0000000000073649
AUTHOR
Sonja Lebus
Large Quadratic Hyperpolarizabilities with Donor–Acceptor Polyenes Exhibiting Optimum Bond Length Alternation: Correlation Between Structure and Hyperpolarizability
Donor-acceptor polyenes of various lengths, and that combine aro- matic electron-donating moieties with powerful heterocyclic electron-withdraw- ing terminal groups, have been synthe- sized and characterized as efficient non- linear optical (NLO) chromophores. Their linear and nonlinear optical proper- ties have been investigated, and variations in these properties have been related to ground-state polarization (dipole p) and structure. In particular, unprecedented quadratic hyperpolarizabilities (p) have been achieved (up to p(0) =I500 x 10-30esu) by reduction of the bond- length alternation (BLA) in the polyenic chain. In each series of homologous com-
Spectral and electrooptical absorption and emission studies on internally hydrogen bonded benzoxazole `double' derivatives: 2,5-bis(benzoxazolyl)hydroquinone (BBHQ) and 3,6-bis(benzoxazolyl)pyrocatechol (BBPC). Single versus double proton transfer in the excited BBPC revisited
Abstract Ground and excited state dipole moments and polarizabilities of 2,5-bis(benzoxazolyl)hydroquinone (BBHQ) and 3,6-bis(benzoxazolyl)pyrocatechol (BBPC) are determined by means of electrooptical absorption and emission measurements. BBHQ is found to exhibit a small, while BBPC a large increase of the static polarizability in the Franck–Condon (FC) excited singlet state. The change of the dipole moments upon excitation to the FC state is zero within experimental error. However, both molecules show dipole moments in the fluorescent states of their phototautomers, of about 5 D, the major component being parallel to the long molecular axis. The experimental and theoretical results strongl…
Elongated push–pull diphenylpolyenes for nonlinear optics: molecular engineering of quadratic and cubic optical nonlinearities via tuning of intramolecular charge transfer
Abstract Push–pull polyenes are of particular interest for nonlinear optics (NLO) as well as model compounds for long-distance intramolecular charge transfer (ICT). In order to tune the ICT phenomenon and control the linear and nonlinear optical properties, we have synthesized and investigated several series of soluble push–pull diphenylpolyenes of increasing length and having various donor (D) and acceptor (A) end groups. Their linear and NLO properties have been studied by performing electro-optical absorption measurements (EOAM) and third-harmonic generation (THG) experiments in solution. Each push–pull molecule exhibits an intense ICT absorption band in the visible characterized by an i…
Intramolecular charge transfer in elongated donor-acceptor conjugated polyenes
Abstract Intramolecular charge transfer (ICT) has been investigated by electro-optical absorption measurements for two series of donor-acceptor polyenes of increasing length. Each molecule undergoes an increase in dipole moment upon photoexcitation. The experimental results indicate that lengthening the polyenic chain linking the donor and acceptor end groups results in a bathochromic shift of the ICT absorption band and induces marked increases of both excited state and transition dipoles, whereas the ground-state dipole is relatively unaffected. As a result, marked photoinduced changes in the dipole moment (up to 33 D) were obtained with the longest molecules (up to 27 A) leading to highl…
Intramolecular charge transfer and enhanced quadratic optical non-linearities in push pull polyenes
Abstract Push-pull polyenes, which have an electron-donating group (D) and an electron-withdrawing group (A) grafted on opposite ends of a conjugated polyenic chain, are of particular interest as model compounds for long-distance intramolecular charge transfer (ICT), as well as potent non-linear optical chromophores. Several series of push-pull polyenes of increasing length, combining aromatic donor moieties and various acceptor groups, have been prepared and studied. Their linear and non-linear optical properties have been investigated by performing electro-optical absorption measurements (FOAM) and electric-field-induced second-harmonic generation (EFISH) experiments in solution. Each mol…
Deviations from Kleinman symmetry of the second-order polarizability tensor in molecules with low-lying perpendicular electronic bands
Abstract 4-Nitroaniline (pNA) and 3,5-dinitro-aniline (3,5-DNA) were studied by electric field induced second harmonic generation (EFISH) and electrooptical absorption measurements (EOAM) in dioxane solution at T = 298 K. The measurements were carried out for two polarization conditions, the electric field vector of the linearly polarized incident light being parallel or perpendicular to the static electric field. The second-order polarizability tensor of pNA is confirmed to be Kleinman symmetric, while a strong deviation from index permutation symmetry is observed for 3,5-DNA. The latter is quantitatively interpreted by contributions of a low-lying electronic band with transition dipole pe…