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A porphyrin-related macrocycle from carbazole and pyridine building
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blocks: synthesis and metal coordinationw
Lena Arnold, Hassan Norouzi-Arasi,* Manfred Wagner, Volker Enkelmann and
Klaus Müllen*
Received 5th August 2010, Accepted 28th October 2010
DOI: 10.1039/c0cc03052j
In this communication, we report the synthesis of a novel
porphyrin-related macrocycle. The core modifications result in
aromatic building blocks connected exclusively via aryl–aryl
bonds. The concept of synthesis permits the formation of a
cavity similar to that of a porphyrin combined with the ability
to bind metal ions to provide neutral metal complexes.
Porphyrins are by far the most intensively studied nitrogen-
containing macrocycles, due to their biological importance as
well as their ability to function as efficient metal-complexing
ligands.1 The great interest derives from their unique properties
such as photo-, chemical-, and thermal stability, as well as
their optical characteristics. Their broad areas of application
range from catalysis, organic electronics and nonlinear optics
to photodynamic therapy.2 These outstanding qualities have
inspired the study of different porphyrin-analogues, which are
contracted, expanded or isomeric with respect to porphyrin.3
The main motivation for the replacement of one or more
pyrrole units in the porphyrin core is to control and tune the
properties of resulting compounds.1 Pyriporphyrins, where
one pyrrole unit is replaced by pyridine, suffer from instability
due to the surrounding meso-carbons at the pyridine moiety.4
To the best of our knowledge, no porphyrin-related macrocycle
with the pyrrolenine and pyrrole units replaced by pyridine and
carbazole moieties, respectively, has been reported so far
(Scheme 1). By this approach unstable meso-carbons are avoided.
Herein we present a new synthetic pathway for porphyrin-
related macrocycle 3 via Suzuki–Miyaura cross-coupling
reaction of carbazole and pyridine moieties. The facile palladium-
catalyzed route towards compound 3 is straightforward and the
Scheme 1 Modifications of porphyrin macrocycle by replacing
pyrrole and pyrrolenine units by carbazole and pyridine.
Max Planck Institute for Polymer Research, Ackermannweg 10,
55128 Mainz, Germany. E-mail: norouzi@mpip-mainz.mpg.de,
muellen@mpip-mainz.mpg.de; Fax: +49 6131 379350;
Tel: +49 6131 379150
w Electronic supplementary information (ESI) available: Experimental
and analytical data for all described compounds. CCDC 787489 and
787490. For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/c0cc03052j
970 Chem. Commun., 2011, 47, 970–972
macrocyclization occurs in a one-pot reaction. The molecular
design permits the formation of a cavity similar to that
of a porphyrin as well as the ability to bind metal ions. The
coordination properties of 3 were investigated by the formation
of a cobalt complex.
Porphyrins consist of four pyrrole units linked by four
meso-carbon atoms in a planar arrangement with a 18p
aromatic character. For symmetrically substituted porphyrins,
the degenerate trans-NH-tautomers are most favored, resulting
in two pyrrolic and two imine-type nitrogens. To combine
these properties in the new design, carbazole and pyridine
moieties were chosen as building blocks. Although pyridine is
an electron deficient moiety, it can act as a good Lewis base
due to the availability of the nitrogen lone pair electrons. On
the other hand, carbazole is an electron rich molecule which
can bind metals in its deprotonated form.5
A ring size similar to that of a porphyrin was realized by
using the 1,8-disubtituted carbazole derivative 1, which was
synthesized following the procedure described in the literature
(Scheme 2).6 The tert-butyl groups were chosen due to their
stability in the applied synthetic transformations and their
bulkiness preventing aggregation of the formed macrocycle. In
contrast to the previously reported unsuccessful attempts to
introduce boronic acid groups into the 1,8-position of the
carbazole moiety,7 we were able to synthesize diboronic-ester 2
in 50% yield. This was done by an in situ protection of the
carbazole NHs of compound 1 with CO2 followed by the
introduction of the boronic-ester groups using 2-isopropoxy-
4,4,5,5-tetramethyl-1,3,2-dioxaborolane.8 The macrocyclization
towards compound 3 succeeded under palladium-catalyzed
Suzuki–Miyaura coupling reaction conditions.9 The demanding
fourfold cross-coupling reaction proceeded in 15% yield.
The ability of macrocycle 3 to act as a metal ligand was
investigated by the insertion of cobalt(II)-ion into the ring
Scheme 2 Synthesis of compounds 3 and 4.
This journal is c The Royal Society of Chemistry 2011

cavity. The cobalt complex 4 was obtained by refluxing
macrocycle 3 with cobalt(II)acetate in DMF (Scheme 1).
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The 1H NMR signals for the carbazole NH protons
(9.66 ppm, CD2Cl2, 298 K) in the ring cavity of macrocycle
3 are shifted downfield compared to precursor 1 (8.26 ppm).10
This can be attributed to the presence of hydrogen bonding.
