π-Conjugated Organic Materials
J. Phys. Chem. B, Vol. 109, No. 11, 2005 4879
(11) Wang, D.; Gong, X.; Heeger, P. S.; Rininsland, F.; Bazan, G. C.;
Heeger, A. J. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 49.
(12) Gierschner, J.; Oelkrug, D. In Encyclopedia of Nanoscience and
Nanotechnology; Nalwa, H., Ed.; American Scientific Publisher: Stevenson
Ranch, CA, 2004; Vol. 8, p 219.
(13) Hulliger, J.; Ko¨nig, O.; Hoss, R. AdV. Mater. 1995, 7, 719.
(14) Bongiovanni, G.; Botta, C.; Bre´das, J. L.; Cornil, J.; Ferro, D. R.;
Mura, A.; Piaggi, A.; Tubino, R. Chem. Phys. Lett. 1997, 278, 146.
(15) Gierschner, J.; Lu¨er, L.; Oelkrug, D.; Musluoglu, E.; Behnisch, B.;
Hanack, M. AdV. Mater. 2000, 12, 757.
(16) Gierschner, J.; Lu¨er, L.; Oelkrug, D.; Musluoglu, E.; Behnisch, B.;
Hanack, M. Synth. Met. 2001, 121, 1695.
(17) Bongiovanni, G.; Botta, C.; Di Silvestro, G.; Loi, M. A.; Mura,
A.; Tubino, R. Chem. Phys. Lett. 2001, 345, 386.
(18) Loi, M. A.; Mura, A.; Bongiovanni, G.; Botta, C.; Di Silvestro,
G.; Tubino, R. Synth. Met. 2001, 121, 1299.
(19) Gierschner, J.; Egelhaaf, H.-J.; Mack, H.-G.; Oelkrug, D.; Mart´ınez
AÄ lvarez, R.; Hanack, M. Synth. Met. 2003, 137, 1449.
(20) Botta, C.; Destri, S.; Pasini, M.; Picouet, P.; Bongiovanni, G.; Mura,
A.; Uslenghi, M.; Di Silvestro, G.; Tubino, R. Synth. Met. 2003, 139, 791.
(21) Calzaferri, G.; Huber, S.; Maas, H.; Minkowski, C. Angew. Chem.,
Int. Ed. 2003, 42, 3732.
(22) Huber, S.; Calzaferri, G. Chem. Phys. Chem. 2004, 5, 239.
(23) Scaiano, J. C.; Garc´ıa, H. Acc. Chem. Res. 1999, 32, 783.
(24) Cardin, D. J. AdV. Mater. 2002, 14, 553.
(25) Nijegorodov, N. I.; Downey, W. S. J. Phys. Chem. 1994, 98, 5639.
(26) Stammel, C.; Fro¨lich, R.; Wolff, C.; Wenck, H.; de Meijere, A.;
Mattay, J. Eur. J. Org. Chem. 1942, 7, 1709.
(27) Ichimura, K.; Watanabe, S. J. Polym. Sci.: Polym. Chem. Ed. 1982,
20, 1419.
(28) Hamai, S.; Hirayama, F. J. Phys. Chem. 1983, 87, 83.
(29) Pogantsch, A.; Heimel, G.; Zojer, E. J. Chem. Phys. 2002, 117,
5921.
(30) Dierksen, M.; Grimme, S. J. Chem. Phys. 2004, 120, 3544.
(31) Stewart, J. J. P. J. Comput. Chem. 1989, 10, 209. Stewart, J. J. P.
J. Comput. Chem. 1989, 10, 221. Stewart, J. J. P. J. Comput. Chem. 1991,
12, 320.
(32) Gierschner, J.; Mack, H.-G.; Lu¨er, L.; Oelkurg, D. J. Chem. Phys.
2002, 116, 8596.
(33) Claudio, G. C.; Bittner, E. Chem. Phys. 2002, 276, 81.
(34) Stewart, J. J. P. In Encyclopedia of Computational Chemistry, von
Rague´ Schleyer, P., Ed.; Wiley: New York, 1998; Vol. 4, p 2579.
(35) Kwasniewski, S. P.; Claes, L.; Franc¸ois, J.-P.; Deleuze, M. S. J.
Chem. Phys. 2003, 118, 7823.
with the corresponding experimental spectra; they show that
the compounds display a moderate Stokes shift, which translates
into a large spectral overlap. These optical characteristics allow
for efficient energy transport between molecules in a head-to-
tail arrangement, as further supported by the fact that the
calculated hopping time is much faster than the radiative lifetime
(∼10-12 vs 10-9 s). The energy transfer rates can be further
improved by a proper choice of the substitution scheme. In view
of the overall good agreement observed between the experi-
mental and theoretical data, our quantum-chemical approach
could thus prove to be a cost-effective and reliable tool to design,
prior to chemical synthesis, new derivatives with optimized
properties.
