Synthesis and physicochemical characterization of bis(macrocycles) involving a porphyrin and a meso-substituted corrole - X-ray crystal structure of a [(free-base porphyrin)-corrole]bis(pyridine)cobalt complex

Article abstract of DOI:10.1002/ejic.200400756

A very efficient, simple synthesis of face-to-face porphyrin-corrole free-bases bearing substituents at the meso positions of the corrole ring is reported. Starting from the (porphyrin-aldehyde)zinc species 1Zn, porphyrin-corrole free-bases (3M, 3C) are obtained in two steps, in fairly good yields (40-43%), compared to 11 steps for their corrole β-pyrrole- substituted counterparts. Moreover, the possibility to directly synthesize the free-base (porphyrin-corrole)cobalt complex (5M or 5C) allows for the further preparation of heterodimetallic derivatives. Crystals of the bis(pyridine) adduct of 5M have been grown; the molecular structure clearly shows that the two pyridine molecules are coordinated to the cobalt ion in endo and exo positions, leading to an open-mouth geometry of the bis(macrocycle). The structure of 5M(py)₂also shows intermolecular π-π interactions along the [100] direction, leading to stacking of the complexes. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejic.200400756

FULL PAPER
Synthesis and Physicochemical Characterization of Bis(macrocycles) Involving
a Porphyrin and a meso-Substituted Corrole – X-ray Crystal Structure of a
[(Free-base porphyrin)–corrole]bis(pyridine)cobalt Complex
Jean-Michel Barbe,*[a] Fabien Burdet,[a] Enrique Espinosa,[a] and Roger Guilard*[a]
Keywords: Bis(macrocycles) / Porphyrins / Corroles / Synthetic methods / X-ray diffraction
A very efficient, simple synthesis of face-to-face porphyrin–
corrole free-bases bearing substituents at the meso positions
of the corrole ring is reported. Starting from the (porphyrin–
aldehyde)zinc species 1Zn, porphyrin–corrole free-bases
(3M, 3C) are obtained in two steps, in fairly good yields (40–
43%), compared to 11 steps for their corrole β-pyrrole-substi-
tuted counterparts. Moreover, the possibility to directly syn-
thesize the free-base (porphyrin–corrole)cobalt complex (5M
or 5C) allows for the further preparation of heterodimetallic
derivatives. Crystals of the bis(pyridine) adduct of 5M have
been grown; the molecular structure clearly shows that the
two pyridine molecules are coordinated to the cobalt ion in
endo and exo positions, leading to an open-mouth geometry
of the bis(macrocycle). The structure of 5M(py)2also shows
intermolecular π–π interactions along the [100] direction,
leading to stacking of the complexes.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
between the porphyrin and the corrole rings. Indeed, cor-
roles can coordinate metal ions in higher oxidation states
than porphyrins.[11,12] Therefore, complexation of the bis-
(macrocycle) by a cobalt ion could directly generate the
active species in the O2 four-electron catalytic cycle, i.e. co-
balt(ii) in the porphyrin and cobalt(iii) in the corrole
ring.[13] We recently demonstrated that this mixed-valence
species is a good catalyst for the 4e reduction of O2 to
water.[14]
Most investigated porphyrin–corrole bis(macrocycles)
were substituted at the β-pyrrole positions by electron-do-
nating groups.[9] However, recent syntheses of meso-substi-
tuted corroles allow significant variation of the substituents
on the corrole ring, particularly at the meso positions.[15–23]
Electron-withdrawing substituents on the bis(macrocycle)
corrole ring enhance the Lewis acid character of the com-
plexed metal ion [namely cobalt(iii)], the main parameter in
stabilizing the dioxygen adduct. Therefore, the stability of
the dioxygen adduct formed during the catalytic process in-
creases with the Lewis acid character of the corrole-coordi-
nated metal ion. By adapting the new procedures, involving
the reaction of dipyrromethanes with an aromatic aldehyde,
we could prepare new porphyrin–corrole derivatives with
the corrole counterpart substituted at the meso positions
with mesityl or 2,6-dichlorophenyl groups. Moreover, the
corrole ring is formed in only two steps, allowing for the
synthesis of gram quantities of these model catalysts.
Here we describe the synthesis of these new bis(macro-
cycles), and show the possibility of selectively metalating
the corrole ring by cobalt (or another metal) to access het-
erodimetallic derivatives.
Introduction
Enzyme mimics have always been of great interest. For
example, considerable studies of heme/copper terminal ox-
idases have led to several models of the active site. In ad-
dition, several reviews have been published recently.[1–3]
Concurrently, cofacial bis(porphyrins) were proposed as
synthetic models of the dioxygen reduction site and, par-
ticularly, face-to-face bis(porphyrin)bis(cobalt) complexes
appeared to be very efficient catalysts for the four-electron
reduction of O2 to water in acidic media.[1,2,4,5] Cofacial
heterodimetallic bis(porphyrins) containing one cobalt
atom were later reported, and also proved to be good cata-
lysts for O2 reduction.[1,6–8] Numerous studies on the syn-
thetic models indicate that the catalytic activity originates
from intermetallic cooperation between the two metal
atoms of the bis(porphyrin) complex, tuned by the nature
of the spacer.[1,5] Moreover, the Lewis acid character of one
of the two metals in the bis(porphyrin) complex is a key
factor in stabilizing the dioxygen adduct during catalysis.[1]
Our research in this domain has focused on cofacialbis(-
macrocycles) where a porphyrin and a corrole are held to-
gether by a rigid spacer.[9,10] The originality of this ap-
proach lies in the difference in coordination properties
[a] Laboratoire d’Ingénierie Moléculaire pour la Séparation et les
Applications des Gaz (LIMSAG, CNRS UMR 5633), Faculté
des Sciences, Université de Bourgogne,
6 boulevard Gabriel, 21100 Dijon, France
Fax: +33-3-80396117
E-mail: Roger.Guilard@u-bourgogne.fr
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DOI: 10.1002/ejic.200400756
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Bis(macrocycles) Involving a Porphyrin and a meso-Substituted Corrole
FULL PAPER
role bis(macrocycle) is obtained in only two steps. Scheme 2
gives the overall procedure.
Results and Discussion
5-Mesityldipyrromethane and 5-(2,6-dichlorophenyl)di-
pyrromethane were obtained from a previously described
procedure[24] and used for reaction with 1Zn. 1Zn was used
in the condensation instead of 1 since the reaction requires
the presence of trifluoroacetic acid (TFA), which can pro-
tonate the porphyrin moiety. For 1, larger quantities of
TFA must be used for the condensation reaction, and aci-
dolysis of the reacting dipyrromethane can occur. There-
fore, 1Zn is a more appropriate precursor because no pro-
tonation of the porphyrin core can occur and the final de-
rivatives 2M and 2C are much easier to purify by column
chromatography than their non-metalated counterparts.
1Zn was obtained in 87% yield in classical conditions by
simple metalation of 1 by zinc acetate dihydrate in chloro-
form/methanol (Scheme 2). The remaining aldehyde func-
tion of 1Zn was treated further, with either 5-mesityldipyr-
romethane or 5-(2,6-dichlorophenyl)dipyrromethane, in
dichloromethane in the presence of a catalytic amount of
TFA (aldehyde/TFA = 17:1.3 mmol).[19] Under the best ex-
perimental conditions, in which dipyrromethane was added
in twice the stoichiometric amount (66 mmol, 4 equiv.) with
respect to 1Zn, both 2M and 2C were obtained in yields
close to 30% compared to ca. 6% for stoichiometric
amounts (33 mmol, 2 equiv.).[19] To recover 2M and 2C, the
final reoxidation process was performed using 2,3-dichloro-
5,6-dicyano-1,4-benzoquinone (DDQ) after a 25× dilution
in dichloromethane.[21]2M and 2C were isolated in 27 and
33% yield, respectively. Corrole ring formation is easily evi-
denced in MALDI/TOF by a distribution of peaks centered
Synthesis and Physicochemical Characterization
We recently reported a significant improvement in the
syntheses of β-substituted porphyrin–corrole and bis(cor-
role) bis(macrocycles), allowing the yield in final free-bases
to be almost tripled.[10] However, even if one can introduce
electron-withdrawing substituents (i.e. phenyl groups) at the
β-pyrrole positions of the corrole ring, the synthetic path-
way affording the final free-bases is somewhat long. As an
example, Scheme 1 shows the synthesis of a β-phenyl-sub-
stituted porphyrin–corrole derivative.
