Skip to main content
Log in

Direct proof of electron transfer in a rigid first generation triphenyl amine core dendrimer substituted with a peryleneimide acceptor

  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

The combination of nanosecond transient absorption experiments and single photon timing experiments proved the occurrence of an electron transfer process in the triphenyl amine core dendrimer, N1P1, by demonstrating the presence of an ion-pair absorption for N1P1 in solvents of medium polarity. By means of femtosecond transient absorption measurements the rise time of this ion-pair absorption dominated by the radical anion absorption could be determined, resulting in a value of 180 ps in MeTHF and 138 ps in THF. Furthermore, in femtosecond fluorescence upconversion as well as in monochromatic femtosecond transient absorption, a few ps component was resolved which was assigned to a vibrational and solvent relaxation process of the locally excited singlet state of the peryleneimide.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. N. Osuka, T. Nagata, F. Kobayashi, R. P. Zhang, K. Maruyama, N. Mataga, T. Asahi, T. Ohno and K. Nozaki, Long-lived charge separated states from distance fixed triads consisting of zinc porphyrin, free base porphyrine, and pyromellitimide Chem. Phys. Lett. 1992 3/4 302–308

    Article  Google Scholar 

  2. G. L. Closs and J. R. Miller, Intramolecular long-distance electron transfer in organic molecules Science 1988 240 440–447

    Article  CAS  Google Scholar 

  3. M. R. Roest, J. W. Verhoeven, W. Schuddeboom, J. M. Warman, J. M. Lawson and M. N. Paddon-Row Solvent and distance dependent charge separation in rigid trichromophoric systems J. Am. Chem. Soc. 1996 118 1762–1768

    Article  CAS  Google Scholar 

  4. F. C. De Schryver, D. Declercq, S. Depaemelaere, E. Hermans, A. Onkelinx, J. W. Verhoeven and J. Gelan, Photophysics of linked donor-acceptor systems: through-space and through bond interactions J. Photochem. Photobiol., A 1994 82 171–179

    Article  Google Scholar 

  5. A. Harriman, F. Odobel and J.-P. Sauvage Multistep electron transfer between porphyrin modules assembled around a ruthenium center J. Am. Chem. Soc. 1995 117 9461–9472

    Article  CAS  Google Scholar 

  6. I. M. Dixon, J.-P. Collin, J.-P. Sauvage and L. Flamigni, Porphyrin dyads and triads assembled around iridium(iii)bis-terpyridine: photoinduced electron transfer processes Inorg. Chem. 2001 40 5507–5517

    Article  CAS  Google Scholar 

  7. T. Vosch, J. Hofkens, M. Cotlet, F. Köhn, H. Fujiwara, R. Gronheid, K. Van der Biest, K. T. Weil, A. Herrmann, K. Müllen, S. Mukamel, M. Van der Auweraer and F. C. De Schryver Influence of structural and rotational isomerism on the triplet blinking of individual dendrimer molecules Angew. Chem. Int. Ed. 2001 40 4643–4648

    Article  CAS  Google Scholar 

  8. M. Maus, S. Mitra, M. Lor, J. Hofkens, T. Weil, A. Herrmann, K. Müllen and F. C. De Schryver Intramolecular energy hopping in polyphenylene dendrimers with an increasing number of peryleneimide chromophores J. Phys. Chem. A 2001 105 3961–3966

    Article  CAS  Google Scholar 

  9. G. De Belder, G. Schweitzer, S. Jordens, M. Lor, S. Mitra, J. Hofkens, S. De Feyter, M. Van der Auweraer, A. Herrmann, T. Weil, K. Müllen and F. C. De Schryver Singlet-singlet annihilation in multichromophoric peryleneimide dendrimers determined by fluorescence upconversion ChemPhysChem 2001149–55

    Article  Google Scholar 

  10. G. De Belder, S. Jordens, M. Lor, G. Schweitzer, R. De, T. Weil, A. Herrmann, U.-M. Wiesler, K. Müllen and F. C. De Schryver Femtosecond fluorescence upconversion study of rigid dendrimers containing peryleneimide chromophores at the rim J. Photochem. Photobiol., A 2001 145 61–70

    Article  Google Scholar 

  11. M. Lor, R. De, S. Jordens, G. De Belder, G. Schweitzer, M. Cotlet, J. Hofkens, T. Weil, A. Herrmann, K. Müllen, M. Van der Auweraer and F. C. De Schryver Generation-dependent energy dissipation in rigid dendrimers studied by femtosecond to nanosecond time-resolved spectroscopy J. Phys. Chem. A 2002 106 2083–2090