Acknowledgment. The work in Mons has been supported
by the Belgian Federal Government “Service des Affaires
Scientifiques, Techniques et Culturelles (SSTC)”, in the frame-
work of the “Poˆle d′Attraction Interuniversitaire en Chimie
Supramole´culaire et Catalyse Supramole´culaire (PAI 5/3)”, the
Belgian National Fund for Scientific Research (FNRS/FRFC)
and by the European commission project NANOCHANNEL
(Grant No. HPRN-CT-2002-00323). The work at Georgia Tech
was partly supported by the National Science Foundation (Grants
DMR-0120967 and CHE-0343321) and the IBM Shared Uni-
versity Research Program. The work in Tu¨bingen was supported
by the “Fonds der Chemischen Industrie” and by the European
commission project NANOCHANNEL. H.-G. Mack thanks the
HLRS (Stuttgart, Germany) for access to substantial computer
time. R.M.-A. thanks the Alexander von Humboldt Stiftung
(Germany) for the reinvitation program (2002 and 2003) as well
as the “Beca Internacional Universidad ComplutensesFlores
Valles” (Spain). D.B. and J.C. are FNRS Research Associates.
The authors are very grateful to Prof. J. R. Reimers (University
of Sydney, Australia) for making available a version of his
recently developed DUSHIN program.
(36) Ampac 6.55, Semichem Inc., 7128 Summit, Shawnee, KS 66216,
1997.
(37) Hohenberg, P.; Kohn, W. Phys. ReV. B 1964, 136, 864.
(38) Kohn, W.; Sham, L. J. Phys. ReV. A 1965, 140, 1133.
(39) Koch, H.; Holthausen, M. C. A Chemist’s Guide to Density
Functional Theory; Wiley-VCH: Weinheim, Germany, 2000.
(40) Becke, A. D. Phys. ReV. A 1988, 38, 3098.
Supporting Information Available: Schemes 1 and 2
describing the synthetic routes toward compounds I-IX and
X-XI, respectively, and text giving the characterization data
for all compounds and related references. This material is
(41) Lee, C.; Yang, W.; Parr, R. G. Phys. ReV. B 1988, 37, 785.
(42) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
(43) Zerner, M. C.; Loew, G. H.; Kichner, R. F.; Mueller-Westerhoff,
U. T. J. Am. Chem. Soc. 1980, 102, 589. Zerner, M. C. In ReViews in
Computational Chemistry; Lipkowitz, K. W., Boyd, D. B., Eds.; VCH: New
York, 1994; Vol. 2, p 313.
References and Notes
(1) Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.;
Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, A. B. Nature (London)
1990, 347, 539. Friend, R. H.; Gymer, R. W.; Holmes, A. B.; Burroughes,
J. H.; Marks, R. N.; Taliani, C.; Bradley, D. D. C.; dos Santos, D. A.;
Bre´das, J. L.; Lo¨gdlund, M.; Salaneck, W. R. Nature (London) 1999, 397,
121.
(2) Gustafsson, H.; Cao, Y.; Treacy, G. M.; Klavetter, F.; Colaneri,
N.; Heeger, A. J. Nature (London) 1992, 357, 477.
(3) Spreitzer, H.; Becker, H.; Kluge, E.; Kreuder, W.; Schenk, H.;
Demandt, R.; Schoo, H. AdV. Mater. 1998, 10, 1340.
(4) Sariciftci, N. S.; Smilowitz, L.; Heeger, A. J.; Wudl, F. Science
1992, 258, 1474.
(5) Halls, J. J. M.; Walsh, C. A.; Greenham, N. C.; Marseglia, E. A.;
Friend, R. H.; Moratti, S. C.; Holmes, A. B. Nature (London) 1995, 376,
498.
(6) Brabec, C. J.; Sariciftci, N. S.; Hummelen, J. C. AdV. Funct. Mater.
2001, 11, 15.
(7) de Boer, B.; Stalmach, U.; Nijland, H.; Hadziioannou, G. AdV.
Mater. 2000, 12, 1581.
(8) Primary Photoexcitations in Conjugated Polymers: Molecular
Exciton Versus Semiconductor Band Model, Sariciftci, N. S., Ed.; World
Scientific Publishing: Singapore, 1997.
(9) Chen, L.; McBranch, D. W.; Wang, H. L.; Hegelson, R.; Wudl,
F.; Whitten, D. G. Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 12287.
(44) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.;
Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A.
D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi,
M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.;
Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick,
D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.;
Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi,
I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M.
W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon,
M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.10. Gaussian,
Inc.: Pittsburgh, PA, 1998.
(45) Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502.
(46) Martin, J. M. L.; El-Yazal, J.; Franc¸ois, J. P. J. Phys. Chem. 1996,
100, 15358.
(47) Halls, M. D.; Velkovski, J.; Schlegel, H. B. Theor. Chem. Acc.
2001, 105, 413.
(48) Thiel, W. AdV. Chem. Phys. 1996, 93, 703.
(49) Thiel, W. In Modern Methods and Algorithms of Quantum
Chemistry; Grotendorst, J., Ed.; John von Neumann Institute for Comput-
ing: Ju¨lich, Germany, 2000; p 235.
(50) Malagoli, M.; Coropceanu, V.; da Silva Filho, D. A.; Bre´das, J. L.
J. Chem. Phys. 2004, 120, 7490.
(10) McQuade, D. T.; Pullen, A. E.; Swager, T. M. Chem. ReV. 2000,
100, 2537.
(51) de Souza, M. M.; Rumbles, G.; Gould, I. R.; Amer, H.; Samuel, I.
D. W.; Moratti, S. C.; Holmes, A. B. Synth. Met. 2000, 111-112, 539.