Liquid Crystalline Metal-Free Phthalocyanines Designed for Charge and Exciton Transport

[en] A joint theoretical and experimental study of the electronic and structural properties of liquid crystalline metal-free phthalocyanines bearing a strong potential for charge and exciton transport has been performed. The synthesis of such compounds has been triggered by quantum chemical calculations showing that: (i) hole transport is favored in metal-free phthalocyanines by their extremely low reorganization energy (0.045 eV) and large electronic splittings; and (ii) the efficiency of energy transfer along the one-dimensional discotic stacks is weakly affected by rotational disorder due to the two-dimensional character of the molecules. We have synthesized two metal-free phthalocyanines with different branched aliphatic chains on the gram scale to allow for a full characterization of their solid-state properties. The two compounds self-organize in liquid crystalline mesophases, as evidenced by optical microscopy, differential scanning calorimetry, X-ray powder diffraction, and molecular dynamics simulations. They exhibit a columnar rectangular mesophase at room temperature and a columnar hexagonal mesophase at elevated temperature.

Disciplines :

Chemistry
Physics

Author, co-author :

Tant, J.

Geerts, Yves

Lehmann, M.

De Cupere, V.

Zucchi, G.

Laursen, B.W.

Björnholm, T.

Lemaur, Vincent ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux

Marcq, V.

Burquel, A.

More authors (6 more)

Language :

English

Title :

Liquid Crystalline Metal-Free Phthalocyanines Designed for Charge and Exciton Transport

Publication date :

03 November 2005

Journal title :

Journal of Physical Chemistry B

ISSN :

1520-6106

Publisher :

American Chemical Society, United States - District of Columbia

Volume :

109

Issue :

Pages :

20315-20323

Peer reviewed :

Peer Reviewed verified by ORBi

Research unit :

S817 - Chimie des matériaux nouveaux

Research institute :

R400 - Institut de Recherche en Science et Ingénierie des Matériaux

Commentary :

Publié le 8 octobre 2005

Available on ORBi UMONS :

since 10 June 2010

Statistics

Number of views

3 (0 by UMONS)

Number of downloads

0 (0 by UMONS)

