[en] A joint theoretical and experimental study is reported on the structure-polarizability relationship in a novel type of push-pull conjugated system which contains a spacer within the conjugated backbone. The chromo-phores are based on a dithienyl conjugation pathway, spaced by a keto group, and selectively end-capped by a donor and an acceptor. Four chromophores were synthesized, in which the strength of the acceptor group and the length of the conjugated path were varied. The electronic properties of two model compounds were studied theoretically by means of correlated quantum-chemical calculations. The degree of ground-state polarization was varied in the calculations by the application of an external electric field and varied experimentally by the modification of the dielectric constant of a binary mixture of solvents. The linear and nonlinear optical properties of the compounds (measured in solution by hyper-Rayleigh scattering) are discussed in detail.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Maertens, Christophe; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Dubois, Philippe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Boutton, C.; University of Leuven (KUL) > Center for Research on Molecular Electronics and Photonics > Laboratory for Chemical and Biological Dynamics
Persoons, A.; University of Leuven (KUL) > Center for Research on Molecular Electronics and Photonics > Laboratory for Chemical and Biological Dynamics
Kogej, T.; University of Mons-Hainaut (UMH) > Center for Research in Molecular Electronics and Photonics > Laboratory for Chemistry of Novel Materials
Brédas, Jean-Luc; University of Mons-Hainaut (UMH) > Center for Research in Molecular Electronics and Photonics > Laboratory for Chemistry of Novel Materials
Language :
English
Title :
Structure-second-order polarizability relationship in chromophores incorporating a spacer: a joint experimental and theoretical study
BELSPO - Service Public Fédéral de Programmation Politique scientifique FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture F.R.S.-FNRS - Fonds de la Recherche Scientifique IWT - Agentschap voor Innovatie door Wetenschap en Technologie IBM
a) Special issue on Optical Nonlinearities in Chemistry, Chem. Rev. 1994, 94;
b) Materials for Nonlinear Optics - Chemical Perpectives (Eds.: S. R. Marder, J. E. Sohn, G. D. Stucky), ACS Symp. Ser. 1991, 455;
b) Materials for Nonlinear Optics - Chemical Perpectives (Eds.: S. R. Marder, J. E. Sohn, G. D. Stucky), ACS Symp. Ser. 1991, 455;
Nonlinear Optical Properties of Organic Molecules and Crystals (Eds.: D. S. Chemla, J. Zyss), Academic Press, Orlando, 1987.
a) L.-T. Cheng, W. Tam, S. H. Stevenson, G. R. Meredith, G. Rikken, S. R. Marder, J. Phys. Chem. 1991, 95, 10631;
b) L.-T. Cheng, W. Tam, S. H. Stevenson, G. R. Meredith, G. Rikken, S. R. Marder, J. Phys. Chem. 1991, 95, 10643.
M. J. S. Dewar, A. J. Holder, Heterocycles 1989, 28, 1135.
a) V. P. Rao, A. K.-Y. Jen, Y. Cai, Chem. Commun. 1996, 1237;
b) K. Y. Wong, A. K.-Y. Jen, V. P. Rao, K. Drost, R. M. Mininni, Proc. SPIE 1992, 1775, 74 and references therein.
a) S. Gilmour, S. R. Marder, J. W. Perry, L.-T. Cheng, Adv. Mater. 1994, 6, 494;
b) A. K.-Y. Jen, Y. Cai, P. V. Bedworth, S. R. Marder, Adv. Mater. 1997, 9, 132.
M. Blenkle, P. Boldt, C. Bräuchle, W. Grahn, I. Ledoux, H. Nerenz, S. Stadler, J. Wichern, J. Zyss, J. Chem. Soc. Perkin Trans. 2 1996, 1377.
Chem. Eng. News 1996, 4 March, 22.
J. Zyss, in Conjugated Polymeric Materials: Opportunities in Electronics, Optoelectronics, and Molecular Electronics (Eds.: J. L. Brédas, R. R. Chance), NATO ASI Ser., Ser. E: Applied Sciences, Vol. 182, 1990, 451.
a) G. Mignani, M. Barzoukas, J. Zyss, G. Soula, F. Balegroune, D. Grandjean, D. Josse, Organometallics 1991, 10, 3660;
b) D. Hissink, P. F. Van Hutten, G. Hadziioannou, F. Van Bolhuis, J. Organomet. Chem. 1993, 454, 25.
J.-X. Zhang, P. Dubois, R. Jérôme, J. Chem. Soc. Perkin Trans. 2 1997, 1209.
T. Kogej, F. Meyers, S. R. Marder, R. Silbey, J. L. Brédas, Synth. Met. 1997, 55, 1141.
T. Kogej, R. Silbey, S. R. Marder, J. L. Brédas, unpublished results.
M. A. Kessler, O. S. Wolfbeis, Spectrochim. Acta 1991, 47A, 187.
a) J. Kawamata, K. Inoue, H. Kasatani, H. Terauchi, Jpn. J. Appl. Phys. 1992, 31, 254;
b) J. Kawamata, K. Inoue, T. Inabe, M. Kiguchi, M. Kato, Y. Taniguchi, Chem. Phys. Lett. 1996, 249, 29;
c) Y. Kitaoka, T. Sasaki, S. Nakai, Y. Goto, Appl. Phys. Lett. 1991, 59, 19;
d) Y. Goto, A. Hayashi, Y. Kimura, M. Nakayama, J. Cryst. Growth 1991, 108, 688.