    Article  CAS  Google Scholar 

  12. M. Maus, R. De, M. Lor, T. Weil, S. Mitra, U.-W. Wiesler, A. Herrmann, J. Hofkens, T. Vosch, K. Müllen and F. C. De Schryver Intramolecular energy hopping and energy trapping in polyphenylene dendrimers with multiple peryleneimide donor chromophores and a terryleneimide acceptor trap chromophore J. Am. Chem. Soc. 2001 123 7668–7676

    Article  CAS  Google Scholar 

  13. G. Schweitzer, R. Gronheid, S. Jordens, M. Lor, G. De Belder, T. Weil, E. Reuther, K. Müllen and F. C. De Schryver Intramolecular directional energy transfer processes in dendrimers containing perylene and terrylene chromophores, J. Phys. Chem. A, in press

  14. M. Thelakhat and H. W. Schmidt, Synthesis and properties of novel derivatives of 1,3,5-tris(diarylamino) benzenes for electroluminescent devices Adv. Mater. 1998 10 219–223

    Article  Google Scholar 

  15. J. Rommens, A. Vaes, M. Van der Auweraer, F. C. De Schryver, H. Bässler, H. Vestweber and J. Pommerehne, Dual electroluminescence of an aminosubstituted 1,3,5-triphenylbenzene J. Appl. Phys. 1998 84 4487–4494

    Article  CAS  Google Scholar 

  16. M. Lor, J. Thielemans, L. Viaene, M. Cotlet, J. Hofkens, T. Weil, C. Hampel, K. Müllen, J. W. Verhoeven, M. Van der Auweraer and F. C. De Schryver Photoinduced electron transfer in a rigid first generation triphenylamine core dendrimer substituted with a peryleneimide acceptor J. Am. Chem. Soc. 2002 124 9918–9925

    Article  CAS  Google Scholar 

  17. T. Weil, C. Hampel, D. Grebel-Koehler, E. Reuther and K. Müllen, Macromolecules, to be published

  18. U.-M. Wiesler, T. Weil and K. Müllen Nanosized polyphenylene dendrimers Top. Curr. Chem. 2001 212 1–40

    Article  CAS  Google Scholar 

  19. D. F. Eaton, Handbook of Organic Chemistry, ed. J. C. Scaiano, CRC Press, Boca Raton, 1989, vol. 1

  20. M. Maus, E. Rousseau, M. Cotlet, G. Schweitzer, J. Hofkens, M. Van der Auweraer, F. C. De Schryver and A. Krueger, New picosecond laser system for easy tunability over the whole ultraviolet/visible/near infrared wavelength range based on flexible harmonic generation and optical parametric oscillation Rev. Sci. Instrum. 2001 72 36–40

    Article  CAS  Google Scholar 

  21. Program developed in a cooperation between the Management of Technology Institute (Belarusian State University) and The Division of Photochemistry and Spectroscopy (University of Leuven)

  22. D. V. O’Connor and D. Philips, Time-Correlated Single Photon Counting, Academic Press, London, 1984

    Google Scholar 

  23. Y. Karni, S. Jordens, G. De Belder, G. Schweitzer, J. Hofkens, T. Gensch, M. Maus, F. C. De Schryver, A. Herrmann and K. Müllen Intramolecular evolution from a locally excited state to an excimer-like state in a multichromophoric dendrimer evidenced by a femtosecond fluorescence upconversion study Chem. Phys. Lett. 1999 310 73–78

    Article  CAS  Google Scholar 

  24. P. Van Haver, N. Helsen, S. Depaemelaere, M. Van der Auweraer and F. C. De Schryver The influence of solvent polarity on the nonradiative decay of exciplexes J. Am. Chem. Soc. 1991 113 6849–6857

    Article  Google Scholar 

  25. D. Meerschaut, PhD Thesis, kuleuven, 1993, ch. 4

  26. E. P. L. Hunter, M. G. Simic and B. D. Michael, Use of an optical multichannel analyzer for recording absorption spectra of short-lived transients Rev. Sci. Instrum. 1985 56 2199–2204

    Article  CAS  Google Scholar 

  27. G. Schweitzer, L. Xu, B. Craig and F. C. De Schryver A double OPA femtosecond laser system for transient absorption spectroscopy Opt. Commun. 1997 142 283–288