More statistics

Scopus citations^®

101

Scopus citations^®
without self-citations

OpenCitations

Bibliography

Braun, A.; Tcherniac, J. Ber. Dtsch. Chem. Ges. 1907, 40, 2709-2714.
Herbst, W.; Hunger, K. In Industrial Organic Pigments: Production, Properties, Applications; Wiley-VCH: Weinheim, Germany, 1997.
McKeown, N. B. In Phthalocyanine Materials; Cambridge University Press: Cambridge, U.K., 1998.
Simon, J.; André, J.-J. In Molecular Semiconductors: Photoelectrical Properties and Solar Cells; Springer-Verlag: Berlin, 1985.
Wang, M.; Chen, H. Z.; Yang, S. L. J. Photochem. Photobiol., A 1990, 53, 437-441.
Piechocki, C.; Simon, J. J. Am. Chem. Soc. 1982, 104, 5245-5247.
(a) Hanack, M.; Lang, M. Adv. Mater. 1994, 5, 819-833.
(b) van Nostrum, C. F.; Nolte, R. J. M. Chem. Commun. 1996, 2385-2392.
Hatsusaka, K.; Ohta, K.; Yamamoto, I.; Shirai, H. J. Mater. Chem. 2001, 11, 423-433.
Warman, J. M.; van de Craats, A. M. Mol. Cryst. Liq. Cryst. 2003, 396, 41-72.
Blanzat, B.; Barthou, C.; Tercier, N.; André, J.-J.; Simon, J. J. Am. Chem. Soc. 1987, 109, 6193-6194.
Orti, E.; Brédas, J. L.; Clarisse, C. J. Chem. Phys. 1990, 92, 1228-1235.
Schmidt-Mende, L.; Fechtenkötter, A.; Müllen, K.; Moons, E.; Friend, R. H.; MacKenzie, J. D. Science 2001, 293, 1119-1122.
MacDonald, W. A. J. Mater. Chem. 2004, 14, 4-10.
Méry, S.; Haristoy, D.; Nicoud, J.-F.; Guillon, D.; Diele, S.; Monobe, H.; Shimizu, Y. J. Mater. Chem. 2002, 12, 37-41.
(a) Schouten, P. G.; Van der Pol, J. F.; Zwikker, J. W.; Drenth, W.; Picken, S. J. Mol. Cryst. Liq. Cryst. 1991, 195, 291-305.
(b) McKeown, N. B.; Painter, J. J. Mater. Chem. 1994, 4, 1153-1156.
(c) Brewis, M.; Clarkson, G. J.; Helliwell, M.; Holder, A. M.; McKeown, N. B. Chem-Eur. J. 2000, 6, 4630-4636.
Rager, C.; Schmid, G.; Hanack, M. Chem.-Eur. J. 1999, 5, 280-288
Marcus, R. A. Rev. Mod. Phys. 1993, 65, 599-610.
Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148-13168.
Lemaur, V.; da Silva Filho, D. A.; Coropceanu, V.; Lehmann, M.; Geerts, Y.; Piris, J.; Debije, M. G.; van de Craats, A. M.; Senthilkumar, K.; Siebbeles, L. D. A.; Warman, J. M.; Brédas, J. L.; Cornil, J. J. Am. Chem. Soc. 2004, 126, 3271-3279.
Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377.
Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
Amashukeli, X.; Winkler, J. R.; Gray, H. B.; Gruhn, N. E.; Lichtenberger, D. L. J. Phys. Chem. A 2002, 106, 7593-7598.
Gruhn, N. E.; da Silva Filho, D. A.; Bill, T. G.; Malagoli, M.; Coropceanu, V.; Kahn, A.; Brédas, J. L. J. Am. Chem. Soc. 2002, 124, 7918-7919.
Zerner, M. C.; Loew, G. H.; Kichner, R. F.; Mueller-Westerhoff, U. T. J. Am. Chem. Soc. 1980, 102, 589-599.
Brédas, J. L.; Beljonne, D.; Coropceanu, V.; Cornil, J. Chem. Rev. 2004, 104, 4971-5003.
Cornil, J.; Lemaur, V.; Calbert, J. P.; Brédas, J. L. Adv. Mater. 2002, 14, 726-729.
Pietro, W. J.; Marks, T. J.; Ratner, M. A. J. Am. Chem. Soc. 1985, 107, 5837-5852.
Binstead, R. A.; Reimers, J. R.; Hush, N. S. Chem. Phys. Lett. 2003, 378, 654-659.
Weber, P.; Guillon, D.; Skoulios, A. Liq. Cryst. 1991, 9, 369-382.
van de Craats, A. M. Charge Transport in Self-Assembling Discotic Liquid Crystalline Materials. Ph.D. Thesis, Delft University of Technology, 2000.
Förster, T. J. Chem. Soc., Discuss. Faraday Soc. 1959, 27, 7-12.
May, V.; Kühn, O. Charge and Energy Transfer Dynamics in Molecular Systems; Wiley-VCH: Weinheim, Germany, 2000.
Beljonne, D.; Cornil, J.; Silbey, R.; Millié, P.; Brédas, J. L. J. Chem. Phys. 2000, 112, 4749-4758.
(a) Orti, E.; Brédas, J. L.; Clarisse, G. J. Chem. Phys. 1990, 92, 1228-1235.
(b) Oddos-Marcel, L.; Madeore, F.; Bock, A.; Neher, D.; Ferencz, A.; Rengel, H.; Wegner, G.; Kryschi, C.; Trommsdorff, H. P. J. Phys. Chem. 1996, 100, 11850-11856.
Simon, J.; Bassoul, P. Phthalocyanine Based Liquid Crystals: Towards Submicronic Devices. In Phthalocyanines; Properties and Applications; Leznoff, C. C., Lever, A. B. P, Eds.; VCH: Weinheim, Germany, 1989.
Clarkson, G. J.; Hassan, B. M.; Maloney, D. R.; McKeown, N. B. Macromolecules 1996, 29, 1854-1856.
Görlach, B.; Dachtler, M.; Glaser, T.; Albert, K.; Hanack, M. Chem.-Eur. J. 2001, 7, 2459-2465.
Young, J. G.; Onyebuagu, W. J. Org. Chem. 1990, 55, 2155-2159.
Clarkson, G. J.; McKeown, N. B.; Treacher, K. E. J. Chem. Soc., Perkin Trans. 1 1995, 1817-1823.
Collings, P. J.; Hird, M. In Introduction to Liquid Crystals: Chemistry and Physics; Taylor & Francis: London, U.K., 1997.
Barberá, J.; Rakitin, O. A.; Blanca Ros, M.; Torroba, T. Angew. Chem., Int. Ed. 1998, 37, 296-299.
Suarez, M.; Lehn, J.-M.; Zimmerman, S. C.; Skoulios, A.; Heinrich, B. J. Am. Chem. Soc. 1998, 120, 9526-9532.
van der Pol, J. F.; Neeleman, E.; Zwikker, J. W.; Nolte, R. J. M.; Drenth, W.; Aerts, J.; Visser, R.; Picken, S. J. Liq. Cryst. 1989, 6, 557-592.
Levelut, A. M. J. Chim. Phys. 1983, 80, 149-161.
Sleven, J.; Cardinaels, T.; Binnemans, K.; Nelis, D.; Mullens, J.; Hinz-Huebner, D.; Meyer, G. Liq. Cryst. 2003, 30, 143-148.
Ivanov, D. A. Personal communication.
Because force fields generally fail in describing the correct geometry of conjugated backbones, we have also calculated the splittings when imposing to the phthalocyanine core the geometry optimized at the DFT level; similar numbers are obtained in both cases.
Ban, K.; Nishizawa, K.; Ohta, K.; Shirai, H. J. Mater. Chem. 2000, 10, 1083-1090.
Cornil, J.; dos Santos, D. A.; Crispin, X.; Silbey, R.; Brédas, J. L. J. Am. Chem. Soc. 1998, 120, 1289-1299.
Hoppe, H.; Sariciftci, N. S. J. Mater. Res. 2004, 19, 1924-1945.
Mayo, S. L.; Olafson, B. D.; Goddard, W. A. J. Phys. Chem. 1990, 94, 8897-8909.
Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A.; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024-10035.
Accelrys, formerly Molecular Simulations Inc., 9685 Scranton Road, San Diego, CA., 1997.