adjacent meso aryls, allowed the specific identification of the
meso aryl substituents distinguished remarkably also by a
peculiar spread of 5-Ph and anthracene resonances.
1H NMR chemical shifts of 3–Cl have been calculated using
the GIAO-B3LYP method for the optimized (DFT-B3LYP
with the LANL2D basis set for Pd and 6-31G** for other atoms)
geometry. This is a satisfactory qualitative agreement for the
considered set of theoretical and experimental data readily
demonstrated by linear correlation between the calculated and
experimental chemical shifts values (Fig. S25, ESIz).
In conclusion, meso-anthriporphyrin is the new porphyrinoid,
which belongs to the group of aceneporphyrins. Potentially an
anthracene ring may be able to participate in various metal–arene
bonding modes. This study demonstrates considerable parallel in
the coordination properties of meso-anthriporphyrin and its lower
benzologues: p-benziporphyrin and 1,4-naphthiporphyrin toward
palladium(II). In contrast to palladium(II) p-benziporphyrin and
palladium(II) 1,4-naphthiporphyrin complexes, which undergo
facile intramacrocyclic contractions in basic conditions,1,9 the
alternative mechanism is operating for palladium(II) meso-anthri-
porphyrin resulting in the C1–Cmeso cleavage.
Fig. 3 Molecular structure of 2–Cl: (top) perspective view; (middle)
side view with phenyl groups omitted for clarity; (bottom) geometry of
the interaction between palladium(II) and the anthracene moiety. The
thermal ellipsoids represent 50% probability.
We thank Professors Zbigniew Ciunik and Tadeusz Lis for
valuable discussions. Financial support from the NCN (Grant
2011/01/N/ST5/0255) is kindly acknowledged. DFT calculations
were carried out at the Poznan and Wroc"aw Supercomputer
´
Centers.
Notes and references
_
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3 M. Pawlicki and L. Latos-Grazynski, in Handbook of
Porphyrin Science, ed. K. M. Kadish, K. M. Smith and
R. Guilard, World Scientific Publishing, Singapore, 2010,
pp. 104–192.
Scheme 3 Synthesis of 3–X: (a) K2CO3, MeCN, 12 h, 16% for 3–Cl.
NOE measurements. The palladium(II) cation acquires a typical
square planar coordination geometry15,16 whereas four donating
atoms (three pyrrolic nitrogen atoms and one carbonyl oxygen
atom) are provided by the acyclic oligopyrrole. The NOE
correlations (Fig. S7, ESIz), which result from the unique
through-space interactions between appended anthracene and
4 M. Toganoh and H. Furuta, in Handbook of Porphyrin Science, ed.
K. M. Kadish, K. M. Smith and R. Guilard, World Scientific
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Fig. 4 DFT-optimized structure of 3–Cl. C light gray, H white,
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c
5006 Chem. Commun., 2012, 48, 5004–5006
This journal is The Royal Society of Chemistry 2012