Synthesis and characterization of copper undecaarylcorroles and the first undecaarylcorrole free base

Article abstract of DOI:10.1002/ejic.201201158

The Suzuki cross-coupling reaction of copper β-octabromo-meso- triarylcorroles with arylboronic acids led to various copper peraryl-substituted corroles 4a-c, 5a-c, and 6a-c. The crystal structures of complexes 4b, 5a, 5b, 6a, 6b, and 6c show that their s

Full text of DOI:10.1002/ejic.201201158

SHORT COMMUNICATION
DOI: 10.1002/ejic.201201158
Synthesis and Characterization of Copper Undecaarylcorroles and the First
Undecaarylcorrole Free Base
Di Gao,[a] Gabriel Canard,*[a] Michel Giorgi,[b] and Teodor Silviu Balaban[a]
Keywords: Corroles / Cross-coupling / Macrocycles / Copper / Porphyrinoids
The Suzuki cross-coupling reaction of copper β-octabromo-
meso-triarylcorroles with arylboronic acids led to various
copper peraryl-substituted corroles 4a–c, 5a–c, and 6a–c. The
crystal structures of complexes 4b, 5a, 5b, 6a, 6b, and 6c
show that their saddling dihedral angles strongly depend on
the nature of the meso substituents, whereas the β-aryl sub-
stituents induce a significant redshift of their UV/Vis absorp-
tion maxima. Copper corrole 5c was successfully demet-
alated to produce the corresponding undecaarylcorrole free
base 7. The crystal structure of 7 revealed that the introduc-
tion of 11 bulky aryl groups on the corrole ring did not pro-
duce unusual distortions in the macrocycle of the free base.
the copper ion can be easily removed under mild conditions
to afford the corresponding free bases.[15] This reactivity of-
fers a protection/deprotection strategy to produce function-
alized free-base corroles.[16]
Introduction
The discovery of the first simple methods for the one-pot
syntheses of meso-substituted corroles by Gross et al.[1] and
by Paolesse et al.[2] was the starting point for the optimiza-
tion of corroles syntheses.[3] Over the last decade, different
strategies have been proposed to introduce functional
groups on corrole free bases or on metallocorroles.[4] These
advances in the synthesis and functionalization of corroles
were used to prepare simple and very sophisticated syn-
thetic corroles[5] and led to their application in the fields of
catalysis,[6] medicine,[7] sensors,[8] and solar cells.[9] The most
interesting feature of corroles is their ability to stabilize
metal ions in high oxidation states such as FeIV[10] or re-
Ghosh et al. recently disclosed the synthesis of three cop-
per undecaaryl-substituted corroles through Suzuki cou-
pling, and one of these derivatives was characterized by sin-
gle-crystal X-ray diffraction.[17] This prompted us to report
our more-advanced results involving the preparation of nine
different copper undecaarylcorroles and the structures of
six of them, which were solved by X-ray diffraction. The
copper ion could be removed from one of these metallocor-
roles to produce the corresponding free base, whose struc-
ture was also ascertained by single-crystal X-ray diffraction.
These crystal structures show that the saddling dihedral
angles of the copper corroles are strongly influenced by
meso substitution, whereas an increase in the steric hin-
drance was not found to produce unusual distortions in the
macrocycle of the free base. In contrast, the introduction of
bulky β-aromatic substituents induces a significant redshift
of all bands in the UV/Vis spectra of the fully aryl-substi-
tuted compounds, which can have interesting applications
in molecular electronics and solar cells.
cently AuIII [11]
Among all the metallocorroles, copper cor-
.