Compared to porphyrins, where the 1H NMR signals for the
internal NHs are shifted upfield to approximately 4 ppm, in
macrocycle 3 no specific diamagnetic ring current is observed,
which is due to the lack of annulene conjugation in the ring.1
The structure of macrocycle 3 was further elucidated by
X-ray crystallography (Fig. 1).z The molecule is nonplanar
with C2n symmetry, the pyridine moieties being twisted ‘‘up’’
and the carbazoles twisted ‘‘down’’, resulting in a saddle-
like conformation. The carbazole moieties span an angle of
a = 162.61 and the average dihedral angle between the carbazole
plane and the pyridine plane is F = 45.11. The cavity of
macrocycle 3 is rectangular (N(2)–N(4) 3.90 Å; N(1)–N(3)
4.86 Å) with the shortest distance between the carbazole
nitrogens, resulting in a slightly smaller ring size than in the case
of porphyrins (4.2 Å), but still large enough to bind 3d transition
metal ions with effective ionic radii between 0.5–0.9 Å.11
Complexation of macrocycle 3 with cobalt(II) was analyzed
by MALDI-TOF mass spectrometry, FT-IR, UV/Vis,
1
H NMR, X-ray and XPS spectroscopy (see ESIw).
The insertion of cobalt into the macrocycle was monitored
by 1H NMR spectroscopy. For this purpose, a NMR tube
with a solution of macrocycle 3 in DMF-d7 and an excess of
Co(OAc)2 was heated to 403 K (Fig. 2). The formation of the
cobalt complex could be observed by the disappearance of the
signals for the macrocycle and the appearance of new signals.
The signals for the cobalt complex are broad and highly
shifted compared to macrocycle 3, which is caused by contact
and pseudocontact contributions and is typical for para-
magnetic species.12 Most peaks are shifted downfield with
the highest shifted signal appearing at 45.41 ppm and one
signal shifted upfield to 8.49 ppm. The high downfield-shift is
attributed to a s-contact shift mechanism in Co(II)–pyridyl
complexes.13 Upfield-shifts can be explained by a p-contact
shift contribution at this position.14
Fig. 1 Crystal structure of macrocycle 3 (a/b) and cobalt complex 4
(c/d) with top view and side view each. The side view is showing the
saddle-like conformation (for b/d the hydrogen atoms are omitted).
THF solvate molecules are omitted for clarity; the ellipsoids correspond
to 50% probability; dihedral angles are shown in the molecules e.g.
F(N(1)–C(1)–C(34)–C(29)) = 43.61.
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Fig. 2 1H NMR study of the cobalt insertion into the macrocycle
(a) full range spectra; (b) aromatic region. For labelling see Fig. 1.
Spectra recorded in DMF-d7 at 500 MHz and 403 K with acquisition
time of 1.1 s, sweep width 119 ppm and a delay of 2 s.
FT-IR spectroscopy showed the absence of NH stretching
vibrations at 3487 cm1 for the cobalt complex 4 (Fig. S6, ESIw).
An X-ray structure determination of complex 4 revealed
that neither the saddle-like conformation nor the distances
between the nitrogens (N(2)–N(4) 3.88 Å; N(1)–N(3) 4.67 Å)
change upon complexation.z This is reflected in the negligible
change of a = 162.01 and the average dihedral angle
(F = 42.21, Fig. 1c). In addition to the four nitrogen atoms,
two solvent molecules are axially coordinated by oxygen
atoms to the cobalt(II)-ion. A THF molecule is coordinated
from above the saddle and a water molecule from below. The
coordination polyhedron around the cobalt(II)-ion can be
described as distorted octahedral. The cobalt–carbazole nitrogen
bond distances (Co–N(2) 1.95 Å; Co–N(4) 1.93 Å) are
significantly shorter than those of cobalt–pyridine nitrogens
(Co–N(1) 2.32 Å; Co–N(3) 2.35 Å) or the cobalt–oxygens
(Co–O(1) 2.27 Å; Co–O(2) 2.22 Å). This indicates some degree
of p-donation from the sp2-hybridized carbazole nitrogen to the
metal center.8 Carbazole usually undergoes ionisation and
behaves as an amido-N donor in organometallic chemistry, and
the Co–N(2,4) distances are well within the range of Co–Namido
distances noted for similar complexes (1.91–1.93 Å).5,15
Unfortunately, no EPR data of complex 4 could be
obtained at 298 K and 8 K, which may be due to a high-spin
Co(II) species.16 Therefore, XPS data were recorded to clarify
the oxidation state of the cobalt ion (Fig. S7, ESIw). The Co
2p3/2 peak at 779.4 eV and the multiple structure of the signal
are in agreement with the literature data for Co(II) compounds
and with theoretical calculations on the free Co2+ ion
considering spin–orbit and electrostatic electron–electron
interactions.17 As described in the literature a spin–orbit
splitting DE = Eb2p1/2  Eb2p3/2 higher than 15 eV (Eb are
the binding energies for the Co2p and Co3p lines) corresponds
to high-spin Co(II) complexes.18 In the case of complex 4 DE is
equal to 15.6 eV, thus the neutral cobalt complex appears to be
a high-spin Co(II) species.
