Metal-Free Phthalocyanines Bearing Eight Alkylsulfonyl Substituents: Design, Synthesis, Electronic Structure, and Mesomorphism of New Electron-Deficient Mesogens

Tylleman, B.; Gbabode, G.; Amato, C.; Buess-Herman, Claudine; Lemaur, Vincent; Cornil, Jérôme; Gomez Aspe, R.; Geerts, Yves; Sergeyev, Sergey

doi:10.1021/cm900383c

Article (Scientific journals)

Metal-Free Phthalocyanines Bearing Eight Alkylsulfonyl Substituents: Design, Synthesis, Electronic Structure, and Mesomorphism of New Electron-Deficient Mesogens

Tylleman, B.; Gbabode, G.; Amato, C. et al.

2009 • In Chemistry of Materials, 21 (13), p. 2789-2797

Peer Reviewed verified by ORBi

Permalink
https://hdl.handle.net/20.500.12907/22296

DOI
10.1021/cm900383c

Files (1)Send to Details Statistics Bibliography Similar publications

Files

Full Text

cmn401.pdf

Author postprint (4.7 MB)

Request a copy

All documents in ORBi UMONS are protected by a user license.

Send to

RIS BibTex APA Chicago Permalink X Linkedin

Details

Abstract :

[en] This paper describes the synthesis and physicochemical characterization of novel metal-free phthalocyanines Pc(SO2R)8, bearing eight peripheral alkylsulfonyl substituents. The key synthetic step is the efficient eightfold oxidation of sulfanyl (SR) into sulfonyl (SO2R) functions in the precursor Pc(SR)8. Quantum-chemical calculations show a considerable stabilization of the HOMO and LUMO levels of Pc(SO2R)8 as a result of the presence of the strongly electron-withdrawing groups, while the HOMO-LUMO gap remains nearly unaffected. The redox behavior and electronic spectra of Pc(SO2R)8 were investigated by cyclic voltammetry and electronic absorption spectroscopy, respectively, to confirm the theoretical predictions. Particularly noteworthy is the first reduction potential of -0.14 V vs the saturated calomel electrode (SCE), which falls within the empirically established air-stability window for n-type semiconductors. Supramolecular structures of mesophases of Pc(SO2R)8 and their synthetic precursors Pc(SR)8 were studied in detail with the aid of powder X-ray diffraction in combination with differential scanning calorimetry and polarized light optical microscopy. As it was demonstrated earlier for many different discotic mesogens, installation of either linear or swallow-tail branched peripheral alkyl substituents plays an important role in the formation of mesophases. However, an unusual behavior was found for the Pc(SO2R)8 series: swallow-tail alkyl chains resulted in higher order in columnar mesophases compared to the linear analogues.

Disciplines :

Chemistry
Physics

Author, co-author :

Tylleman, B.

Gbabode, G.

Amato, C.

Buess-Herman, Claudine

Lemaur, Vincent ; Université de Mons > Unités externes > Materia Nova ASBL

Cornil, Jérôme ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux

Gomez Aspe, R.

Geerts, Yves

Sergeyev, Sergey

Language :

English

Title :

Metal-Free Phthalocyanines Bearing Eight Alkylsulfonyl Substituents: Design, Synthesis, Electronic Structure, and Mesomorphism of New Electron-Deficient Mesogens

Publication date :

14 July 2009

Journal title :

Chemistry of Materials

ISSN :

0897-4756

Publisher :

American Chemical Society, United States - District of Columbia

Volume :

Issue :

Pages :

2789-2797

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 en ligne le 12 juin 2009

Available on ORBi UMONS :

since 10 June 2010

Statistics

Number of views

14 (0 by UMONS)

Number of downloads

0 (0 by UMONS)

