[en] The kinetics of photoinduced charge transfer reactions in covalently linked donor-acceptor molecules often undergoes dramatic changes when these molecules self-assemble from a molecular dissolved state into a nanoaggregate. Frequently, the origin of these changes is only partially understood. In this paper, we describe the intermolecular spatial organization of three homologous arrays, consisting of a central perylene bisimide (PERY) acceptor moiety and two oligo(p-phenylene vinylene) (OPV) donor units, in nanoaggregates and identify both face-to-face (H-type) and slipped (J-type) stacking of the OPV and PERY chromophores. For the J-type aggregates, short intermolecular OPV-PERY distances are created that give rise to a charge-transfer absorption band. The proximity of the donor and acceptor groups in the J-type aggregates enables a highly efficient photoinduced charge separation with a rate (kcs > 1012 s-1) that significantly exceeds the rate of the intramolecular charge transfer of the same compounds when molecularly dissolved, even in the most polar media. In the H-type aggregates, on the other hand, the intermolecular OPV-PERY distance is not reduced compared to the intramolecular separation, and hence, the rates of the electron transfer reactions are not significantly affected compared to the molecular dissolved state. Similar to the forward electron transfer, the kinetics of the charge recombination in the aggregated state can be understood by considering the different interchromophoric distances that occur in the H- and J-type aggregates. These results provide the first consistent rationalization of the remarkable differences that are observed for photoinduced charge-transfer reactions of donor-acceptor compounds in molecularly dissolved versus aggregated states.
Disciplines :
Chemistry Physics
Author, co-author :
Beckers, E.H.A.
Meskers, S.C.J.
Schenning, A.P.H.J.
Chen, Z.
Würthner, F.
Marsal, Philippe
Beljonne, David ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
Advances in Chemical Physics; Jortner, J., Bixon, M., Ed.; Wiley-Interscience: New York, 1999; Vols. 106 and 107.
Electron Transfer in Chemistry; Balzani, V., Ed.; Wiley-VCH: Weinheim, 2001; Vols. 1-5
Gust, D.; Moore, T. A.; Moore, A. L. Acc. Chem. Res. 1993, 26, 198-205.
Gust, D.; Moore, T. A.; Moore, A. L. Acc. Chem. Res. 2001, 34, 40-48.
Paddon-Row, M. N. Acc. Chem. Res. 1994, 27, 18-25.
Guldi, D. M. Chem. Soc. Rev. 2002, 31, 22-36.
Van der Boom, T.; Hayes, R. T.; Zhao, Y.; Bushard, P. J.; Weiss, E. A.; Wasielewski, M. R. J. Am. Chem. Soc. 2002, 124, 9582-9590.
Van Hal, P. A.; Meskers, S. C. J.; Janssen, R. A. J. Appl. Phys. A 2004, 79, 41-46.
Fujitsuka, M.; Masuhara, A.; Kasai, H.; Oikawa, H.; Nakanishi, H.; Ito, O.; Yamashiro, T.; Aso, Y.; Otsubo, T. J. Phys. Chem. B 2001, 105, 9930-9934.
Fuller, M. J.; Sinks, L. E.; Rybtchinski, B.; Giaimo, J. M.; Li, X.; Wasielewski, M. R. J. Phys. Chem. A 2005, 109, 970-975.
Rybtchinski, B.; Sinks, L. E.; Wasielewski, M. R. J. Am. Chem. Soc. 2004, 126, 12268-12269.
Wurthner, F.; Chen, Z.; Hoeben, F. J. M.; Osswald, P.; You, C.-C.; Jonkheijm, P.; van Herrikhuyzen, J.; Schenning, A. P. H. J.; van der Schoot, P. P. A. M.; Meijer, E. W.; Beckers, E. H. A.; Meskers, S. C. J.; Janssen, R. A. J. J. Am. Chem. Soc. 2004, 126, 10611-10618.
Peeters, E.; Van Hal, P. A.; Meskers, S. C. J.; Janssen, R. A. J.; Meijer, E. W. Chem.-Eur. J. 2002, 8, 4470-4474.
