[en] Two donor-bridge-acceptor compounds containing triphenylamine (TPA) donors and perylenemonoimide (PMI) acceptors have been studied by spectroscopic techniques and quantum chemical computation. Both systems have been observed to emit prompt and delayed fluorescence under certain conditions indicating that forward and reverse electron transfer (ET) processes can occur between the locally excited and the charge separated states. The experimental and computational results show that the TPA and PMI chromophores are better coupled by almost 50% in the meta isomers which undergo ET more readily than the para isomers. Quantum chemical calculations indicate that this unexpected situation is the result of a phenyl group on the side of the bridge being advantageously positioned in the meta isomers. This leads to more extensive delocalisation of the TPA HOMO into the bridge enhancing the total through bond electronic coupling between the TPA and PMI chromophores. The calculations also indicate a strong angle dependence of the total coupling in both isomers. The experimental results are discussed in the context of the high temperature limit of Marcus's theory of non-adiabatic ET.
Disciplines :
Chemistry Physics
Author, co-author :
Bell, T.D.M.
Stefan, A.
Lemaur, Vincent ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
A. C. Grimsdale K. Müllen The chemistry of organic nanomaterials Angew. Chem., Int. Ed. 2005 44 5592-5629.
J. Cremer P. Bäuerle Perylene-oligothiophene-perylene triads for photovoltaic applications Eur. J. Org. Chem. 2005 3715-3723.
B. K. Kaletas R. Dobrawa A. Sautter F. Würthner M. Zimine L. De Cola R. M. Williams Photoinduced Electron and Energy Transfer Processes in a Bichromophoric Pyrene-Perylene Bisimide System J. Phys. Chem. A 2004 108 1900-1909.
E. H. A. Beckers S. C. J. Meskers A. P. H. J. Schenning Z. Chen F. Würthner R. A. J. Janssen Charge Separation and Recombination in Photoexcited Oligo(p-phenylene vinylene): Perylene Bisimide Arrays Close to the Marcus Inverted Region J. Phys. Chem. A 2004 108 6933-6937.
F. Würthner A. Sautter C. Thalacker Substituted diazadibenzoperylenes: new functional building blocks for supramolecular chemistry Angew. Chem., Int. Ed. 2000 39 1243-1245.
B. Rybtchinski L. E. Sinks M. R. Wasielewski Combining Light-Harvesting and Charge Separation in a Self-Assembled Artificial Photosynthetic System Based on Perylenediimide Chromophores J. Am. Chem. Soc. 2004 126 12268-12269.
K. Tomizaki R. S. Loewe C. Kirmaier J. K. Schwartz J. L. Retsek D. F. Bocian D. Holten J. S. Lindsey Synthesis and photophysical properties of light-harvesting arrays comprised of a porphyrin bearing multiple perylene-monoimide accessory pigments J. Org. Chem. 2002 67 6519-6534.
R. S. Loewe K.-y. Tomizaki F. Chevalier J. S. Lindsey Synthesis of perylene-porphyrin dyads for light-harvesting studies J. Porphyrins Phthalocyanines 2002 6 626-642.
C. Jung B. K. Müller D. C. Lamb F. Nolde K. Müllen C. Bräuchle A New Photostable Terrylene Diimide Dye for Applications in Single Molecule Studies and Membrane Labeling J. Am. Chem. Soc. 2006 128 5283-5291.
F. C. De Schryver T. Vosch M. Cotlet M. Van der Auweraer K. Müllen J. Hofkens Energy Dissipation in Multichromophoric Single Dendrimers Acc. Chem. Res. 2005 38 514-522.
A. C. Grimsdale T. Vosch M. Lor M. Cotlet S. Habuchi J. Hofkens F. C. De Schryver K. Müllen Synthesis of and excited state processes in multichromophoric dendritic systems J. Lumin. 2005 111 239-253.
F. Stracke C. Blum S. Becker K. Müllen A. J. Meixner Two and multilevel spectral switching of single molecules in polystyrene at room temperature Chem. Phys. 2004 300 153-164.
A. Margineanu J. Hofkens M. Cotlet S. Habuchi A. Stefan J. Qu C. Kohl K. Müllen J. Vercammen Y. Engelborghs T. Gensch F. C. De Schryver Photophysics of a Water-Soluble Rylene Dye: Comparison with Other Fluorescent Molecules for Biological Applications J. Phys. Chem. B 2004 108 12242-12251.