More statistics

Scopus citations^®

Scopus citations^®
without self-citations

OpenCitations

Bibliography

Adam, D.; Schuhmacher, P.; Simmerer, J.; Haussling, L.; Siemensmeyer, K.; Etzbach, K. H.; Ringsdorf, H.; Haarer, D. Nature 1994, 371, 141.
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.; Bredas, J.-L.; Cornil, J. J. Am. Chem. Soc. 2004, 126, 3271.
Sergeyev, S.; Pisula, W.; Geerts, Y. H. Chem. Soc. Rev. 2007, 36, 1902.
Laschat, S.; Baro, A.; Steinke, N.; Giesselmann, F.; Haegele, C.; Scalia, G.; Judele, R.; Kapatsina, E.; Sauer, S.; Schreivogel, A.; Tosoni, M. Angew. Chem., Int. Ed. 2007, 46, 4832.
Kumar, S. Chem. Soc. Rev. 2006, 35, 83.
Watson, M. D.; Fechtenkötter, A.; Müllen, K. Chem. Rev. 2001, 101, 1267.
Wu, J.; Pisula, W.; Müllen, K. Chem. Rev. 2007, 107, 718.
Ohta, K.; Hasebe, H.; Ema, H.; Fujimoto, T.; Yamamoto, I. J. Chem. Soc., Chem. Commun. 1989, 1610.
Ohta, K.; Watanabe, T.; Fujimoto, T.; Yamamoto, I. J. Chem. Soc, Chem. Commun. 1989, 1611.
Nishida, J.; Naraso; Murai, S.; Fujiwara, E.; Tada, H.; Tomura, M.; Yamashita, Y. Org. Lett. 2004, 6, 2007.
Lehmann, M.; Kestemont, G.; Aspe, R. G.; Buess-Herman, C.; Koch, M. H. J.; Debije, M. G.; Piris, J.; de Haas, M. P.; Warman, J. M.; Watson, M. D.; Lemaur, V.; Cornil, J.; Geerts, Y. H.; Gearba, R.; Ivanov, D. A. Chem.-Eur. J. 2005, 11, 3349.
Foster, E. J.; Jones, R. B.; Lavigueur, C.; Williams, V. E. J. Am. Chem. Soc 2006, 128, 8569.
Nolde, F.; Pisula, W.; Müller, S.; Kohl, C.; Müllen, K. Chem. Mater. 2006, 18, 3715.
Saidi-Besbes, S.; Grelet, E.; Bock, H. Angew. Chem., Int. Ed. 2006, 45, 1783.
Cho, J.-Y.; Domercq, B.; Jones, S. C.; Yu, J.; Zhang, X.; An, Z.; Bishop, M.; Barlow, S.; Marder, S. R.; Kippelen, B. J. Mater. Chem. 2007, 17, 2642.
Bisoyi, H. K.; Kumar, S. New J. Chem. 2008, 32, 1974.
Jones, B. A.; Facchetti, A.; Wasielewski, M. R.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 15259.
Klauk, H.; Zschieschang, U.; Pflaum, J.; Halik, M. Nature 2007, 445, 745.
De Vusser, S.; Steudel, S.; Myny, K.; Genoe, J.; Heremans, P. Appl. Phys. Lett. 2006, 88, 162116.
Jung, T.; Yoo, B.; Wang, L.; Dodabalapur, A.; Jones, B. A.; Facchetti, A.; Wasielewski, M. R.; Marks, T. J. Appl. Phys. Lett. 2006, 88, 183102.
Gregory, P. J. Porphyrins Phthalocyanines 2000, 4, 432.
McKeown, N. B. Phthalocyanine Materials: Synthesis, Structure and Function; University Press: Cambridge, 1998; p 194.
Ali, H.; Van Lier, J. E. Chem. Rev. 1999, 99, 2379.
de la Torre, G.; Claessens, C. G.; Torres, T. Chem. Commun. 2007, 2000.
Iino, H.; Hanna, J.; Bushby, R. J.; Movaghar, B.; Whitaker, B. J.; Cook, M. J. Appl. Phys. Lett. 2005, 87, 132102.
Sergeyev, S.; Pouzet, E.; Debever, O.; Levin, J.; Gierschner, J.; Cornil, J.; Gomez-Aspe, R.; Geerts, Y. H. J. Mater. Chem. 2007, 17, 1777.
Sergeyev, S.; Debever, O.; Pouzet, E.; Geerts, Y. H. J. Mater. Chem. 2007, 17, 3002.