Neuteboom, E. E.; Meskers, S. C. J.; Van Hal, P. A.; van Duren, S. K. J.; Meijer, E. W.; Janssen, R. A. J.; Dupin, H.; Pourtois, G.; Cornil, J.; Lazzaroni, R.; Brédas, J.-L.; Beljonne, D. J. Am. Chem. Soc. 2003, 125, 8625-8638.
Beckers, E. H. A.; Meskers, S. C. J.; Schenning, A. P. H. J.; Chen, Z.; Würthner, F.; Janssen, R. A. J. J. Phys. Chem. A 2004, 108, 6933-6937.
Ramos, A. M.; Beckers, E. H. A.; Offermans, T.; Meskers, S. C. J.; Janssen, R. A. J. J. Phys. Chem. A 2004, 108, 8201-8211.
Ramos, A. M.; Meskers, S. C. J.; Beckers, E. H. A.; Prince, R. B.; Brunsveld, L.; Janssen, R. A. J. J. Am. Chem. Soc. 2004, 126, 9630-9644.
Schenning, A. P. H. J.; van Herrikhuyzen, J.; Jonkheijm, P.; Chen, Z.; Würthner, F.; Meijer, E. W. J. Am. Chem. Soc. 2002, 124, 10252-10253.
Neuteboom, E. E.; Van Hal, P. A.; Janssen, R. A. J. Chem.-Eur. J. 2004, 10, 3907-3918.
Herz, L. M.; Daniel, C.; Silva, C.; Hoeben, F. J. M.; Schenning, A. P. H. J.; Meijer, E. W.; Friend, R. H.; Phillips, R. T. Phys. Rev. B 2003, 68, 045203/1-045203/7.
Hoeben, F. J. M.; Herz, L. M.; Daniel, C.; Jonkheijm, P.; Schenning, A. P. H. J.; Silva, C.; Meskers, S. C. J.; Beljonne, D.; Phillips, R. T.; Friend, R. H.; Meijer, E. W. Angew. Chem., Int. Ed. 2004, 43, 1976-1979.
Herz, L. M.; Silva, C.; Friend, R. H.; Phillips, R. T.; Setayesh, S.; Becker, S.; Marsitsky, D.; Müllen, K. Phys Rev. B 2001, 64, 195203/1-195203/9.
Li, X.; Sinks, L. E.; Rybtchinski, B.; Wasielewski, M. R. J. Am. Chem. Soc. 2004, 126, 10810-10811.
Hofkens, J.; Vosch, T.; Maus, M.; Kohn, F.; Cotlet, M.; Weil, T.; Herrmann, A.; Müllen, K.; De Schryver, F. C. Chem. Phys. Lett. 2001, 333, 255-263.
Chen, Z.; Debije, M. G.; Debaerdemaeker, T.; Osswald, P.; Würthner, F. ChemPhysChem 2004, 5, 137-140.
Leroy-Lhez, S.; Baffreau, J.; Perrin, L.; Levillain, E.; Allain, M.; Blesa, M.-J.; Hudhomme, P. J. Org. Chem. 2005, 70, 6313-6320.
Tributsch, H.; Pohlmann, L. Science 1998, 279, 1891-1895.
Struijk, C. W.; Sieval, A. B.; Dakhorst, J. E. J.; van Dijk, M.; Kimkes, P.; Koehorst, R. B. M.; Donker, H.; Schaafsma, T. J.; Picken, S. J.; van de Craats, A. M.; Warman, J. M.; Zuilhof, H.; Sudhölter, E. J. R. J. Am. Chem. Soc. 2000, 122, 11057-11066.
Schmidt-Mende, L.; Fechtenkotter, A.; Müllen, K.; Moons, E.; Friend, R. H.; MacKenzie, J. D. Science 2001, 293, 1119-1122.
Hudson, S. D.; Jung, H. T.; Percec, V.; Cho, W. D.; Johansson, G.; Ungar, G.; Balagurusamy, V. S. K. Science 1997, 278, 449-452.
Apperloo, J. J.; Janssen, R. A. J.; Malenfant, P. R. L.; Fréchet, J. M. J. J. Am. Chem. Soc. 2001, 125, 6916-6924.