F. Meyers, S. R. Marder, B. M. Pierce, J. L. Brédas, J. Am. Chem. Soc. 1994, 116, 10703.
J. A. Pople, D. L. Beveridge, P. A. Dobosh, J. Chem. Phys. 1967, 47, 2026.
J. Ridley, M. C. Zerner, Theor. Chim. Acta 1973, 32, 11.
a) Solvents and Solvent Effects in Organic Chemistry (Ed.: C. Reichardt) VCH, Weinheim, 1988;
b) C. J. F. Böttcher, Theory of Electric Polarization: Dielectrics in Static Fields, Elsevier, Amsterdam, 1973, 135;
c) A. Willetts, J. E. Rice, D. M. Burland, D. P. Shelton, J. Chem. Phys. 1992, 97, 7590.
B. J. Orr, J. F. Ward, Mol. Phys. 1971, 20, 513.
I. D. L. Albert, T. J. Marks, M. A. Ratner, J. Phys. Chem. 1996, 100, 9714.
S. R. Marder, C. B. Gorman, F. Meyers, J. W. Perry, G. Bourhill, J. L. Brédas, B. M. Pierce, Science 1994, 265, 632.
S. F. Cyvin, J. E. Rauch, J. C. Decius, J. Chem. Phys. 1965, 43, 4083.
C. Maertens, C. Detrembleur, P. Dubois, R. Jérôme, P.-A. Blanche, P. Lemaire, Chem. Mater. 1998, 10, 1010.
C. Maertens, J.-X. Zhang, P. Dubois, R. Jérôme, J. Chem. Soc. Perkin Trans. 2 1996, 713.
S. V. Tsukerman, L. A. Kutulya, V. F. Lavruskin, Zh. Obs. Khim. 1964, 34, 3597.
I. Cabrera, O. Althoff, H.-T. Man, H. N. Yoon, Adv. Mater. 1994, 6, 43.
a) W. Liptay, Angew. Chem. 1969, 81, 195; Angew. Chem. Int. Ed. Engl. 1969, 8, 177;
a) W. Liptay, Angew. Chem. 1969, 81, 195; Angew. Chem. Int. Ed. Engl. 1969, 8, 177;
b) C. N. R. Rao, S. Singh, V. P. Senthilnathan, Chem. Soc. Rev. 1976, 5, 297;
c) M. Stähelin, D. M. Burland, J. E. Rice, Chem. Phys. Lett. 1992.
L. Onsager, J. Am. Chem. Soc. 1936, 58, 1486.
E. McRae, J. Phys. Chem. 1957, 61, 562.
The maximum of absorption of 10-5 M solutions of 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio)phenolate or Reichardt's dye in DMSO/ toluene mixtures were determined by UV/Vis analysis. The use of the formula ENT = (28591/λmax(nm) - 30.7)/32.4 leads to the values of ENT given in Figure 4. For a review, see: C. Reichardt, Chem. Rev. 1994, 94, 2319.
E. Bosch, M. Rosés, J. Chem. Soc. Faraday Trans. 1992, 88, 3541.
J. F. Oudar, D. S. Chemla, Chem. Phys. 1977, 66, 2664; J. L. Oudar, J. Chem. Phys. 1977, 67, 446.
J. F. Oudar, D. S. Chemla, Chem. Phys. 1977, 66, 2664; J. L. Oudar, J. Chem. Phys. 1977, 67, 446.
E. Engler, P. Laszlo, J. Am. Chem. Soc. 1971, 93, 1318.
O. B. Nagy, M. Wa Muanda, J. B. Nagy, J. Chem. Soc. Faraday Trans. 1 1978, 74, 2210.
R. Radeglia, S. Dähne, J. Mol. Structure 1970, 5, 399.
S. R. Marder, J. W. Perry, G. Bourhill, C. B. Gorman, B. G. Tiemann, K. Mansour, Science 1993, 261, 186.
M. Blanchard-Desce, V. Alain, P. V. Bedworth, S. R. Marder, A. Fort, C. Runser, M. Barzoukas, S. Lebus, R. Wortmann, Chem. Eur. J. 1997, 3, 1091.
J. O. Morley, R. M. Morley, R. Docherty, M. H. Charlton, J. Am. Chem. Soc. 1997, 119, 10192.
D. Ziessow, M. Carroll, Ber. Bunsenges, 1972, 76, 61.
See, for instance: E. Hendrickx, K. Clays, A. Persoons, C. Dehu, J. L. Brédas, J. Am. Chem. Soc. 1995, 117, 3547.