When starting from the porphyrin–aldehyde precursor (1
in Scheme 1), the target compound is obtained in 11 steps
due to the step-by-step nature of this approach, which
firstly requires the formation of a dipyrromethane. This di-
pyrromethane is then coupled with a pyrrole–aldehyde to
obtain the final corrole ring by formation of an a,c-biladi-
ene. Each pyrrole precursor is obtained in three to five
steps, depending upon the substitution at the β-pyrrole po-
sitions (Scheme 1). Notably, a symmetrical corrole ring is
prepared in only eight steps since only one pyrrole deriva-
tive is needed. Another drawback of this multistep synthetic
route is that any variation in the structure of the desired
bis(macrocycle) requires the synthesis of a new pyrrole pre-
cursor (Scheme 1). Nevertheless, this is still the only method
that allows the insertion of electron-donating substituents
at the β-pyrrole positions of the corrole ring.[9,10]
An alternative to these β-substituted derivatives would
be the meso-substituted ones. Indeed, the new methods
leading to meso-substituted corrole rings[15–23] can be
adapted to the synthesis of porphyrin–corrole derivatives.
In the present case, starting from 1Zn, the porphyrin–cor-
1
at 1253.92 (2M) and 1307.34 (2C), and by H NMR reso-
nance signals of the corrole (Table 1). Notably, no signal
Scheme 1.
Eur. J. Inorg. Chem. 2005, 1032–1041
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J.-M. Barbe, F. Burdet, E. Espinosa, R. Guilard
FULL PAPER
Scheme 2.
could be attributed to the inner NH protons of the corrole of the NH groups of the corrole ring of 2M and 2C (see
ring.
Exp. Sect.).
Similarly, the corrole ring is evidenced in UV/Vis spec-
2M and 2C can be demetalated by washing with one mo-
troscopy by two extra Q bands at 610 and 638 nm, and 617 lar hydrochloric acid solution to afford the free bases 3M
and 636 nm for 2M and 2C, respectively. At the same time, and 3C in 43 and 40% yield, respectively (Scheme 2). UV/
the unique Soret band is slightly blue-shifted by 7 nm for Vis spectroscopy reveals 3M and 3C formation by one extra
both derivatives compared to that of 1Zn (Table 2). This Q band at ca. 510 nm when compared to 2M and 2C
1
shift is generally interpreted in terms of the mutual influ- (Table 2). H NMR spectra of 3M and 3C feature two sig-
ence of the porphyrin and corrole rings, thus increasing the nals corresponding to the NH protons of the porphyrin
HOMO–LUMO gap and therefore shifting the transition at free-base at δ = –5.43 and –4.69 ppm, and at δ = –5.63
lower wavelengths.[25,26]
and –4.97 ppm, for 3M and 3C, respectively. Again, no sig-
Corrole ring formation is further indicated by the disap- nal is observed for the same protons in the corrole ring.
pearance of the C=O stretching band at 1680 cm–1 of the
When treated with excess cobalt acetate tetrahydrate and
aldehyde function of 1Zn and the concomitant appearance sodium acetate in dichloromethane/methanol, 2M and 2C
of a new band around 3360 cm–1 relative to the vibration lead to 4M and 4C in ca. 85% yield, as confirmed by the
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Bis(macrocycles) Involving a Porphyrin and a meso-Substituted Corrole
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1
Table 1. H NMR spectroscopic data of the investigated compounds.
Porphyrin ring[c]
CH3
Corrole ring[c]
Hmesityl
Com-
pound[a,b]
Solvent
NH
CH2CH3
CH2CH3
Hmeso
CH3mesityl
Hβ
1
CDCl3 –3.24, –3.04
CDCl3
C6D6
1.89
1.88
1.83
2.50, 3.50, 3.65
2.48, 3.48, 3.63
2.60, 2.92, 3.19
4.26
4.08
3.86
9.99, 10.16
10.02, 10.12
1Zn
2M[d]
9.07, 9.66 0.93, 1.48, 2.36
7.55, 9.44 0.84, 1.45, 2.20
9.92, 10.00 0.80, 2.14, 2.65
9.94, 9.94 0.71, 2.17, 2.29
7.23
6.97
7.35
7.33
7.51, 7.81,
8.04, 8.28
7.55, 7.55,
8.11, 8.39
8.22, 8.58,
8.69, 9.00
8.23, 8.55,
8.73, 8.96
3M[d]
4M
C6D6 –5.43, –4.69
C5D5N
1.85
1.72
1.68
2.25, 2.56, 3.07
3.00, 3.36, 3.51
2.93, 3.33, 3.49
3.88
3.97
3.89
5M
C5D5N –3.72, –3.38
Hdichlorophenyl
6.87, 7.09, 7.43
Hβ
2C[d]
3C[d]
4C
C6D6
1.75
1.88
1.70
1.67
2.68, 3.16, 3.28
2.31, 2.84, 3.12
2.97, 3.46, 3.50
2.88, 3.39, 3.47
3.81
3.89
3.94
3.88
9.31, 9.56
8.66, 9.39
9.89, 9.95
9.90, 9.91
7.49, 7.91,
7.93, 8.43
7.41, 7.64,
8.16, 8.37
8.30, 8.59,
8.81, 9.12
8.32, 8.64,
8.78, 9.09
C6D6 –5.63, –4.97
C5D5N
7.24, 7.41, 7.64
7.70, 7.86, 8.01
7.71, 7.86, 8.00
5C
C5D5N –4.10, –3.49
[a] Dimethylxanthene unit protons omitted. [b] See Schemes 1 and 2 for structures of the compounds. [c] Coupling constants given in the
Exp. Sect. [d] Corrole NH protons not detected.
Table 2. UV/Vis data of the investigated compounds in CH2Cl2.
Compound
λmax [nm] (ε×10–3 L mol–1 cm–1)
1
403 (141)
406 (346)
399 (252)
397 (238)
393 (231)
389 (189)
399 (296)
396 (217)
389 (197)
389 (160)
502 (11.2)
535 (6.1)
536 (16.9)
540 (14.6)
544 (11.9)
538 (19.0)
541 (9.9)
538 (16.1)
543 (10.1)
539 (19.3)
540 (11.9)
571 (5.2)
625 (2.)
1Zn
2M
3M
4M
5M
2C
332 (23.6)
572 (16.0)
574 (18.1)
574 (17.4)
575 (16.7)
576 (8.2)
573 (20.7)
574 (15.6)
575 (15.4)
573 (9.2)
610 (5.9)
608 (8.3)
638(4.2)
633 (5.2)
508 (12.7)
507 (14.6)
628 (4.5)
636 (3.8)
617 (5.8)
616 (6.8)
3C
509 (10.9)
501 (11.1)
506 (16.7)
4C
5C
627 (4.7)
hypsochromic shift of the Soret band and by the presence
of only two major Q bands (Scheme 2 and Table 2). The
spectra of the two species recorded in pyridine are interest-
ing (see Exp. Sect. for data). Figure 1 shows the UV/Vis
spectra of both 4M and 4C in CH2Cl2 and pyridine. In
dichloromethane, the data are close to those of pure zinc
monoporphyrins, the only difference being the shoulder on
the Soret band of the porphyrin corresponding to that of
the corrole ring. In contrast, major differences arise when
pyridine is used as a solvent. For example, all Q bands are
red-shifted and a new absorption appears in the range 620–
625 nm. Such a band is specific of the coordination of two
pyridine molecules on the cobalt(iii) ion of the corrole moi-
ety.[10,27–29] Therefore, the coordination of two pyridine
molecules is expected on the cobalt atom in endo and exo
positions. The spectra in pyridine exhibit another band, at
456 nm, for both 4M and 4C complexes, corresponding to
the Soret band of the corrole ring. In 1H NMR spectra
recorded in deuterated pyridine all resonance signals appear
Figure 1. UV/Vis spectra of 4M and 4C recorded in CH2Cl2 and
pyridine.