Percec, V.; Glodde, M.; Bera, T. K.; Miura, Y.; Shiyanovskaya, I.; Singer, K. D.; Balagurusamy, V. S. K.; Heiney, P. A.; Schnell, I.; Rapp, A.; Spiess, H. W.; Hudson, S. D.; Duan, H. Nature 2002, 419, 384-387.
Hoeben, F. J. M.; Jonkheijm, P.; Meijer, E. W.; Schenning, A. P. H. J. Chem. Rev. 2005, 105, 1491-1546.
Kasha, M. Rad. Res. 1963, 20, 55-70.
Würthner, F.; Thalacker, C.; Diele, S.; Tschierske, C. Chem. Eur. J. 2001, 7, 2245-2253.
Weigang, O. E. J. Chem. Phys. 1960, 33, 892-899.
Sadrai, M.; Bird, G. R.; Potenza, J. A.; Schugar, H. J. Acta Crystallogr. C 1990, C46, 637-640.
Van Herrikhuyzen, J.; Syamakumari, A.; Schenning, A. P. H. J.; Meijer, E. W. J. Am. Chem. Soc. 2004, 126, 10121-10127.
For aggregates of 3, the CT band is at 740 nm (1.68 eV), while the CT band in 7 is found at 640 nm (1.94 eV). In a first approximation, the difference in the energy of the CT bands (0.26 eV) scales with the difference between reduction potentials of the acceptor units (0.22 eV). This allows one to predict that the CT absorption in aggregates of 1 should be ∼0.15 eV above that of 7, i.e., at ∼2.1 eV or 590 nm, which overlaps with the normal absorption of aggregate.
Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902-3909.
Leclère, Ph.; Hennebicq, E.; Calderone, A.; Brocorens, P.; Grimsdale, A. C.; Müllen, K.; Brédas, J. L.; Lazzaroni, R. Prog. Polym. Sci. 2003, 28, 55-81.
Weller, A. Z. Phys. Chem. 1982, 133, 93-8.
In this equations Eox(D) and Ered(A) are the oxidation and reduction potentials of the donor and acceptor molecules or moieties measured in a solvent with relative permittivity εref; E(S1) is the energy of the excited state from which the electron transfer occurs and Rcc is the center-to-center distance of the positive and negative charges in the charge-separated state. The radii of the positive and negative ions are given by r+ and r-, εs is the relative permittivity of the solvent, -e is the electron charge, and ε0 is the vacuum permittivity.
Marcus, R. A. Rev. Mod. Phys. 1993, 65, 599-610.
It should be noted here that differences in rate constants for the charge separation and recombination rates between the three studied compounds in the same solvent cannot be directly related to the supramolecular structure. The observed differences originate from the different acceptor strength induced by the substituents on the bay position of the perylene bisimide moiety.
Lemaur, V.; Steel, M.; Beljonne, D.; Brédas, J.-L.; Cornil, J. J. Am. Chem. Soc. 2005, 127, 6077-6086.
Lokey, R. S.; Iverson, B. L. Nature 1995, 375, 303-305.
Nguyen, J. Q.; Iverson, B. L. J. Am. Chem. Soc. 1999, 121, 2639-2640.
Zych, A. J.; Iverson, B. L. J. Am. Chem. Soc. 2000, 122, 8898-8909.
Ghosh, S.; Ramakrishnan, S. Macromolecules 2005, 38, 676-686.
Rybtchinski, B.; Sinks, L. E.; Wasielewski, M. R. J. Phys. Chem. A 2004, 108, 7497-7505.
Piotrowiak, P. Chem. Soc. Rev. 1999, 28, 143-150.
Schenning, A. P. H. J.; Jonkheijm, P.; Peeters, E.; Meijer, E. W. J. Am. Chem. Soc. 2001, 123, 409-416.
Peeters, E.; Ramos, A. M.; Meskers, S. C. J.; Janssen, R. A. J. J. Chem. Phys. 2000, 112, 9445-9454.
Demmig, S.; Langhals, H. Chem. Ber. 1988, 121, 225-230.