roles are one of the most extensively studied, as these com-
plexes exhibit both diamagnetic and paramagnetic proper-
ties that strongly depend on the temperature and on the
substitution of the macrocycle.[12] This behavior was attrib-
uted to an energetically favorable Cu(dx2–y2)–corrole(π) or-
bital interaction, which allows these complexes to be de-
scribed as a CuIII corrole that is in equilibrium with a CuII
corrole π cation radical, in which the two unpaired electrons
are strongly antiferromagnetically coupled.[13] This orbital
interaction provides the driving force for the saddling of the
corrole macrocycle, which is strongly sensitive to peripheral
substituents.[14] Copper corroles are also attractive because
Results and Discussion
Synthesis
[a] Aix Marseille Université, CNRS, iSm2 UMR 7313,
13397 Marseille, France
Fax: +33-4-91289146
Copper β-octabromo-meso-triarylcorrole derivatives are
useful synthons to introduce substituents at the β positions
of the corrole macrocycle through palladium-catalyzed re-
actions. These derivatives have been successfully used to
prepare β-octakis(trifluoromethyl)-meso-triarylcorroles by
palladium-catalyzed trifluoromethylation, whereas a Heck
E-mail: gabriel.canard@univ-amu.fr
Homepage: http://www.ism2.univ-cezanne.fr
[b] Aix Marseille Université, FR 1739 – Fédération des Sciences
Chimiques de Marseille – Spectropole,
13397 Marseille, France
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201201158.
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D. Gao, G. Canard, M. Giorgi, T. S. Balaban
SHORT COMMUNICATION
procedure has been used to transform them into meso-triar- complex 3 was used, the yields were always low, even if
yltetrabenzocorroles.[18] These results prompted us to study more catalyst and more reactants were added every 24 h.
their possible derivatization by a very simple Suzuki cross- The progress of all reactions was monitored by periodic
coupling reaction that has been used to introduce four aryl TLC examination of the reaction mixture; the TLC plates
groups on the corrole free bases.[19] For this purpose, we usually showed the presence of more than five different col-
chose various arylboronic acids and copper β-octabromo- ored compounds. When the starting compound was fully
corroles 1–3, which bear electron-donating or electron-with- consumed and no further evolution of the reaction was ap-
drawing groups at the meso positions (Table 1).
parent, additional amounts of catalyst and boronic acid
Under typical conditions [Pd2(dba)3, K2CO3, toluene, were added until no evolution of the mixture composition
100 °C], corroles 1–3 underwent smooth Suzuki cross-cou- was detected. The competing dehalogenation reaction[20]
plings with three different arylboronic acids to afford cop- and tedious chromatographic purification of the products
per fully aryl-substituted corroles 4a–c, 5a–c, and 6a–c. A are the main causes for the low isolated yields (Table 1, en-
large excess amount of the boronic acid was required to tries 3, 5, 7–9). The use of pentafluorophenyl- and pyr-
afford decent isolated yields, and these yields were strongly idylboronic acids did not give any perceptible results, but
dependent on the nature of the starting corroles and the these reagents probably require other cross-coupling condi-
arylboronic acids. For example, when electron-deficient tions.
Table 1. Suzuki cross-coupling preparation of copper fully aryl-substituted corroles.
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Synthesis and Characterization of Copper Undecaarylcorroles
The stabilities of corrole free bases are known to increase donating groups. In contrast, the lowest χ values are ob-
as the electron deficiency of the peripheral substitution in- served for complexes 6a–c, which bear strong electron-with-
creases.[21] Therefore, we examined the demetalation of 5c, drawing groups at the meso position, whereas the β substit-
which bears sufficient electron-withdrawing groups uents are either electron-donating or electron-withdrawing
(Scheme 1). Reductive demetalation of 5c with concentrated groups. Given that the HOMOs and LUMOs of copper cor-
[15d]
H2SO4 and FeCl2
gave, as expected, corresponding free roles have large amplitudes at the meso positions but only
base 7 in good yield. As far as we know, 7 is the first unde- small ones at the β positions, the saddling distortion of the
caarylcorrole free base described. The same procedure ap- corrole ring is extremely sensitive to the nature of the meso
plied to 5a resulted in complete degradation of the starting substituent. It is interesting to note that the saddling dihe-
material, which reveals the low stability of the correspond- dral angle of 4b (60°) is close to the value reported for an
ing free base.