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J.-M. Barbe, F. Burdet, E. Espinosa, R. Guilard
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in the diamagnetic region (δ = 0–10 ppm) while in non-co- zation of 5M in cyclohexane/pyridine furnished crystals of
ordinating solvents (CDCl3 or C6D6) broad signals appear 5M(py)2.
over a wider range for the corrole counterpart. This behav-
ior is attributed to the presence, in non-coordinating sol-
vents, of a high-spin CoIII (S = 1) species while in coordi-
nating solvents a low-spin CoIII (S = 0) is expected.[11]
A
detailed study of these spectral characteristics will be pub-
lished separately.[30]
Demetalation of 4M and 4C using 1 m hydrochloric acid
affords 5M and 5C in yields ranging from 59 to 63%
(Scheme 2). No demetalation of the (corrole)cobalt moiety
occurs, as demonstrated in MALDI/TOF mass spectrome-
try by single ionic patterns at m/z = 1246.98 and 1300.8,
which correspond to the 5M and 5C molecular ions, respec-
tively. The relative “protective action” of the cobalt-con-
taining corrole ring during metalation is interesting. Indeed,
direct demetalation from 2M and 2C affords 3M and 3C in
lower yields (around 40%). Other porphyrin–corrole and
bis(corrole) bis(macrocycles) show such behavior; the free-
bases exhibiting instability relative to the metalated deriva-
tives.[31,32]1H NMR spectra of 5M and 5C, recorded in [D5]-
pyridine, do not differ significantly from those of 4M and
4C, apart from the NH proton resonances of the porphyrin
pyrrole units, which are centered at δ = –3.72 and
–3.38 ppm for 5M, and δ = –4.10 and –3.49 ppm for 5C
(Table 1). The UV/Vis spectrum of 5M recorded in CH2Cl2
Figure 3. ORTEP view of the 5M(py)2 complex. Ellipsoids drawn
closely resembles that of 5C (Figure 2). Due to the lower at 50% probability level; hydrogen atoms omitted for clarity.
molar absorptivity of the absorption bands on the corrole,
both spectra exhibit characteristic features of free-base
monoporphyrins, with four Q bands between 500 and
630 nm and a Soret band at 389 nm. This latter band is
Structural Study
broadened slightly by overlap with the Soret band of the
A single-crystal X-ray diffraction analysis of 5M(py)2 re-
corrole ring. With pyridine as solvent, similar UV/Vis spec- vealed the molecular structure of the monometallic co-
tra are again obtained for 5M and 5C (Figure 2). The band balt(iii) complex (Figure 3). The CoIII ion is coordinated
close to 620–625 nm increases in intensity, in accordance to the four pyrrole nitrogen atoms (4Npyrrole) in a planar
with the coordination of two pyridine molecules on the co- conformation (the metal ion is only 0.011 Å out of the
balt atom in the corrole. As observed for 4M and 4C, 5M 4Npyrrole mean plane), lying slightly out of the 4Npyrrole
and 5C exhibit a band at 456 nm in pyridine corresponding centroid Ct1 at 0.070 Å. Two kinds of Co–Npyrrole distances
to the Soret band of the corrole moiety. Finally, crystalli- are observed in the complex [1.869(4)–1.875(4) and
1.896(4)–1.898(4) Å, each group involving the nitrogen
atoms in trans positions], indicating a slightly distorted
4Npyrrole square coordination. In addition, two pyridine
(py) nitrogen atoms (Npy) are in apical positions from the
metal centre at 1.969(4) and 1.978(4) Å, completing a close
square-bipyramidal coordination geometry. These coordi-
nation distances and geometry are very similar to those re-
ported for related complexes. Thus, for the [5,10,15-tris-
(pentafluorophenyl)corrole]cobalt(iii) complex,[33] M–Npyrrole
and M–Npy distances are 1.873–1.900 and 1.994 Å for the
monomer, and 1.868–1.899 and 1.989–2.000 Å for the di-
mer. In the face-to-face homodimetallic bis(corrole) com-
plex [(BCA)Co2(py)3],[28] bearing three coordinated pyri-
dine molecules (one inside and two out of the complex cav-
ity), M–Npyrrole and M–Npy distances are 1.879–1.905 and
1.976–1.979 Å for the hexacoordinate metal centre. In this
latter structure, the coordination distances of the pentaco-
ordinate metal centre, [1.875(4)–1.894(4) for Npyrrole and
1.946(5) Å for Npy], compare well with those of the mono-
Figure 2. UV/Vis spectra of 5M and 5C recorded in CH2Cl2 and
pyridine.
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Bis(macrocycles) Involving a Porphyrin and a meso-Substituted Corrole
FULL PAPER
metallic (corrole–porphyrin)cobalt(iii) complex, where the centroid of the other macrocycle are 7.23 and 6.86 Å,
spacer is a biphenylenyl unit, [(PCB)H2Co(py)],[10] which respectively. Thus, the latter complex exhibits a short
binds one pyridine molecule out of the complex cavity. The “macrocycle-to-macrocycle” distance due to the folding of
corresponding distances were 1.882(3)–1.902(3) (Npyrrole
)
its spacer, which in the relaxed planar conformation corre-
and 1.945(4) Å (Npy). Thus, from penta- to hexacoordinate sponds to the distance observed for the anthracenyl moiety.
(corrole)cobalt(iii) species having pyridine in apical posi- Therefore, thanks to its flexibility, the dimethylxanthene
tions, the most relevant difference in coordination geometry spacer is of great interest for tuning potential metal···metal
concerns: (i) elongation of M–Npy by about 0.03 Å and (ii) or metal···molecule···metal interactions in face-to-face
displacement of the metal centre towards the 4Npyrrole mean macrocyclic complexes.
plane (Ͻ4NpyrroleϾ); the Co···Ͻ4NpyrroleϾ distance being
In 5M(py)2, the slip angle α, defined as the average angle
0.202(1) and 0.252(1) Å for pentacoordinate cases in [(PCB) between the vector joining Ct1···Ct2 and the unit vectors
H2Co(py)] and [(BCA)Co2(py)3] and 0.009(1) and normal to the two macrocyclic least-squares planes [α = (α1
0.011(1) Å for hexacoordinate ones in [(BCA)Co2(py)3] and + α2)/2], is 24.0° and the lateral shift L = sinα·d(Ct1···Ct2)
5M(py)2.
is 2.80 Å [d(Ct1···Ct2) = 6.90 Å]. These values are larger
In the molecular structure of the 5M(py)2complex both than those found in [(BCA)Co2(py)3] (α = 14.7°, L =
macrocycles exhibit a small distortion from planarity, the 1.84 Å), even if α and L slightly differ in their definitions
root mean square deviation of the 23 and 24 atoms from in the two complexes.[28]
the corrole and porphyrin least-squares planes being 0.112
and 0.078 Å, respectively. While the corrole macrocycle
shows a ruffled conformation, as indicated by the displace-
ments of the alternated meso-carbon atoms above and be-
low the corrole mean plane, the porphyrin moiety is closely
planar. Thus, for the corrole ring, the meso-carbon atom
C10 lies 0.210(4) Å above the mean plane, whereas C5 and
C15 lie –0.159(4) and –0.175(4) Å below this plane. With
the porphyrin, only five atoms lie more than 0.1 Å out of
the mean plane [C55, C60, C61, C68, and C71 at 0.128(4),
–0.108(4), –0.122(4), –0.105(4), and –0.207(4) Å, respec-
tively]. [(BCA)Co2(py)3] and [(PCB)H2Co(py)] complexes
have similar macrocycle conformations.[10,28]
Both H(–N) hydrogen atoms were found unambiguously
in the porphyrin cavity, on N7 and N5, and are involved
in hydrogen-bonding interactions with N6 and N8 pyrrole
nitrogen atoms [d(N–H) = 0.95(5) and 0.99(5) Å, d(H···N)
= 2.23(5) and 2.11(5) Å and α(N–H···N) = 120(4) and
127(4)°, respectively].
The coordination of one of the pyridine molecules within
the complex cavity leads to a large open-mouth face-to-face
geometry (the interplanar angle between the macrocycle
mean planes β is 43.2°) due to the important steric effects
with the porphyrin moiety. Nevertheless, the spacer is
folded through the Csp3–O direction (the dihedral angle be-
tween both half parts is 28.9°), allowing for a short pyri-
dine–porphyrin contact that balances the repulsive steric ef-
fect by the attractive (Cpy–)H···π-system interaction (the
4Npyrrole porphyrin centroid Ct2 distance to the closest Hpy
atom is 2.22 Å, and the four H···Ct2···Npyrrole angles range
between 80 and 100°). The anchored sites of both macro-
cycles at the spacer and at the corrole–porphyrin moieties
are 4.64 and 4.79 Å, respectively, apart. The small differ-
ence in distances (0.15 Å) suggests that, while steric repul-
sion mainly drives the corrole macrocycle orientation (lead-
ing to the large β angle), both the spacer folding and the
attractive H···π–porphyrin interaction avoid a larger differ-
ence. Further support for both this attractive interaction
and the role of the spacer follows from a comparison of the
molecular structures of (BCA)Co2(py)3 and 5M(py)2, where
Figure 4. Stacking of 5M(py)2 complexes along the [1 0 0] direction,
including solvent molecules. Ellipsoids drawn at 50% probability
the distances from the hexacoordinate metal centre to the level; hydrogen atoms omitted for clarity.
