ORGANIC
LETTERS
2006
Vol. 8, No. 7
1311-1314
Design and Synthesis of Bismacrocyclic
Hexaazatriphenylene Derivatives
Patrick Secondo and Fre´de´ric Fages*
GCOM2 UMR 6114 CNRS, UniVersite´ de la Me´diterrane´e, Faculte´ des Sciences de
Luminy, Case 901, 13288 Marseille Cedex 9, France
Received January 5, 2006
ABSTRACT
The first examples of bismacrocyclic derivatives of 2,3,6,7,10,11-hexaphenyl-1,4,5,8,9,12-hexaazatriphenylene are described. They are obtained
by the condensation of a linear trisbenzil precursor with hexaaminobenzene.
1,4,5,8,9,12-Hexaazatriphenylene (HAT) derivatives are disk-
shaped aromatic molecules that are receiving considerable
attention because of their easy synthetic accessibility,
diversity in peripheral functionality, electron deficiency,
coordination properties, and π-complexation ability. As a
result of such versatility, HATs were exploited in a variety
of applications, including discotic liquid crystals,1 self-
assembled organogels,2 n-type semiconducting3 and magnetic
materials,4 photoprobes and photoreagents of DNA,5 fluo-
rescent dyes,6 and octupolar nonlinear optical chromophores.7
The coordination chemistry of HATs is particularly rich.8
The appealing feature of these planar ligands is that they
provide a symmetrical array of three bidentate diimine
chelating sites, which renders them unique systems on which
to base the generation of solid-state infinite coordination
networks with intriguing topologies.8 HATs also allowed
building of discrete, low-nuclearity metal complexes with
well-defined nanoscale architectures.9 In light of these data,
it occurred to us that HAT derivatives in which the
phenanthroline-type subsites would be laterally bridged
through the ortho positions to the nitrogen atoms could
represent attractive building blocks for the generation of
ordered structures with controlled nuclearity and topography
and new topology.10 Indeed, such systems could provide
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(b) Arikainen, E. O.; Boden, N.; Bushby, R. J.; Lozman, O. R.; Vinter, J.
G.; Wood, A. Angew. Chem., Int. Ed. 2000, 39, 2333-2336. (c) Gearba,
R. I.; Lehman, M.; Levin, J.; Ivanov, D. A.; Koch, M. H. J.; Barbera´, J.;
Debije, M. G.; Piris, J.; Geerts, Y. H. AdV. Mater. 2003, 15, 1614-1618.
(2) Ishi-I, T.; Hirayama, T.; Murakami, K.; Tashiro, H.; Thiemann, T.;
Kubo, K.; Mori, A.; Yamasaki, S.; Akao, T.; Tsuboyama, A.; Mukaide, T.;
Ueno, K.; Mataka, S. Langmuir 2005, 21, 1261-1268.
(3) Kaafarani, B. R.; Kondo, T.; Yu, J.; Zhang, Q.; Dattilo, D.; Risko,
C.; Jones, S. C.; Barlow, S.; Domercq, B.; Amy, F.; Kahn, A.; Bre´das,
J.-L.; Kippelen, B.; Marder, S. R. J. Am. Chem. Soc. 2005, 127, 16358-
16359 and references therein.
(6) (a) Hirayama, T.; Yamasaki, S.; Ameku, H.; Ishi-i, T.; Thiemann,
T.; Mataka, S. Dyes Pigm. 2005, 67, 105-110. (b) Ishi-i, T.; Murakami,
K.; Imai, Y.; Mataka, S. Org. Lett. 2005, 7, 3175-3178.
(7) Cho, B. R.; Lee, S. K.; Kim, K. A.; Son, K. N.; Kang, T. I.; Jeon, S.
J. Tetrahedron Lett. 1998, 39, 9205-9208.
(8) Kitagawa, S.; Masaoka, S. Coord. Chem. ReV. 2003, 246, 73-88.
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Eur. J. 1999, 5, 102-112. (b) Masaoka, S.; Furukawa, S.; Chang, H.-C.;
Mizutani, T.; Kitagawa, S. Angew. Chem., Int. Ed. 2001, 40, 3817-3819.
(c) Latterini, L.; Pourtois, G.; Moucheron, C.; Lazzaroni, R.; Bre´das, J.-L.;
Kirsch-De Mesmaeker, A.; De Schryver, F. Chem.-Eur. J. 2000, 6, 1331-
1336.
(4) Marshall, S. R.; Rheingold, A. L.; Dawe, L. N.; Shum, W. W.;
Kitamura, C.; Miller, J. S. Inorg. Chem. 2002, 41, 3599-3601.
(5) Blasius, R.; Moucheron, C.; Kirsch-De Mesmaeker, A. Eur. J. Inorg.
Chem. 2004, 3071-3979.
(10) Frey, J. F.; Kraus, T.; Heitz, V.; Sauvage, J.-P. Chem. Commun.
2005, 5310-5312.
10.1021/ol060025o CCC: $33.50
© 2006 American Chemical Society
Published on Web 03/01/2006