analogous copper β-octabromocorrole substituted by two
p-methoxyphenyl groups and one p-methylphenyl group
(68.2°).[23] Therefore, β-aryl groups and β-bromine atoms
seem to exercise the same steric effect on the saddling of
copper corroles. Nevertheless, this β-substitution effect can-
not be restricted to a simple consequence of increased steric
hindrance. For example, one can consider that the steric
hindrance of the β-aryl groups in 6a is equal to that of the
β-aryl groups in 6b and 6c. Therefore, the variation of χ
from 24° in 6b to 33° in 6c is probably due to electrostatic
effects or due to the π–π stacking interactions between the
β- and meso-aryl groups. Such an increase in the ring sad-
dling is also observed for 5a and 5b, who have χ values of
41 and 57°, respectively.
Scheme 1. Synthesis of fully aryl-substituted corrole free base 7.
Crystal Structures of Copper Corroles 4b, 5a, 5b, 6a, 6b,
and 6c
Slow diffusion of n-heptane into concentrated dichloro-
methane solutions of 4b, 5a, 5b, 6a, 6b, and 6c yielded dif-
fracting single crystals suitable for X-ray structure analysis
(Figure 1 and Figure S1 in the Supporting Information).
Details of the structure determinations are given in Table S1
and S2 (Supporting Information). All of the crystal struc-
tures exhibit square-planar coordination of the Cu atom,
and the average Cu–N distance is 1.9 Å with a maximum
deviation of 0.02 Å of the copper ion from the mean plan
of the four nitrogen atoms. Interestingly, these structures
show four sets of π–π stacking interactions between the aryl
groups. Each meso-aryl group interacts with the two adja-
cent β-aryl substituents, and the two β-aryl substituents of
each pyrrole unit are involved in a different π–π interaction.
The direct pyrrole–pyrrole link allows the two remaining
aryl groups to interact with each other. The most intriguing
feature of the copper corroles is that they are inherently
saddled.[22] The saddling was attributed to a specific cop-
per(d)–corrole(π-HOMO) orbital interaction that can be re-
inforced by steric congestion at the macrocycle periph-
ery.[14,23] This saddling distortion is usually illustrated
through the value of the saddling dihedral χ between the
two adjacent B and C pyrrole units (Table 2).[14] Com-
pounds 4b, 5a, 5b, 6a, 6b, and 6c are all saddled, and their
χ values range from 24 to 60° (Figure 2). The highest value
Figure 1. ORTEP views of copper corrole (a) 5b and (b) 6c (solvent
molecules are omitted for clarity). Four other similar structures are
of χ is reached by 4b, which is fully substituted by electron- reported in the Supporting Information.
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D. Gao, G. Canard, M. Giorgi, T. S. Balaban
SHORT COMMUNICATION
Table 2. Soret band maxima and saddling dihedral angles of copper SQUEEZE procedure (from PLATON).[24] As in the two
first-described structures of meso-triarylcorrole,[2b,25] the lo-
corroles and corrole free bases.
cations of the three internal protons were not assignable.
Their electron densities were then distributed equally over
the four core nitrogen atoms (Supporting Information). As
in the structures of the copper complexes, all the peripheral
aryl groups are involved in π–π stacking interactions. In 7,
the mean plane of the ring (based on the 19 external atoms
of the skeleton) is deformed from planarity as a result of
the steric hindrance of the internal protons. The pyrrole
rings are tilted upwards and downwards alternately. The C
and D pyrrole rings are the most coplanar pyrrole units
(dihedral angle = 4.33°) and are used to define the mean
plane of the macrocycle. The A and B pyrrole rings are
titled out of the mean plane in opposite directions by 17.3
and 20.7°. These values are close to the ones observed (18.1
and 17.3°) for the meso-triphenylcorrole free base[26] and
show that the introduction of eight bulky aryl groups at the
β positions does not induce supplementary constraints on
the corrole macrocycle.