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1037

J.-M. Barbe, F. Burdet, E. Espinosa, R. Guilard
FULL PAPER
Moreover, the pyridine molecules are almost staggered
around the metal centre; the dihedral angle between their
mean planes being 87.9°. While this almost perpendicular
orientation has also been observed in [(BCA)Co2(py)3]
(88.2°)[28] and [(Me4Ph5Cor)Co(py)2] (83.7°),[27] in the
[5,10,15-tris(pentafluorophenyl)corrole]cobalt(iii) complex
a mutually parallel arrangement between both pyridine
molecules is found for the monomer and dimer.[33]
In the 5M(py)2 crystal structure, the stacking of com-
plexes is driven by two kinds of π–π interactions along the
[100] direction (Figure 4). Hence, while the porphyrin ring
interacts with the adjacent equivalent moiety of another
molecule (the shortest distance is 3.57 Å for two equivalent
meso-C atoms), at the other side of the complex the outer
pyridine molecule makes a π–π interaction with an equiva-
lent molecule of the closest complex (the shortest C–C dis-
tance being 3.33 Å). In the former case, the centroid–
centroid distance is quite large (7.50 Å), indicating an im-
portant lateral shift between the macrocycles. In the second
case, the centroid–centroid distance is 3.63 Å, reflecting sig-
nificant overlap between the π-systems of both pyridine
molecules.
Experimental Section
General Remarks: All analytical grade reagents, obtained from
commercial suppliers, were used without further purification. 5-
Mesityldipyrromethane, 5-(2,6-dichlorophenyl)dipyrromethane,[24]
5-(13,17-diethyl-2,3,7,8,12,18-hexamethylporphyrin-5-yl)-4-formyl-
9,9-dimethylxanthene[13,31,32] (1) were synthesized according to re-
ported procedures. 1H NMR spectra were recorded at 500 MHz
with a Bruker DRX-500 Avance spectrometer of the “Centre de
Spectrométrie Moléculaire de l’Université de Bourgogne” of the
FR 2604. Chemical shifts are expressed in ppm relative to residual
peaks of chloroform (δ = 7.26 ppm), pyridine (δ = 7.19, 7.55,
8.71 ppm) or benzene (δ = 7.16 ppm). UV/Vis spectra were col-
lected with a Varian Cary 1 spectrophotometer in dichloromethane
solution. Infrared spectra were measured in the attenuated total
reflectance mode (ATR) with a Bruker Vector 22 Fourier transform
spectrometer. MALDI/TOF mass spectra were obtained with a
Bruker ProFLEX III spectrometer using dithranol as matrix.
Microanalyses were performed with a Fisons EA 1108 CHNS in-
strument.
[13,17-Diethyl-5-(5-formyl-9,9-dimethylxanthen-4-yl)-2,3,7,8,12,18-
hexamethylporphyrin]zinc(II) (1Zn): A solution of porphyrin 1
(0.200 g, 0.291 mmol, 1 equiv.), zinc acetate dihydrate (0.128 g,
0.582 mmol, 2 equiv.), and sodium acetate trihydrate (0.396 g,
The relative orientation of the inner pyridine in front of 2.91 mmol, 10 equiv.) in a chloroform (35 mL)/methanol (15 mL)
mixture was heated to reflux for 15 min. After cooling to room
temperature, dichloromethane (50 mL) was added. The reaction
mixture was then washed with water (3×100 mL), dried with mag-
nesium sulfate, filtered and the solvents were evaporated. The re-
sulting solid was chromatographed on silica gel using first toluene
as eluent and then dichloromethane to collect a pink fraction. After
concentration, the solid was recrystallized from dichloromethane/
two methyl groups of the mesityl substituents
(Cmethyl···Ctpy···Cmethyl = 160°) seems to indicate a further
stabilisation by two quite weak C–H···aromatic ring interac-
tions (H···Ctpy distances are 3.83 and 4.41 Å). A variable
1H NMR analysis down to 220 K, to visualize tentatively
any interaction involving a methyl proton of a mesityl
group with a pyridine molecule, found no significant varia-
tion in signal shape or chemical shift for the protons con-
cerned.
1
heptane. 1Zn was obtained in 87% yield (0.190 g, 0.253 mmol). H
MNR (CDCl3, 300 K): δ = 1.88 (t, 3JH,H = 7.85 Hz, 6 H, CH3CH2-
porphyrin), 1.92 (s, 6 H, CH3-dimethylxanthene) 2.48 (s, 6 H, CH3-
porphyrin), 3.48 (s, 6 H, CH3-porphyrin), 3.63 (s, 6 H, CH3-por-
3
phyrin), 4.08 (m, 4 H, CH3CH2-porphyrin), 7.05 (t, JH,H
=
3
4
7.68 Hz, 1 H, H-dimethylxanthene), 7.30 (dd, JH,H = 7.39, JH,H
Summary and Conclusion
= 1.19 Hz, 1 H, H-dimethylxanthene), 7.51 (s, 1 H, CHO), 7.60 (t,
3JH,H = 7.71 Hz, 1 H, H-dimethylxanthene), 7.71 (dd, 3JH,H = 7.90,
1Zn reacts with an aryldipyrromethane to afford good
yields of (free-base corrole–porphyrin)zinc complexes (2M
and 2C). Further metalation of the corrole ring by cobalt
followed by demetalation of the porphyrin moiety gives the
(free-base porphyrin–corrole)cobalt complex, which is a
precursor of heterodimetallic derivatives. The “protective”
3
4JH–H = 1.43 Hz, 1 H, H-dimethylxanthene), 7.87 (d, JH,H
=
3
4
6.40 Hz, 1 H, H-dimethylxanthene), 7.93 (dd, JH,H = 7.95, JH,H
= 1.01 Hz, 1 H, H-dimethylxanthene), 10.02 (s, 1 H, Hmeso-porphy-
rin), 10.12 (s, 2 H, Hmeso-porphyrin). MS (MALDI/TOF): m/z =
747.30 [M – H]+; 748.28 calcd. for C46H44N4O2Zn. UV/Vis
(CH2Cl2): λmax (ε × 10–3 Lmol–1 cm–1) = 332.0 (23.6), 406.0 (346),
effect of the zinc ion in the porphyrin ring is evidenced 536.1 (16.9), 572.1 (16.0) nm. IR ν = 2959 (C–H), 2923 (C–H),
˜
2861 (C–H), 1680 (C=O) cm–1. C46H44N4O2Zn (750.27): calcd. C
73.64, H 5.91, N 7.47; found C 73.63, H 6.07, N 7.48.
throughout the synthetic pathway and, especially, during
the first step, leading to the formation of the corrole, where
lower amounts of TFA are required than for the reaction
carried out from 1. Therefore, acidolysis of the dipyrrome-
{5-[5-(5,15-Dimesitylcorrol-10-yl)-9,9-dimethylxanthen-4-yl]-13,17-
diethyl-2,3,7,8,12,18-hexamethylporphyrin}zinc(II) (2M): (Porphy-
thane reactant avoided, and reaction yields in bis(macro- rin)zinc complex 1Zn (0.20 g, 0.27 mmol, 1 equiv.) and mesityldip-
yrromethane (0.28 g, 1.07 mmol, 4 equiv.) were dissolved in 16 mL
of a solution of trifluoroacetic acid (0.02 mmol, 0.08 equiv.) in
CH2Cl2 (10 μL of TFA in 100 mL of CH2Cl2). The reaction mix-
ture was then stirred for 5 h, diluted 25× with CH2Cl2 (400 mL)
cycle) are obviously increased.
In the presence of pyridine, the bis(pyridine) adduct of
5M crystallized. The structure of 5M(py)2was solved, exhib-
iting coordination of the two pyridine molecules on the co-
balt atom of the corrole ring in endo and exo positions.
Another interesting feature is that the complexes are
stacked along the [100] direction through π–π interactions.