A. Herrmann T. Weil V. Sinigersky U.-M. Wiesler T. Vosch J. Hofkens F. C. De Schryver K. Müllen Polyphenylene dendrimers with perylene diimide as a luminescent core Chem.–Eur. J. 2001 7 4844-4853.
F. Kulzer F. Koberling T. Christ A. Mews T. Basché Terrylene in p-terphenyl: single-molecule experiments at room temperature Chem. Phys. 1999 247 23-34.
M. W. Holman D. M. Adams Using single-molecule fluorescence spectroscopy to study electron transfer ChemPhysChem 2004 5 1831-1836.
D. M. Adams L. Brus C. E. D. Chidsey S. Creager C. Creutz C. R. Kagan P. V. Kamat M. Lieberman S. Lindsay R. A. Marcus R. M. Metzger M. E. Michel-Beyerle J. R. Miller M. D. Newton D. R. Rolison O. Sankey K. S. Schanze J. Yardley X. Zhu Charge Transfer on the Nanoscale: Current Status J. Phys. Chem. B 2003 107 6668-6697.
R. Gronheid A. Stefan M. Cotlet J. Hofkens J. Qu K. Müllen M. Van der Auweraer J. W. Verhoeven F. C. De Schryver Reversible intramolecular electron transfer at the single-molecule level Angew. Chem., Int. Ed. 2003 42 4209-4214.
M. Cotlet S. Masuo G. Luo J. Hofkens M. van der Auweraer J. Verhoeven K. Müllen X. S. Xie F. De Schryver Probing conformational dynamics in single donor–acceptor synthetic molecules by means of photoinduced reversible electron transfer Proc. Natl. Acad. Sci. U. S. A. 2004 101 14343-14348.
M. Cotlet S. Masuo M. Lor E. Fron M. Van der Auweraer K. Müllen J. Hofkens F. De Schryver Probing the influence of O2 on photoinduced reversible electron transfer in perylene diimide-triphenylamine-based dendrimers by single-molecule spectroscopy Angew. Chem., Int. Ed. 2004 43 6116-6120.
T. D. M. Bell A. Stefan S. Masuo T. Vosch M. Lor M. Cotlet J. Hofkens S. Bernhardt K. Müllen M. van der Auweraer J. W. Verhoeven F. C. De Schryver Electron transfer at the single-molecule level in a triphenylamine-perylene imide molecule ChemPhysChem 2005 6 942-948.
M. Lor J. Thielemans L. Viaene M. Cotlet J. Hofkens T. Weil C. Hampel K. Müllen J. W. Verhoeven M. Van der Auweraer 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.
M. Lor S. Jordens G. De Belder G. Schweitzer E. Fron L. Viaene M. Cotlet T. Weil K. Müllen J. W. Verhoeven M. Van der Auweraer F. C. De Schryver Direct proof of electron transfer in a rigid first generation triphenylamine core dendrimer substituted with a peryleneimide acceptor Photochem. Photobiol. Sci. 2003 2 501-510.
K. Ohta G. L. Closs K. Morokuma N. J. Green Stereoelectronic effects in intramolecular long-distance electron transfer in radical anions as predicted by ab initio MO calculations J. Am. Chem. Soc. 1986 108 1319-1320.
P. Karafiloglou J.-P. Launay Electron Pair (De)Coupling in Aniline Radical Cation and Its Implications for Organic “Mixed Valence” Systems J. Phys. Chem. A 1998 102 8004-8012.
S. Anderson Phenylene ethynylene pentamers for organic electroluminescence Chem.–Eur. J. 2001 7 4706-4714.
M. Maus M. Cotlet J. Hofkens T. Gensch F. C. De Schryver J. Schaffer C. A. M. Seidel An Experimental Comparison of the Maximum Likelihood Estimation and Nonlinear Least-Squares Fluorescence Lifetime Analysis of Single Molecules Anal. Chem. 2001 73 2078-2086.
V. Lemaur M. Steel D. Beljonne J.-L. Bredas J. Cornil Photoinduced Charge Generation and Recombination Dynamics in Model Donor/Acceptor Pairs for Organic Solar Cell Applications: A Full Quantum-Chemical Treatment J. Am. Chem. Soc. 2005 127 6077-6086.