Tylleman, B.; Gomez-Aspe, R.; Gbabode, G.; Geerts, Y. H.; Sergeyev, S. Tetrahedron 2008, 64, 4155.
March, J. Advanced Organic Chemistry; Wiley and Sons: New York, 1985; p 242.
Ridley, J.; Zerner, M. Theor. Chim. Acta 1973, 32, 111.
Dela Escosura, A.; Martínez-Díaz, M.V.; Guldi, D. M.; Torres, T. J. Am. Chem. Soc. 2006, 128, 4112.
De la Torre, G.; Martinez-Diaz, M. V.; Ashton, P. R.; Torres, T. J. Org. Chem. 1998, 63, 8888.
Maya, E. M.; Garcia, C.; Garcia-Fmtos, E. M.; Vazquez, P.; Torres, T. J. Org. Chem. 2000, 65, 2733.
De La Escosura, A.; Martinez-Diaz, M. V.; Thordarson, P.; Rowan, A. E.; Nolte, R. J. M.; Torres, T. J. Am. Chem. Soc. 2003, 125, 12300.
de la Escosura, A.; Martinez-Diaz, M. V.; Barbera, J.; Torres, T. J. Org. Chem. 2008, 73, 1475.
del Rey, B.; Keller, U.; Torres, T.; Rojo, G.; Agulló- López, F.; Nonell, S.; Martí, C.; Brasselet, S.; Ledoux, I.; Zyss, J. J. Am. Chem. Soc. 1998, 120, 12808.
Tant, J.; Geerts, Y. H.; Lehmann, M.; de Cupere, V.; Zucchi, G.; Laursen, B. W.; Bjornholm, T.; Lemaur, V.; Marcq, V.; Burquel, A.; Hennebicq, E.; Gardebien, F.; Viville, P.; Beljonne, D.; Lazzaroni, R.; Cornil, J. J. Phys. Chem. B 2005, 109, 20315.
Ban, K. Z.; Nishizawa, K.; Ohta, K.; Shirai, H. J. Mater. Chem. 2000, 10, 1083.
Ban, K.; Nishizawa, K.; Ohta, K.; de Craats, A. M. V.; Warman, J. M.; Yamamoto, I.; Shirai, H. J. Mater. Chem. 2001, 11, 321.
Lux, A.; Rozenberg, G. G.; Petritsch, K.; Moratti, S. C.; Holmes, A. B.; Friend, R. H. Synth. Met. 1999, 102, 1527.
Carpino, L. A. J. Org. Chem. 1973, 38, 2600.
Gueugnot, S.; Alami, M.; Linstrumelle, G.; Mambu, L.; Petit, Y.; Larcheveque, M. Tetrahedron 1996, 52, 6635.
Schapman, F.; Youssef, B.; About-Jaudet, E.; Bunel, C. Eur. Polym. J. 2000, 36, 1865.
Wu, J.; Fechtenkoetter, A.; Gauss, J.; Watson, M. D.; Kastler, M.; Fechtenkötter, C.; Wagner, M.; Müllen, K. J. Am. Chem. Soc. 2004, 126, 11311.
Kastler, M.; Pisula, W.; Wasserfallen, D.; Pakula, T.; Müllen, K. J. Am. Chem. Soc. 2005, 127, 4286.
Swarts, J. C.; Langner, E. H. G.; Krokeide-Hove, N.; Cook, M. J. J. Mater. Chem. 2001, 11, 434.
González-Rodríguez, D.; Claessens, C. G.; Torres, T.; Liu, S.; Echegoyen, L.; Vila, N.; Nonell, S. Chem.-Eur. J. 2005, 11, 3881.
Lever, A. B. P.; Pickens, S. R.; Minor, P. C.; Licoccia, S.; Ramaswamy, B. S.; Magnell, K. J. Am. Chem. Soc. 1981, 103, 6800.
Wang, Z.; Kim, C.; Facchetti, A.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 13362.
Pisula, W.; Tomovic, Z.; El Hamaoui, B.; Watson, M. D.; Pakula, T.; Müllen, K. Adv. Funct. Mater. 2005, 15, 893.
Pisula, W.; Kastler, M.; Wasserfallen, D.; Mondeshki, M.; Piris, J.; Schnell, I.; Müllen, K. Chem. Mater. 2006, 18, 3634.
Collard, D. M.; Lillya, C. P. J. Am. Chem. Soc. 1991, 113, 8577.
Kumar, S.; Varshney, S. K. Angew. Chem., Int. Ed. 2000, 39, 3140.
Fechtenkötter, A.; Tchebotareva, N.; Watson, M.; Müllen, K. Tetrahedron 2001, 57, 3769.