Work towards the preparation of heterodimetallic com-
plexes and their use as catalysts for the reduction of di-
oxygen is being carried out.
and
a solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ; 0.182 g, 0.80 mmol, 3 equiv.) in toluene (4 mL) was added
with stirring. After a further 5 min, the reaction mixture was chro-
matographed on silica gel and eluted with CH2Cl2. The first col-
lected, violet, fraction was concentrated, washed with pentane and
dried under vacuum, yielding 0.091 g (27%, 0.07 mmol) of 2M. 1H
MNR (C6D6, 330 K): δ = 0.93 (s, 6 H, CH3-mesityl), 1.48 (s, 6 H,
1038
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2005, 1032–1041

Bis(macrocycles) Involving a Porphyrin and a meso-Substituted Corrole
FULL PAPER
3
3
CH3-mesityl), 1.83 (t, JH,H = 7.71 Hz, 6 H, CH3CH2-porphyrin),
mesityl), 7.09 (br. s, 1 H, H-dimethylxanthene), 7.33 (t, JH,H
=
3
2.11 (s, 6 H, CH3-dimethylxanthene), 2.36 (s, 6 H, CH3-mesityl), 7.62 Hz, 1 H, H-dimethylxanthene), 7.37 (t, JH,H = 7.50 Hz, 1 H,
3
2.60 (s, 6 H, CH3-porphyrin), 2.92 (s, 6 H, CH3-porphyrin), 3.19
H-dimethylxanthene), 7.42 (br. dd, JH,H = 6.32 Hz, 1 H, H-di-
(s, 6 H, CH3-porphyrin), 3.86 (m, 4 H, CH3CH2-porphyrin), 6.81 methylxanthene), 7.55 (m, 6 H, Hβ-corrole + Hmeso-porphyrin),
3
4
(s, 2 H, Hmeta–mesityl), 7.01 (dd, JH,H = 7.18, JH,H = 1.46 Hz, 1
7.91 (dd, 3JH,H = 7.73, 4JH,H = 1.74 Hz, 1 H, H-dimethylxanthene),
7.94 (br. dd, JH,H = 8.03 Hz, 1 H, H-dimethylxanthene), 8.11 (br.
3
3
H, H-dimethylxanthene), 7.15 (t, JH,H = 7.50 Hz, 1 H, H-dimeth-
3
ylxanthene), 7.17 (t, JH,H = 7.86 Hz, 1 H, H-dimethylxanthene),
s, 2 H, Hβ-corrole), 8.39 (br. s, 2 H, Hβ-corrole), 9.44 (s, 1 H, Hmeso
porphyrin) ppm. MS (MALDI/TOF): m/z = 1191.06 [M]+; 1190.63
for C82H78N8O. UV/Vis (CH2Cl2): λmax
(ε×10–3 Lmol–1 cm–1) = 397.0 (238), 508.0 (12.7), 544.0 (11.9),
-
7.23 (s, 2 H, Hmeta-mesityl), 7.34 (dd, 3JH,H = 7.28, 4JH,H = 1.51 Hz,
3
1 H, H-dimethylxanthene), 7.51 (br. d, JH,H = 3.06 Hz, 2 H, Hβ- calcd.
3
4
corrole), 7.72 (dd, JH,H = 7.91, JH,H = 1.53 Hz, 1 H, H-dimeth-
3
4
ylxanthene), 7.75 (dd, JH,H = 7.97, JH,H = 1.52 Hz, 1 H, H-di-
methylxanthene), 7.81 (d, JH,H = 4.38 Hz, 2 H, Hβ-corrole), 8.04
574.0 (17.4), 608.1 (8.35), 633.0 (5.24) nm. IR ν = 3388 (N–H),
˜
3
3349 (N–H), 3278 (N–H), 2960 (C–H), 2921 (C–H), 2859 (C–H)
cm–1. C82H78N8O·2MeOH (1255.66): calcd. C 80.35, H 6.90, N
8.92; found C 80.77, H 6.68, N 8.73.
3
3
(d, JH,H = 3.88 Hz, 2 H, Hβ-corrole), 8.28 (d, JH,H = 4.58 Hz, 2
H, Hβ-corrole), 9.07 (s, 2 H, Hmeso-porphyrin), 9.66 (s, 1 H, Hmeso
porphyrin). MS (MALDI/TOF): m/z = 1253.92 ([M]+·); 1254.54
calcd. for C82H76N8OZn. UV/Vis (CH2Cl2): λmax (ε
10–3 Lmol–1 cm–1) = 399.0 (252), 540.0 (14.6), 574.0 (18.1), 610.0
-
4-[5,15-Bis(2,6-dichlorophenyl)corrol-10-yl]-5-(13,17-diethyl-
×
2,3,7,8,12,18-hexamethyl
porphyrin-5-yl)-9,9-dimethylxanthene
(3C): This compound was obtained as described for 3M, starting
from 2C (0.06 g, 0.046 mmol), in 40% yield (0.023 g, 0.018 mmol).
1H NMR (CDCl3, 300 K): δ = –5.63 (br. s, 1 H, NH-porphyrin),
(5.91), 638.0 (4.17) nm. IR ν = 3366 (N–H), 2960 (C–H), 2918 (C–
˜
H), 2850 (C–H) cm–1. C82H76N8OZn (1254.95): calcd. C 78.48, H
6.10, N 8.93; found C 78.21, H 6.21, N 8.87.
3
–4.97 (br. s, 1 H, NH-porphyrin), 1.88 (t, JH,H = 7.77 Hz, 6 H,
(5-{5-[5,15-Bis(2,6-dichlorophenyl)corrol-10-yl]-9,9-dimethyl- CH3CH2-porphyrin), 2.21 (s, 6 H, CH3-dimethylxanthene), 2.31 (s,
xanthen-4-yl}-13,17-diethyl-2,3,7,8,12,18-hexamethylporphyrin)-
zinc(II) (2C): This compound was synthesized as described above
for 2M, starting from 1Zn (0.20 g, 0.27 mmol, 1 equiv.) and (2,6-
dichlorophenyl)dipyrromethane (0.31 g, 1.07 mmol, 4 equiv.), in
6 H, CH3-porphyrin), 2.84 (br. s, 6 H, CH3-porphyrin), 3.12 (br. s,
6 H, CH3-porphyrin), 3.89 (m, 4 H, CH3CH2-porphyrin), 7.17 (br.
d, JH,H = 7.07 Hz, 1 H, H-dimethylxanthene), 7.24 (m, 5 H, H-
3
dimethylxanthene + Hmeta-dichlorophenyl), 7.41 (m, 4 H, Hpara
-
1
33% yield (0.12 g, 0.09 mmol). H NMR (C6D6, 330 K): δ = 1.75
dichlorophenyl + Hβ-corrole), 7.64 (br. s, 4 H, Hmeta-dichlo-
3
3
4
(t, JH,H = 7.74 Hz, 6 H, CH3CH2-porphyrin), 2.14 (s, 6 H, CH3- rophenyl + Hβ-corrole), 7.90 (dd, JH,H = 6.55, JH,H = 2.96 Hz, 1
3
4
dimethylxanthene), 2.68 (s, 6 H, CH3-porphyrin), 3.16 (s, 6 H, CH3-
H, H-dimethylxanthene), 7.95 (dd, JH,H = 8.06, JH,H = 1.51 Hz,
porphyrin), 3.28 (s, 6 H, CH3-porphyrin), 3.81 (m, 4 H, CH3CH2- 1 H, H-dimethylxanthene), 8.16 (br. s, 2 H, Hβ-corrole), 8.37 (br.
3
porphyrin), 6.87 (t, JH,H = 8.31 Hz, 2 H, Hpara-dichlorophenyl),
6.89 (dd, 3JH,H = 7.19, 4JH,H = 1.30 Hz, 1 H, H-dimethylxanthene),
s, 2 H, Hβ-corrole), 8.66 (br. s, 2 H, Hmeso-porphyrin), 9.39 (s, 1 H,
Hmeso-porphyrin) ppm. MS (MALDI/TOF): m/z = 1244.43 [M]+·;
1244.38 calcd. for C76H62Cl4N8O. UV/Vis (CH2Cl2): λmax
(ε×10–3 Lmol–1 cm–1) = 395.9 (217), 509.0 (10.9), 543.0 (10.1),
3
4
7.09 (dd, JH,H = 8.24, JH,H = 1.15 Hz, 2 H, Hmeta-dichlo-
rophenyl), 7.11 (t, 3JH,H = 7.63 Hz, 1 H, H-dimethylxanthene), 7.18
3
3
(t, JH,H = 7.69 Hz, 1 H, H-dimethylxanthene), 7.28 (dd, JH,H
=
574.0 (15.6), 616.0 (6.77) nm. IR ν = 3359 (N–H), 3312 (N–H),
˜
7.25, JH,H = 1.54 Hz, 1 H, H-dimethylxanthene), 7.43 (dd, JH,H 3280 (N–H), 2960 (C–H), 2922 (C–H), 2859 (C–H) cm–1.
4
3
4
= 8.38, JH,H = 1.02 Hz, 2 H, Hmeta-dichlorophenyl), 7.49 (br. d,
3JH,H = 3.12 Hz, 2 H, Hβ-corrole), 7.75 (m, 2 H, H-dimethylxan-
thene), 7.91 (br. d, 3JH,H = 3.86 Hz, 2 H, Hβ-corrole); 7.93 (d, 3JH,H
C76H62Cl4N8O·CH2Cl2·H2O (1348.14): calcd. C 68.60, H 4.93, N
8.31; found C 68.55, H 4.58, N 8.02.