    Article  CAS  Google Scholar 

  28. J. B. Birks, Photophysics of Aromatic Molecules, Wiley-Interscience, London, 1970, pp. 301–305

    Google Scholar 

  29. M. Van der Auweraer, F. C. De Schryver and A. Gilbert, Influence of starting conformations on intramolecular exciplex formation in ω-phenyl-α-N,N-dimethylaminoalkanes J. Am. Chem. Soc. 1980 102 4007–4017

    Article  Google Scholar 

  30. H. Heitele, P. Finckh, S. Weeren, F. Pöllinger and M. E. Michel-Beyerle Solvent polarity effects on intramolecular electron transfer 1. Energetic aspects J. Phys. Chem. 1989 93 5173–5179

    Article  CAS  Google Scholar 

  31. D. V. O’Connor and W. R. Ware, Exciplex photophysics III. Kinetics of fluorescence quenching of a-cyanonaphthalene by dimethylcyclopentene-1,2 in hexane J. Am. Chem. Soc. 1976 98 4706–4711

    Article  Google Scholar 

  32. H. Heitele, F. Pöllinger, T. Häberle, M. E. Michel-Beyerle and H. A. Staab, Energy-gap and temperature dependence of photoinduced electron transfer in porphyrin-quinone cyclophanes J. Phys. Chem. 1994 98 7402–7410

    Article  CAS  Google Scholar 

  33. R. M. Stratt and M. Maroncelli, Nonreactive dynamics in solution: the emerging molecular view of solvation dynamics and vibrational relaxation J. Phys. Chem. 1996 100 12981–12996

    Article  CAS  Google Scholar 

  34. L. Reynolds, J. A. Gardecki, S. J. V. Frankland, M. L. Horng and M. Maroncelli, Dipole solvation in nondipolar solvents: experimental studies of reorganization energies and solvation dynamics J. Phys. Chem. 1996 100 10337–10354

    Article  CAS  Google Scholar 

  35. P. Changenet, P. Plaza, M. M. Martin and Y. H. Meyer, Role of intramolecular torsion and solvent dynamics in the charge-transfer kinetics in triphenylphosphine oxide derivatives and DMABN J. Phys. Chem. A 1997 101 8186–8194

    Article  CAS  Google Scholar 

  36. Y. Kimura, J. C. Alfano, P. K. Walhout and P. F. Barbara, Ultrafast transient absorption spectroscopy of the solvated electron in water J. Phys. Chem. 1994 98 3450–3458

    Article  CAS  Google Scholar 

  37. J. S. Baskin, L. Banares, S. Pedersen and A. H. Zewail, Femtosecond real-time probing of reactions 20. Dynamics of twisting, alignment, and IVR in the trans-stilbene isomerization reaction J. Phys. Chem. 1996 100 11920–11933

    Article  CAS  Google Scholar 

  38. D. J. Nesbitt and R. W. Field, Vibrational energy flow in highly excited molecules: role of intramolecular vibrational redistribution J. Phys. Chem. 1996 100 12735–12756

    Article  CAS  Google Scholar 

  39. D. Gosztola, M. P. Niemczyk, W. Svec, A. S. Lukas and M. R. Wasielewski, Excited doublet states of electrochemically generated aromatic imide and diimide radical anions J. Phys. Chem. A 2000 104 6545–6551

    Article  CAS  Google Scholar 

  40. T. Shida, Electronic Spectra of Radical ions, Elsevier, Amsterdam, 1988

    Google Scholar 

  41. J. Bonvoisin, J.-P. Launay, M. Van der Auweraer and F. C. De Schryver Organic mixed-valence systems: intervalence transition in partly oxidized aromatic polyamines. Electrochemical and optical studies J. Phys. Chem. 1994 98 5052–5057

    Article  CAS  Google Scholar 

  42. J. Gardecki, M. L. Horng, A. Papazyan and M. Maroncelli, Ultrafast measurements of the dynamics of solvation in polar and non-dipolar solvents J. Mol. Liq. 1995 65/66 49–57

    Article  CAS  Google Scholar 

  43. J. A. I. Oksanen, P. Martinsson, E. Akesson, P. H. Hynninen and V. Sundström Transient hole burning and solvation dynamics of chlorophyll b monomers in various solvent environments J. Phys. Chem. 1998 102 4328–4336

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Additional information

Dedicated to the memory of Nobel Laureate, Lord George Porter FRSC FRS OM.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Lor, M., Jordens, S., De Belder, G. et al. Direct proof of electron transfer in a rigid first generation triphenyl amine core dendrimer substituted with a peryleneimide acceptor. Photochem Photobiol Sci 2, 501–510 (2003). https://doi.org/10.1039/b212450e

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/b212450e

Navigation