R. J. Cave M. D. Newton Generalization of the Mulliken–Hush treatment for the calculation of electron transfer matrix elements Chem. Phys. Lett. 1996 249 15-19.
J. Ridley M. Zerner Intermediate neglect of differential overlap (INDO) technique for spectroscopy. Pyrrole and the azines Theor. Chim. Acta 1973 32 111-134.
A. K. Rappe C. J. Casewit K. S. Colwell W. A. Goddard, III W. M. Skiff UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations J. Am. Chem. Soc. 1992 114 10024-10035.
R. A. Marcus Theory of electron-transfer reactions. VI. Unified treatment for homogeneous and electrode reactions J. Chem. Phys. 1965 43 679-701.
S. Bernhardt and K. Müllen, unpublished data.
T. Vosch M. Cotlet J. Hofkens K. Van Biest M. Lor K. Weston P. Tinnefeld M. Sauer L. Latterini K. Müllen F. C. De Schryver Probing Foerster Type Energy Pathways in a First Generation Rigid Dendrimer Bearing Two Perylene Imide Chromophores J. Phys. Chem. A 2003 107 6920-6931.
J. R. Lackowicz, Principles of Fluorescence Spectroscopy, Plenum Press, New York, 2nd edn, 1999.
D. V. O’Connor 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.
M. Liu S. Chakrabarti D. H. Waldeck A. M. Oliver M. N. Paddon-Row Pendant unit effect on electron tunneling in U-shaped molecules Chem. Phys. 2006 324 72-84.
M. Liu D. H. Waldeck A. M. Oliver N. J. Head M. N. Paddon-Row Observation of Dynamic Solvent Effect for Electron Tunneling in U-Shaped Molecules J. Am. Chem. Soc. 2004 126 10778-10786.
A. M. Napper N. J. Head A. M. Oliver M. J. Shephard M. N. Paddon-Row I. Read D. H. Waldeck Use of U-shaped Donor–Bridge–Acceptor Molecules To Study Electron Tunneling through Nonbonded Contacts J. Am. Chem. Soc. 2002 124 10171-10181.
A. M. Napper I. Read D. H. Waldeck N. J. Head A. M. Oliver M. N. Paddon-Row An Unequivocal Demonstration of the Importance of Nonbonded Contacts in the Electronic Coupling between Electron Donor and Acceptor Units of Donor–Bridge–Acceptor Molecules J. Am. Chem. Soc. 2000 122 5220-5221.
S.-Z. Lu X.-Y. Li W. Liu Electronic coupling matrix elements of U-shaped donor–bridge–acceptor molecules and influence of mediated benzene solvent Chem. Phys. Lett. 2005 414 71-75.
M. B. Zimmt D. H. Waldeck Exposing Solvent’s Roles in Electron Transfer Reactions: Tunneling Pathway and Solvation J. Phys. Chem. A 2003 107 3580-3597.
A. M. Napper I. Read R. Kaplan M. B. Zimmt D. H. Waldeck Solvent Mediated Superexchange in a C-Clamp Shaped Donor–Bridge–Acceptor Molecule: The Correlation between Solvent Electron Affinity and Electronic Coupling J. Phys. Chem. A 2002 106 5288-5296.
I. Read A. Napper R. Kaplan M. B. Zimmt D. H. Waldeck Solvent-Mediated Electronic Coupling: The Role of Solvent Placement J. Am. Chem. Soc. 1999 121 10976-10986.
N. R. Lokan M. N. Paddon-Row M. Koeberg J. W. Verhoeven Solvent-Mediated Intramolecular Electron Transfer in U-Shaped Systems with Different “Bite Sizes” J. Am. Chem. Soc. 2000 122 5075-5081.
R. A. Marcus H. Eyring Chemical and electrochemical electron-transfer theory Annu. Rev. Phys. Chem. 1964 15 155-196.
R. A. Marcus N. Sutin Electron transfers in chemistry and biology Biochim. Biophys. Acta 1985 811 265-322.
A. Weller Photoinduced electron transfer in solution: exciplex and radical ion pair formation free enthalpies and their solvent dependence Z. Phys. Chem. 1982 133 93-98.
D. V. Matyushov G. A. Voth A perturbation theory for solvation thermodynamics: Dipolar-quadrupolar liquids J. Chem. Phys. 1999 111 3630-3638.