Mixed Cobalt(III)–Zinc(II) Complex 4M: Two solutions, one of 3M
(0.050 g, 0.040 mmol, 1 equiv.) in dichloromethane (7 mL) and an-
other of cobalt(ii) acetate tetrahydrate (0.025 g, 0.1 mmol, 2.5
equiv) and sodium acetate trihydrate (0.027 g, 0.2 mmol, 5 equiv.)
in methanol (3 mL), were combined and the mixture was heated to
reflux for 15 min. After cooling, dichloromethane (50 mL) was
added and the resulting solution was washed with water
(3×50 mL), dried with magnesium sulfate, filtered and the solvents
were evaporated under vacuum. The residue was then chromato-
3
= 4.51 Hz, 2 H, Hβ-corrole), 8.43 (d, JH,H = 4.61 Hz, 2 H, Hβ-
corrole), 9.31 (s, 2 H, Hmeso-porphyrin), 9.56 (s, 1 H, Hmeso-porphy-
rin). MS (MALDI/TOF): m/z = 1307.34 ([M]+·); 1308.29 calcd. for
C76H60Cl4N8OZn. UV/Vis (CH2Cl2): λmax (ε×10–3 Lmol–1 cm–1) =
399.0 (296), 538.0 (16.1), 573.0 (20.7), 616.9 (5.81), 636.1 (3.81) nm.
IR ν = 3357 (N–H), 2960 (C–H), 2918 (C–H), 2850 (C–H) cm–1.
˜
C76H60Cl4N8OZn (1308.57): calcd. C 69.76, H 4.62, N 8.56; found
C 69.97, H 4.82, N 8.32.
4-(13,17-Diethyl-2,3,7,8,12,18-hexamethylporphyrin-5-yl)-5-(5,15-di- graphed on basic alumina and eluted with CH2Cl2/MeOH (98:2).
mesitylcorrol-10-yl)-9,9-dimethylxanthene (3M): A solution of 2M
(0.06 g, 0.048 mmol) in dichloromethane (60 mL) was stirred vigor-
ously in the presence of hydrochloric acid (1 m, 3×60 mL) in a
separating funnel. The organic layer was washed with water
(3×60 mL), dried with magnesium sulfate, filtered and the solvents
were evaporated. The resultant solid residue was chromatographed
on basic alumina and eluted with CH2Cl2. The first eluting fraction
was concentrated and recrystallized from dichloromethane/meth-
anol to yield 3M as a violet solid (43%, 0.024 g, 0.02 mmol). 1H
NMR (CDCl3, 300 K): δ = –5.43 (br. s, 1 H, NH-porphyrin), –4.69
The violet solid collected from concentration of the first fraction
was recrystallized from CH2Cl2/MeOH, leading to 4M in 86% yield
1
(0.045 mg, 0.034 mmol). H NMR (C5D5N, 330 K): δ = 0.80 (s, 6
3
H, CH3-mesityl), 1.72 (t, JH,H = 7.61 Hz, 6 H, CH3CH2-porphy-
rin), 2.14 (s, 6 H, CH3-mesityl), 2.36 (s, 6 H, CH3-dimethylxan-
thene), 2.65 (s, 6 H, CH3-mesityl), 3.00 (s, 6 H, CH3-porphyrin),
3.36 (s, 6 H, CH3-porphyrin), 3.51 (s, 6 H, CH3-porphyrin), 3.97
3
4
(m, 4 H, CH3CH2-porphyrin), 6.46 (dd, JH,H = 7.25, JH,H
=
3
4
1.57 Hz, 1 H, H-dimethylxanthene), 6.77 (dd, JH,H = 7.26, JH,H
= 1.58 Hz, 1 H, H-dimethylxanthene), 7.23 (m, 2 H, 2 H-dimeth-
(br. s, 1 H, NH-porphyrin), 0.84 (br. s, 6 H, CH3-mesityl), 1.45 ylxanthene), 7.31 (s, 2 H, Hmeta-mesityl), 7.35 (s, 2 H, Hmeta-mes-
3
4
(br. s, 6 H, CH3-mesityl), 1.85 (t, JH,H = 7.76 Hz, 6 H, CH3CH2- ityl), 7.97 (dd, 3JH,H = 8.04, JH,H = 1.42 Hz, 1 H, H-dimethylxan-
3
4
porphyrin), 2.20 (s, 6 H, CH3-dimethylxanthene), 2.25 (s, 6 H, CH3-
porphyrin), 2.43 (s, 6 H, CH3-mesityl), 2.56 (br. s, 6 H, CH3-por-
phyrin), 3.07 (br. s, 6 H, CH3-porphyrin), 3.88 (m, 4 H, CH3CH2-
thene), 8.04 (dd, JH,H = 7.89, JH,H = 1.58 Hz, 1 H, H-dimeth-
3
ylxanthene), 8.22 (d, JH,H = 3.96 Hz, 2 H, Hβ-corrole), 5.58 (d,
3JH,H = 4.61 Hz, 2 H, Hβ-corrole), 8.69 (m, partially overlapped by
3
porphyrin), 6.81 (br. s, 2 H, Hmeta-mesityl), 6.97 (br. s, 2 H, Hmeta
-
a C5D4HN signal, Hβ-corrole), 9.00 (d, JH,H = 4.64 Hz, 2 H, Hβ-
Eur. J. Inorg. Chem. 2005, 1032–1041
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1039

J.-M. Barbe, F. Burdet, E. Espinosa, R. Guilard
FULL PAPER
corrole), 9.92 (s, 2 H, Hmeso-porphyrin), 10.00 (s, 1 H, Hmeso-por-
for C82H78N8O. UV/Vis (CH2Cl2): λmax (ε×10–3 L mol–1 cm–1) =
389.0 (189), 507.0 (14.6), 541.0 (9.91), 576.0 (8.20), 628.0 (4.50) nm.
UV/Vis (pyridine): λmax (ε×10–3 Lmol–1 cm–1) = 399.9 (192), 456.0
phyrin). MS (MALDI/TOF): m/z = 1309.84 [M]+·; 1310.45 calcd.
for
C82H73N8OZnCo.
UV/Vis
(CH2Cl2):
λmax
(ε×10–3 Lmol–1 cm–1) = 393.0 (231), 538.0 (19.0), 575.1 (16.7) nm. (39.2), 505.1 (16.4), 538.9 (11.1), 576.0 (br.) (13.1), 582.1 (br.)
UV/Vis (pyridine): λmax (ε×10–3 L mol–1 cm–1) = 340.0 (39.4), (12.9), 624.0 (20.5) nm. IR ν = 3276 (N–H), 2961 (C–H), 2918 (C–
˜
420.0 (302), 456.0 (34.7), 510.1 (6.96), 550.1 (21.8), 587.0 (16.3),
H), 2858 (C–H) cm–1. C82H75CoN8O (1247.48): calcd. C 80.35, H
623.0 (19.8) nm. IR ν 2958 (C–H), 2920 (C–H), 2858 (C–H) cm–1. 6.90, N 8.92; found C 80.77, H 6.68, N 8.73.
˜
C82H73CoN8OZn (1310.86): calcd. C 75.13, H 5.61, N 8.55; found
C 75.40, H 5.70, N 8.80.