Compd.
M
R1
R2
λmax [nm][a]
433[b]
405, 468[b]
463
χ
1-H
1
4a
4b
4c
Cu
p-H3COC6H4
H
Br
p-H3COC6H4
p-H3CC6H4
p-FC6H4
464 60.1
461
2-H
2
5a
5b
5c
Cu p-H3CO2CC6H4
H
Br
415
442
451 41.9
446 57.3
439
p-H3COC6H4
p-H3CC6H4
p-FC6H4
3-H
3
6a
6b
6c
Cu
C6F5
H
Br
406[b]
427
413 31.8
419 24.7
421 33.3
p-H3COC6H4
p-H3CC6H4
p-FC6H4
7-H
7
3 H p-H3CO2CC6H4
3 H
H
424
453
p-FC6H4
[a] Recorded in dichloromethane. [b] Ref.[13]
Figure 3. View of the X-ray structure of corrole free base 7.
Electronic Absorption Spectra
Copper meso-triarylcorroles are known to show hyper-
spectra that are strongly sensitive to the nature of the 5
and 15 meso substituents.[27] These groups are involved in
phenyl-to-Cu(dx2–y2) charge transfers that contribute to the
main peaks of the Soret region. This contribution is also
observed in the UV/Vis spectra of copper undecaarylcor-
roles in which the Soret band is redshifted from 413 nm in
6a to 463 nm in 4a (Table 2) The introduction of β-bulky
aryl groups induces redshifts of the Soret band, which are
Figure 2. Views of the X-ray saddled structures of copper corroles
4b, 5a, 5b, 6a, 6b, and 6c along the Cu–C10 axis (aryl groups and
solvent molecules are omitted for clarity).
Crystal Structure of Corrole Free Base 7
Crystals of 7 were grown by slow diffusion of n-heptane close to the ones produced by the β-bromine atoms
into a concentrated dichloromethane solution of 7. The (Table 2). Moreover, variation of the para substituent of the
structure of 7 (Figure 3) suffered from disordered and un- β-aryl group has no significant or interpretable effect on the
identified solvent molecules in the lattice, which were not location of the Soret maxima. These results indicate that
included in the refinement but were taken care of by the the redshifts produced by β-aryl substitution are mostly due
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Synthesis and Characterization of Copper Undecaarylcorroles
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Conclusions
We have prepared nine new copper β-octaaryl-meso-tri-
arylcorroles by a simple Suzuki cross-coupling procedure.
The crystal structures of six saddle copper complexes were
fully resolved and show that their saddling dihedrals in-
crease with the electron-donating efficiency of the meso sub-
stituents. This macrocyclic deformation is reinforced by the
steric hindrance of the β-aryl groups with χ values close to
those produced by β-octabromination. Another conse-
quence of the undecaaryl substitution is the redshift of the
UV/Vis absorption maxima, which are still sensitive to the
nature of the meso substituents. The electrochemical data
of these copper complexes are currently under study as are
their hole/electron transport properties. Reductive demet-
alation of one copper derivative afforded the first example
of an undecaarylcorrole free base in which the 11 peripheral
aryl groups do not produce supplementary distortions in
the macrocycle. This protection/deprotection strategy opens
the way to produce other fully aryl-substituted metallocor-
roles, and this is currently under investigation.
CCDC-899348 (for 4b), -899349 (for 5a), -899350 (for 5b), -899351
(for 6a), -901041 (for 6b), -899352 (for 6c), and -899353 (for 7)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
Supporting Information (see footnote on the first page of this arti-
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Acknowledgment
D. G. gratefully acknowledges the China Scholarship Council for
financial support.
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Received: September 25, 2012
Published Online: November 20, 2012
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