Enhanced nonlinear optical properties and thermal stability of donor-acceptor substituted oligothiophenes

Abstract Linear and nonlinear optical properties of a series of novel donor-acceptor substituted α-oligothiophenes were investigated by means of electrooptical absorption measurements (EOAM) and electric field induced second harmonic generation (EFISH). The second-order polarizabilities β(−2ω; ω, ω) were related to dipole changes Δμ ag and transition dipoles μ ag associated with low-lying charge-transfer (CT) excitations by using the perturbational two-level approximation. Systematic variation of the donor and acceptor groups led to compounds with exceptional nonlinearity and thermal stability. Too strong donor/acceptor pairs, however, yielded structures in the charge-resonance (CR) limit with small or vanishing Δμ ag and β .

[1]  V. P. Rao,et al.  Novel push-pull thiophenes for second order nonlinear optical applications , 1993 .

[2]  L. Brooker Absorption and Resonance in Dyes , 1942 .

[3]  V. P. Rao,et al.  Experimental studies of the second-order nonlinear optical response of a novel class of tricyanovinylated thiophene compounds , 1995 .

[4]  J. Oudar,et al.  Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment , 1977 .

[5]  V. P. Rao,et al.  Functionalized Fused Thiophenes: A New Class of Thermally Stable and Efficient Second-Order Nonlinear Optical Chromophores , 1994 .

[6]  Peter Krämer,et al.  Intramolecular charge transfer in elongated donor-acceptor conjugated polyenes , 1995 .

[7]  David J. Williams,et al.  Introduction to Nonlinear Optical Effects in Molecules and Polymers , 1991 .

[8]  D. Seyferth Houben-Weyl methoden der organischen chemie , 1978 .

[9]  David P. Shelton,et al.  Problems in the comparison of theoretical and experimental hyperpolarizabilities , 1992 .

[10]  J. Oudar,et al.  Optical nonlinearities of conjugated molecules. Stilbene derivatives and highly polar aromatic compounds , 1977 .

[11]  J. Murrell The theory of the electronic spectra of organic molecules , 1963 .

[12]  Peter Krämer,et al.  Second-order polarizability of donor-acceptor substituted oligothiophenes : substituent variation and conjugation length dependence , 1993 .

[13]  R. Wortmann,et al.  Electrooptical absorption measurements of phototautomerizing systems: S0 and S1 static polarizabilities of bipyridinediols , 1992 .

[14]  F. Effenberger,et al.  SYNTHESIS AND SOLVATOCHROMIC PROPERTIES OF DONOR-ACCEPTOR-SUBSTITUTED OLIGOTHIOPHENES , 1995 .

[15]  T. Suga,et al.  Intramolecular hydrogen bonding in hydroxy-keto-steroids. , 1972, Journal of the Chemical Society. Perkin transactions 1.

[16]  C. Bosshard,et al.  Organic Nonlinear Optical Materials , 2001, CLEO/Europe Conference on Lasers and Electro-Optics.

[17]  H. Mower,et al.  Cyanocarbon Chemistry. VI.1 Tricyanovinylamines , 1958 .

[18]  P. M. Lundquist,et al.  Organic Glasses: A New Class of Photorefractive Materials , 1996, Science.

[19]  Peter Krämer,et al.  Deviations from Kleinman symmetry of the second-order polarizability tensor in molecules with low-lying perpendicular electronic bands , 1993 .

[20]  Joseph Zyss,et al.  Nonlinear optical properties of organic molecules and crystals , 1987 .

[21]  G. T. Phillips,et al.  The absorption spectra and synthesis of some 2,2′-bithienyl derivatives , 1967 .

[22]  P. Cahill,et al.  Anomalous-dispersion phase-matched second-harmonic generation. , 1989, Optics letters.

[23]  P. N. Butcher,et al.  The Elements of Nonlinear Optics , 1990 .

[24]  R. D. Schuetz,et al.  The Preparation and Properties of a Few ι-(N,N-Dialkylamino)-alkyl-2-thienyl Sulfide Hydrochlorides and 2-Thiophenethiol , 1953 .

[25]  Peter Krämer,et al.  Dipolar NLO‐phores with large off‐diagonal components of the second‐order polarizability tensor , 1997 .

[26]  R. Wortmann,et al.  Excited state dipole moments and polarizabilities of centrosymmetric and dimeric molecules. I. Model study of a bichromophoric molecule , 1988 .

[27]  D. Beratan,et al.  Approaches for Optimizing the First Electronic Hyperpolarizability of Conjugated Organic Molecules , 1991, Science.

[28]  Robert J. Twieg,et al.  DESIGN OF OPTIMIZED PHOTOREFRACTIVE POLYMERS : A NOVEL CLASS OF CHROMOPHORES , 1996 .

[29]  B. F. Levine,et al.  Second and third order hyperpolarizabilities of organic molecules , 1975 .