{5,15-Bis(2,6-dichlorophenyl)-10-[5-(13,17-diethyl-2,3,7,8,12,18-
hexamethylporphyrin-5-yl)-9,9-dimethylxanthen-4-yl]corrole}-
cobalt(III) (5C):5C was obtained in 63% yield (0.021 g, 0.016 mmol)
using the same procedure as described for 5M, starting from 4C
Mixed Cobalt(III)–Zinc(II) Complex 4C:4C was prepared as de-
scribed for 4M, starting from 3C (0.050 g, 0.038 mmol, 1 equiv.),
cobalt(ii) acetate tetrahydrate (0.024 g, 0.095 mmol, 2.5 equiv.) and
sodium acetate trihydrate (0.026 g, 0.191 mmol, 5 equiv.). It was
obtained as a violet solid in 87% yield (0.045 g, 0.033 mmol). 1H
NMR (C5D5N, 330 K): δ = 1.70 (t, 3JH,H = 7.64 Hz, 6 H, CH3CH2-
porphyrin), 2.34 (s, 6 H, CH3-dimethylxanthene), 2.97 (s, 6 H, CH3-
porphyrin), 3.46 (s, 6 H, CH3-porphyrin), 3.50 (s, 6 H, CH3-por-
phyrin), 3.94 (m, 4 H, CH3CH2-porphyrin), 6.12 (dd, 3JH,H = 7.30,
1
(0.035 g, 0.026 mmol). H NMR (C5D5N, 330 K): δ = –4.10 (br. s,
1 H, NH-porphyrin), –3.49 (br. s, 1 H, NH-porphyrin), 1.67 (t,
3JH,H = 7.66 Hz, 6 H, CH3CH2-porphyrin), 2.33 (s, 6 H, CH3-di-
methylxanthene), 2.88 (s, 6 H, CH3-porphyrin), 3.39 (s, 6 H, CH3-
porphyrin), 3.47 (s, 6 H, CH3-porphyrin), 3.88 (m. 4 H, CH3CH2-
3
4
porphyrin), 6.27 (dd, JH,H = 7.28, JH,H = 1.61 Hz, 1 H, H-di-
3
4
methylxanthene), 6.83 (dd, JH,H = 7.34, JH,H = 1.62 Hz, 1 H, H-
dimethylxanthene), 7.14 (t, JH,H = 7.63 Hz, 1 H, H-dimethylxan-
thene), 7.22 (t, JH,H = 7.63 Hz, 1 H, H-dimethylxanthene), 7.71
(t, JH,H = 8.22 Hz, 2 H, Hmeta-dichlorophenyl), 7.86 (dd, JH,H
8.16, JH,H = 1.03 Hz, 2 H, Hmeta-dichlorophenyl), 8.00 (m, 4 H, 2
H-dimethylxanthene + 2 Hmeta-dichlorophenyl), 8.32 (d, JH,H
4.10 Hz, 2 H, Hβ-corrole), 8.64 (d, JH,H = 4.09 Hz, 2 H, Hβ-cor-
role), 8.78 (d, JH,H = 4.68 Hz, 2 H, Hβ-corrole), 9.09 (d, JH,H
3
4JH,H = 1.61 Hz, 1 H, H-dimethylxanthene), 6.91 (dd, 3JH,H = 7.33,
3
3
4JH,H = 1.62 Hz, 1 H, H-dimethylxanthene), 7.11 (t, JH,H
=
3
3
3
=
7.62 Hz, 1 H, H-dimethylxanthene), 7.24 (t, JH,H = 7.66 Hz, 1 H,
H-dimethylxanthene), 7.70 (t, JH,H = 8.23 Hz, 2 H, Hmeta-dichlo-
rophenyl), 7.86 (dd, JH,H = 8.22, JH,H = 1.17 Hz, 2 H, Hmeta
dichlorophenyl), 7.96 (dd, JH,H = 7.93, JH,H = 1.63 Hz, 1 H, H-
dimethylxanthene), 7.99 (dd, JH,H = 7.95, JH,H = 1.73 Hz, 1 H,
H-dimethylxanthene), 8.01 (dd, JH,H = 8.17, JH,H = 1.21 Hz, 1
4
3
3
3
4
=
-
3
3
4
3
3
3
4
=
3
4
4.68 Hz, 2 H, Hβ-corrole), 9.90 (s, 1 H, Hmeso-porphyrin), 9.91 (s,
2 H, Hmeso-porphyrin) ppm. MS (MALDI/TOF): m/z = 1300.80
[M]+·; 1300.29 calcd. for C76H59Cl4N8OCo. UV/Vis (CH2Cl2): λmax
(ε×10–3 Lmol–1 cm–1) = 389.0 (160), 506.0 (16.7), 540.0 (11.9),
573.0 (9.22), 627.0 (4.70) nm. UV/Vis (pyridine): λmax
(ε×10–3 L mol–1 cm–1) = 406.0 (182), 444.0 (46.1), 456.0 (48.6),
506.0 (16.9), 541.0 (11.1), 577.0 (b.) (14.1), 591.0 (16.2), 621.9 (28.2)
3
H, Hmeta-dichlorophenyl), 8.30 (d, JH,H = 4.08 Hz, 2 H, Hβ-cor-
3
3
role), 8.59 (d, JH,H = 4.10 Hz, 2 H, Hβ-corrole), 8.81 (d, JH,H
=
3
4.69 Hz, 2 H, Hβ-corrole), 9.12 (d, JH,H = 4.68 Hz, 2 H, Hβ-cor-
role), 9.89 (s, 2 H, Hmeso-porphyrin), 9.95 (s, 1 H, Hmeso-porphyrin).
MS (MALDI/TOF): m/z
=
1364.16, [M]+·; 1364.20
calcd. for C76H57Cl4N8OZnCo. UV/Vis (CH2Cl2): λmax
(ε×10–3 Lmol–1 cm–1) = 389.0 (197), 501.0 (11.1), 538.9 (19.3),
575.1 (15.4) nm. UV/Vis (pyridine): λmax (ε×10–3 Lmol–1 cm–1) =
337.9 (36.4), 420.0 (323), 456.0 (48.6), 515.1 (6.15), 550.1 (20.0),
nm. IR ν = 3275 (N–H), 2960 (C–H), 2920 (C–H), 2860 (C–H)
˜
cm–1. C76H59Cl4CoN8O·MeOH (1333.14): calcd. C 69.37, H 4.76,
N 8.41; found C 69.11, H 5.11, N 8.04.
590.0 (21.3), 621.9 (31.4) nm. IR ν 2961 (C–H), 2927 (C–H), 2862
˜
(C–H) cm–1. C76H57Cl4CoN8OZn·MeOH (1396.52): calcd. C 66.23,
H 4.40, N 8.02; found C 66.48, H 4.38, N 8.38.
Table 3. Crystal data and structure refinement details for 5M(py)2
Formula
Mw
Crystal system
Space group
a [Å]
C92H85CoN10O·2C6H12
1573.94
{10-[5-(13,17-Diethyl-2,3,7,8,12,18-hexamethylporphyrin-5-yl)-9,9-di-
methylxanthen-4-yl]-5,15-dimesitylcorrole}cobalt(III) (5M): A solu-
tion of 4M (35 mg, 26.7 μmol) in dichloromethane (35 mL) was
vigorously stirred with hydrochloric acid (1 m; 3×50 mL) in a sepa-
rating funnel. The organic layer was then washed with distilled
water (3×50 mL), dried with magnesium sulfate, filtered and the
solvents were evaporated under vacuum. The resultant solid residue
was chromatographed on basic alumina and eluted with dichloro-
methane/methanol (98:2). The first eluting fraction was concen-
trated and then recrystallized from dichloromethane/methanol,
yielding 5M (59%, 0.020 g, 0.016 mmol). 1H NMR (C5D5N,
330 K): δ = –3.72 (br. s, 1 H, NH-porphyrin), –3.38 (br. s, 1 H, NH-
triclinic
¯
P1
13.6160(4)
b [Å]
c [Å]
15.8720(5)
20.1957(7)
α [°]
β [°]
83.092(1)
79.587(1)
γ [°]
81.574(1)
4226.6(2)
V [Å3]
Z
2
dcalcd. [g cm–3]
T [K]
1.237
115(2)
0.260
μ (Mo-Kα) [mm–1]
θ range [°]
Index ranges
3
porphyrin), 0.71 (s, 6 H, CH3-mesityl), 1.68 (t, JH,H = 7.59 Hz, 6
1.74 Ͻ θ Ͻ 24.02
–15 Յ h Յ 15
–18 Յ k Յ 12
–23 Յ l Յ 20
17425
11702 (Rint = 0.0524)
11702/1088
R1 = 0.0700; wR2 = 0.1523
R1 = 0.1385; wR2 = 0.1853
1.024
H, CH3CH2-porphyrin), 2.17 (s, 6 H, CH3-mesityl), 2.29 (s, 6 H,
CH3-dimethylxanthene), 2.65 (s, 6 H, CH3-mesityl), 2.93 (s, 6 H,
CH3-porphyrin), 3.33 (s, 6 H, CH3-porphyrin), 3.49 (s, 6 H, CH3-
porphyrin), 3.89 (m, 4 H, CH3CH2-porphyrin), 6.62 (m, 2 H, H-
Collected reflns
Unique reflns
Data/parameters
R indices [I Ն 2σ(I)]
(all data)
3
dimethylxanthene), 7.29 (t, JH,H = 7.57 Hz, 1 H, H-dimethylxan-
thene), 7.33 (m, 5 H, 4 Hmeta-mesityl + 1 H-dimethylxanthene),
7.96 (dd, 3JH,H = 8.01, 4JH,H = 1.53 Hz, 1 H, H-dimethylxanthene),
8.08 (dd, 3JH,H = 7.53, 4JH,H = 1.54 Hz, 1 H, H-dimethylxanthene),
8.23 (d, 3JH,H = 3.88 Hz, 2 H, Hβ-corrole), 8.55 (d, 3JH,H = 4.64 Hz,
GOF
Δρmax/Δρmin [e·Å–3]
0.373/-0.454
3
2 H, Hβ-corrole), 8.73 (d, JH,H = 4.01 Hz, 2 H, Hβ-corrole), 8.96
3
[a] R1 = Σ||Fo| – |Fc||/Σ|Fo|; wR2 = {Σ[w(Fo – Fc ) ]/Σ[wFo4]}1/2. [b]
2
2 2
(d, JH,H = 4.56 Hz, 2 H, Hβ-corrole), 9.94 (s, 3 H, Hmeso-porphy-
rin) ppm. MS (MALDI/TOF): m/z = 1246.98 [M]+·; 1246.54 calcd.
