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Core-Modified Porphyrinoid: Syntheses and Characterization of
Disilahexaphyrinoid
Janusz Skonieczny,
Lechosław Latos-Grażyński, Ludmiła Szterenberg
Department of Chemistry
University of Wrocław
14 F. Joliot-Curie St., Wrocław 50 383, Poland
e-mail: LLG@wchuwr.pl
Formal replacement of two pyrrolic nitrogen atoms in the hexaphyrin ring with
heteroatoms (O, S, Se) yields a class of diheterohexaphyrins. [1]
In this work the
modified silole has been used as building block in the synthesis of silicon-containing
hexaphyrinoid.
1
A 2,5-bis(p-tolylhydroxymethyl)-3,4-diphenylosilole [2]
reacts with pyrrole
affording 16-silatripyrrane 1. Subsequent an acid catalyzed condensation of 1 and
aldehyde afforded a silole-containing hexaphyrin 2 which contains two built-in silole
units. This is the first example of a silole ring incorporated into the hexaphyrinoid
frame.
All compounds have been characterized using multinuclear NMR spectroscopy
and mass spectrometry. The density functional theory (DFT) has been applied to model
the molecular structure of disilahexaphyrinoid consistent with constrains imposed by
NOE experiments.
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[1] R. Misra, R. Kumar, T. K. Chandrashekar, B. S. Joshi, J. Org. Chem. 2007, 72, 1153.
[2] J. Skonieczny, L. Latos-Grażyński, L. Szterenberg, Chem. Eur. J. 2008, 4861.
2