Chem. Commun., 2011, 47, 970–972 971

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Fig. 3 Electronic absorption spectra in CH2Cl2 of macrocycle 3 (red,
1.8  105 M) and its cobalt complex 4 (blue, 1.2  104 M) and
emission spectra of macrocycle 3 (black).
The absorption spectrum of compound 3 showed two
absorption maxima at 313 nm and 372 nm (CH2Cl2, rt,
Fig. 3). For unsubstituted 3,6-di(tert-butyl)carbazole and
3,6-di-tert-butyl-1,8-di(pyridin-2-yl)-9H-carbazole a band at
about 230 nm is observed and originates from carbazole-
centered transitions.10,19 For macrocycle 3 this band is batho-
chromically shifted to 313 nm. Compound 3 exhibits blue
emission with a maximum at 402 nm. The quantum yield was
estimated to be Ff = 0.36 by calibration with coumarin 1. By
increasing the polarity of the solvent the emission maxima
were bathochromically shifted (Fig. S8, ESIw), indicating an
intrinsic polar character of the emitting state. Therefore, the
absorption maximum at 372 nm is assigned to a weak intra-
molecular charge transfer from the donor to the acceptor
units, pyridine and carbazole respectively. The absorption
maxima for the cobalt complex 4 were bathochromically
shifted to 331 nm and 425 nm. Bands in the region of
425 nm are often assigned to metal-to-ligand charge transfer.6
The blue emission of the free ligand was quenched upon
complexation with cobalt(II).
To gain additional insight into the optical properties
displayed by compound 3, the geometry and electronic
structure were calculated using density functional theory
calculation (DFT, B3LYP/6-31G*, Fig. S10, ESIw). These
calculations revealed that the LUMO and LUMO + 1 are
degenerated, with the LUMO orbitals located on one and the
LUMO + 1 orbitals on the other carbazole moiety. In
contrast, the electronic density of the HOMO is distributed
over both carbazole moieties. The calculated HOMO and
LUMO levels were estimated to be EHOMO = 5.14 and
ELUMO = 1.17 eV. The calculated band gap (3.97 eV) is
similar to the value DEopt = 3.63 eV, derived from absorption
edge measurements.
The cyclic voltammogram of macrocycle 3 showed two
irreversible oxidation waves indicating that the carbazole
moieties are oxidized successively to cation radicals (Fig. S9,
ESIw).20 The HOMO level (EHOMO = 5.36 eV) was estimated
from the first oxidation onset potential of 1.25 V with regard
to an external reference (Fc/Fc+). ELUMO was empirically
calculated to be ELUMO = 1.73 eV, by taking the optical
band gap into account. These results are in good agreement
with DFT calculations (Fig. S10, ESIw). The cobalt complex 4
showed two reversible oxidation waves at E1/2(1) = 0.78 V
and E1/2(2) = 1.05 V. It is suggested that one oxidation wave
occurred at the cobalt atom (Co2+ + L - Co3+ + L) and
the second at the ligand (Co3+ + L - Co3+ + L+).21
972 Chem. Commun., 2011, 47, 970–972
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In summary, by utilization of a facile palladium-catalyzed
cross-coupling reaction, we successfully synthesized macro-
cycle 3 which consists solely of aromatic building blocks. The
design concept permits the formation of a cavity big enough to
complex 3d transition metal ions, which was demonstrated for
cobalt(II). Complexation of other metal ions such as iron,
nickel or copper and studies of their catalytic properties are in
progress.
We thank Dr Hideyuki Higashimura and Dr Nobuyoshi
Koshino for XPS data, and Sumitomo Chemical Co., Ltd. for
financial support.
Notes and references
z Crystal data for 3 and 4: C68H88N4O4.5 3: M = 1032.46,
orthorhombic, space group P22121, a = 8.9009(3) Å,
b = 22.2751(9) Å, c = 29.7836(9) Å, V = 5905.3(4) Å3, Z = 4,
27 036 reflections measured, 11 884 unique reflections, Rint = 0.046,
8509 reflections observed (I > 2s(I)). Refinement on F, R = 0.0532,
Rw = 0.0578. C68H88CoN4O5.5 4: M = 1108.40, orthorhombic, space
group P22121, a = 9.1483(4) Å, b = 21.8882(9) Å, c = 29.7527(9) Å,
V = 5957.7(4) Å3, Z = 4, 29 056 reflections measured, 10 964 unique
reflections, 9174 reflections observed (I > 2s(I)). Refinement on F,
R = 0.0625, Rw = 0.0630. CCDC 787489 and 787490.
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