, JA
Asselberghs, Inge
Wostyn, Kurt
Clays, Koen
Persoons, Andre
Brunschwig, BS
Coles, SJ
Gelbrich, T
Light, ME
Hursthouse, MB
Nakatani, K #
Issue Date: Jan-2003
Publisher: Wiley-v c h verlag gmbh
Series Title: Advanced functional materials vol:13 issue:5 pages:347-357
Abstract: Four series of dyes with dimethylamino electron donor groups and N-R-pyridinium (R = methyl Me, phenyl Ph, 2,4-dinitrophenyl 2,4-DNPh, or 2-pyrimidyl 2-Pym) electron acceptors are studied as their hexafluorophosphate salts. The intramolecular charge-transfer (ICT) energies (E-max) of these compounds decrease within each of the series in the order R = Me > Ph > 2,4-DNPh > 2-Pym, as the electron-accepting ability of the pyridinium ring increases. Hyper-Rayleigh scattering with femtosecond 1300 or 800 nm losers yields fluorescence-free first hyperpolarizabilities beta, and static first hyperpolarizabilities beta(0)[H] are obtained via the two-state model. Dipole moment changes Deltamu(12) for the ICT transitions obtained from Stark spectroscopy afford beta(0)[S] values by using beta(0) = 3Deltamu(12)(mu(12))(2)/2 (E-max)(2) (mu(12) = transition dipole moment). The beta(0)[S] data show that the combination of pyridyl N-arylation with conjugation extension affords large increases in beta(0). The beta(0)[H] data generally agree with this conclusion, but resonance effects may explain some apparent anomalies. X-ray structural studies on various salts reveal that the use of tosylate anions is not a generally applicable approach to engineering noncentrosymmetric structures of pyridinium salts. However, trans-N-phenyl-4-(4-dimethylaminophenyl-4-buta-1,3-dienyl)pyridinium hexafluorophosphate adopts the polar space group Cc, and shows a very large powder second harmonic generation efficiency from a 1907 nm laser; which is similar to that of the well-studied material trans-4'-(dimethylamino)-N-methyl-4-stilbazolium tosylate (DAST).
ISSN: 1616-301X
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

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