base.13 The absorption spectra of both complexes are remarkably
porphyrin-like in appearance, with relatively intense Soret and Q-
like bands. However, 5-isocorroles are not cross conjugated across
the macrocycle, so these bands do not result from porphyrinic
Gouterman-type four orbital transitions,21 but rather from the p
to p* excitation of the extended conjugation of the macrocycle. In
spite of this, the observed extinction coefficients are appreciably
large (2–3 ¥ 104 M-1 cm-1). One notable aspect of both complexes
is the relatively intense low energy absorptions above 800 nm.
Zn1 and Cu1 show bands at 851 and 847 nm, respectively, with
extinction coefficients of 9.6 ¥ 103 and 1.6 ¥ 104 M-1 cm-1. It is
notable that all of the bands are significantly red shifted from
those observed in the free base, with the exception of the high
energy absorptions ~350 nm. Similar low energy absorption bands
are also present in other metal isocorrole complexes; Paolesse’s
10-isocorrole Cu complex exhibits a band at 828 nm,14 and the
Sestune’s Fe, Mn and Re complexes of dimethyl 10-isocorrole all
show transitions above 750 nm.15 These low energy absorptions
appear to be a common attribute of both 5- and 10-isocorrole
metal complexes. Thus, in addition to their use as novel biomimetic
ligand systems, isocorroles may also find applications as near IR
dyes and photonic materials.22
Z = 8, r = 1.544 g cm-3, M = 768.91, Rint= 0.0713, R1 = 0.0795 wR2 = 0.1319
(for 13 712 reflections, 52 573 observed reflections Io > 2s(Io)). Data were
collected at 100(2) K (Bruker-AXS SMART CCD diffractometer with
˚
MoKa radiation, l = 0.71073 A) and corrected for absorption (empirical
SADABS). The structures were solved by direct methods and refined
by full-matrix least-squares procedures (SHELX97). CCDC numbers
808100–808102 contain the supplementary crystallographic data for this
paper.
1 J. L. Sessler, R. S. Zimmerman, C. Bucher, V. Kral and B. Andrioletti,
Pure Appl. Chem., 2001, 73, 1041–1057.
2 F. Jerome, J.-M. Barbe, C. O. Gros, R. Guilard, J. Fischer and R. Weiss,
New J. Chem., 2001, 25, 93–101.
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2001, 66, 550–556.
5 S. Nardis, G. Pomarico, F. R. Fronczek, M. G. H. Vicente and R.
Paolesse, Tetrahedron Lett., 2007, 48, 8643–8646.
6 F. Mandoj, S. Nardis, G. Pomarico and R. Paolesse, J. Porphyrins
Phthalocyanines, 2008, 12, 19–26.
7 M. Stefanelli, J. Shen, W. Zhu, M. Mastroianni, F. Mandoj, S. Nardis,
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9 G. Hohlneicher, D. Bremm, J. Wytko, J. Bley-Escrich, J-P. Gisselbrech,
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5636–5642.
In conclusion, we present the structure of free base 5-isocorrole
along with Cu(II) and Zn(II) metal complexes. These compounds
do show similarities to the previously characterized 10-isocorrole
compounds, even though the position of the sp3 hybridized carbon
is different. There is a reduction in symmetry versus the 10-
isocorroles, and upon formation of metal complexes a slightly
contracted coordination sphere is observed in Cu1. Interestingly,
in both Cu1 and Zn1, the “Q band” region contains low energy
transitions that are significantly bathochromically shifted versus
the free base. We are continuing our work on the fundamental
chemistry and metal binding of the 5-isocorrole macrocycle.
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5766–5774.
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Notes and references
‡ Crystal data for 1 (C34H17Cl3F10N4): monoclinic, space group P21, a =
◦
˚
9.2762(12◦), b = 11.2082(14), c = 14.9861(19) A, a = 90.00 , b = 90.472(2),
3
-3
˚
g = 90.00 , V = 1558.0(3) A , Z = 2, r = 1.658 g cm , M = 777.87, Rint
=
0.0255, R1 = 0.0331 wR2 = 0.0792 (for 6661 reflections, 12 937 observed
reflections Io > 2s(Io)). Cu1 (CuC34H15Cl3F10N4): monoclinic, space◦group
20 L. Simkhovich, P. Iyer, I. Goldberg and Z. Gross, Chem.–Eur. J., 2002,
8, 2595–2601.
˚
P21, a = 9.2791(19), b = 11.191(2), c = 14.859(3) A, a = 90.00 , b =
◦
3
-3
˚
90.678(3), g = 90.00 , V = 1542.9(6) A , Z = 2, r = 1.807 g cm , M =
839.39, Rint= 0.0251, R1 = 0.0302 wR2 = 0.0657 (for 6616 reflections,
12 967 observed reflections Io > 2s(Io)). Crystal data for Zn1 (Zn C34.50H19
F10N4O1.50): monoclinic, space group P21/c, a = 14.503(3), b = 15.212(3),
21 M. J. Gouterman, in The Porphyrins, ed. D. Dolphin, Academic
Press, New York, 1978, Vol. III, pp. 1–165; P. G. Seybold and M. J.
Gouterman, J. Mol. Spectrosc., 1969, 31, 1–13; M. J. Gouterman,
J. Mol. Spectrosc., 1961, 6, 138–163.
◦
◦
3
˚
˚
c = 29.989(6), A, a = 90.00 , b = 91.308(4), g = 90.00 , V = 6614(2) A ,
22 M. Gra¨tzel, Acc. Chem. Res., 2009, 42, 1788–1798.
4386 | Dalton Trans., 2011, 40, 4384–4386
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