GOF = [Σw(|Fo| – |Fc|)2/(No – Nv)]1/2
.
1040
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 1032–1041

Bis(macrocycles) Involving a Porphyrin and a meso-Substituted Corrole
FULL PAPER
[9] R. Guilard, J. M. Barbe, C. Stern, K. M. Kadish, The Porphy-
rin Handbook (Eds.: K. M. Kadish, K. M. Smith, R. Guilard),
Academic Press, New York, 2003, vol. 18, p. 303–349.
[10] J. M. Barbe, F. Burdet, E. Espinosa, C. P. Gros, R. Guilard, J.
Porphyrins Phthalocyanines 2003, 7, 365–374.
[11] C. Erben, S. Will, K. M. Kadish, The Porphyrin Handbook
(Eds.: K. M. Kadish, K. M. Smith, R. Guilard), Academic
Press, New York, 2000, vol. 2, p. 233–300.
[12] R. Paolesse, The Porphyrin Handbook (Eds.: K. M. Kadish,
K. M. Smith, R. Guilard), Academic Press, New York, 2000,
vol. 2, 201–232.
[13] R. Guilard, F. Jérôme, C. P. Gros, J. M. Barbe, Z. P. Ou, J. G.
Shao, K. M. Kadish, C. R. Acad. Sci. Ser. IIc 2001, 4, 245–
254.
X-ray Crystallography: X-ray diffraction experiment and data pro-
cessing: Dark green single-crystals of prismatic morphology were
grown in a mixture of pyridine and cyclohexane. A specimen of
good quality was selected for low-temperature [T = 115(2) K] X-
ray diffraction. The X-ray source was graphite-monochromatized
Mo-Kα radiation (λ = 0.71073 Å) from a sealed tube. Data were
collected with a Nonius KappaCCD diffractometer, equipped with
a nitrogen jet-stream low-temperature system (Oxford Cryosys-
tems).[34] Lattice parameters were obtained by a least-squares fit to
the optimised setting angles of all collected reflections observed up
to the maximum diffraction angle 2θmax = 48°. Intensity data were
recorded as φ and ω scans with κ offsets. Data reduction was per-
formed using the DENZO program.[35] Table 3 shows crystal data
and some experimental details. Structure solution and refinement:
The structure was solved by direct methods using the SIR97 pro-
gram.[36] Refinements were carried out by full-matrix least squares
on F2 using the SHELXL97 program[37] and the complete set of
reflections. The applied weighting scheme was w = 1/[σ2(Fo2) +
[14] K. M. Kadish, L. Frémond, Z. P. Ou, J. Shao, C. Shi, F. C.
Anson, F. Burdet, C. P. Gros, J. M. Barbe, R. Guilard, J. Am.
Chem. Soc., submitted.
[15] Z. Gross, N. Galili, I. Saltsman, Angew. Chem. Int. Ed. 1999,
38, 1427–1429.
[16] L. Simkhovich, N. Galili, I. Saltsman, I. Goldberg, Z. Gross,
Inorg. Chem. 2000, 39, 2704.
[17] R. Paolesse, S. Nardis, F. Sagone, R. G. Khoury, J. Org. Chem.
2001, 66, 550–556.
[18] D. T. Gryko, Chem. Commun. 2000, 2243–2244.
[19] D. T. Gryko, K. Jadach, J. Org. Chem. 2001, 66, 4267–4275.
[20] C. V. Asokan, S. Smeets, W. Dehaen, Tetrahedron Lett. 2001,
42, 4483–4485.
[21] D. T. Gryko, K. E. Piechota, J. Porphyrins Phthalocyanines
2002, 6, 81–97.
[22] D. T. Gryko, B. Koszarna, Org. Biomol. Chem. 2003, 1, 350–
357.
[23] R. Guilard, D. T. Gryko, G. Canard, J.-M. Barbe, B. Koszarna,
S. Brandès, M. Tasior, Org. Lett. 2002, 4, 4491–4494.
[24] B. J. Littler, M. A. Miller, C. H. Hung, R. W. Wagner, D. F.
O’Shea, P. D. Boyle, J. S. Lindsey, J. Org. Chem. 1999, 64,
1391–1396.
[25] J. W. Buchler, D. P. K. Ng, The Porphyrin Handbook (Eds.:
K. M. Kadish, K. M. Smith, R. Guilard), Academic Press,
New York, 2000, vol. 3, p. 245–294.
2
2
(AP)2 + BP] where P = (Fo + 2Fc )/3, A and B being updated
parameters (at convergence, A = 0.0715 and B = 4.8787). Aniso-
tropic thermal parameters were used for non-H atoms. Most hydro-
gen atoms were observed from Fourier synthesis. Hydrogen atoms
were placed at calculated positions using a riding model [except
both H(–Npyrrole) atoms belonging to the free porphyrin moiety,
for which the structural parameters were refined]. All H atoms were
refined with a global isotropic thermal factor. One ethyl group be-
longing to the porphyrin moiety was disordered over two positions,
showing sites occupation factors of 0.58(2)/0.42(2). Two cyclo-
hexane solvent molecules co-crystallized with the complex.
CCDC-240510 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK, Fax: +44-1223/336-033, E-mail: deposit@ccdc.cam.ac.uk].
[26] K. M. Kadish, G. Moninot, Y. Hu, D. Dubois, A. Ibnlfassi,
J. M. Barbe, R. Guilard, J. Am. Chem. Soc. 1993, 115, 8153–
8166.
[27] R. Guilard, C. P. Gros, F. Bolze, F. Jérôme, Z. P. Ou, J. G.
Shao, J. Fischer, R. Weiss, K. M. Kadish, Inorg. Chem. 2001,
40, 4845–4855.
[28] R. Guilard, F. Jérôme, J. M. Barbe, C. P. Gros, Z. P. Ou, J.
Shao, J. Fischer, R. Weiss, K. M. Kadish, Inorg. Chem. 2001,
40, 4856–4865.
Acknowledgments
This work was supported by the CNRS and Air Liquide. F. B.
gratefully acknowledges the “Région Bourgogne” and CNRS for
financial support. The authors also thank Mr. Marcel Soustelle for
his assistance in the synthesis of pyrrole precursors.
[1] J. P. Collman, R. Boulatov, C. J. Sunderland, The Porphyrin
Handbook (Eds.: K. M. Kadish, K. M. Smith, R. Guilard), Ac-
ademic Press, New York, 2003, vol. 11, p. 1–49.
[2] J. P. Collman, R. Boulatov, C. J. Sunderland, L. Fu, Chem. Rev.
2004, 104, 561–588.
[3] E. Kim, E. E. Chufan, K. Kamaraj, K. D. Karlin, Chem. Rev.
2004, 104, 1077–1133.
[29] K. M. Kadish, Z. P. Ou, J. G. Shao, C. P. Gros, J. M. Barbe, F.
Jérôme, F. Bolze, F. Burdet, R. Guilard, Inorg. Chem. 2002, 41,
3990–4005.
[30] F. Burdet, J.-M. Barbe, Z. P. Ou, J. Shao, K. M. Kadish, E.
Espinosa, C. P. Gros, R. Guilard, manuscript in preparation.
[31] F. Jérôme, C. P. Gros, C. Tardieux, J. M. Barbe, R. Guilard,
New J. Chem. 1998, 22, 1327–1329.
[4] J. M. Barbe, R. Guilard, The Porphyrin Handbook (Eds.: K. M.
Kadish, K. M. Smith, R. Guilard), Academic Press, New York,
2000, vol. 3, p. 211–244.
[5] J. P. Collman, P. S. Wagenknecht, J. E. Hutchison, Angew.
Chem. Int. Ed. Engl. 1994, 33, 1537–1554.
[6] R. Guilard, M. A. Lopez, A. Tabard, P. Richard, C. Lecomte,
S. Brandès, J. E. Hutchison, J. P. Collman, J. Am. Chem. Soc.
1992, 114, 9877–9889.
[32] F. Jérôme, C. P. Gros, C. Tardieux, J. M. Barbe, R. Guilard,
Chem. Commun. 1998, 2007–2008.
[33] A. Mahammed, I. Giladi, I. Goldberg, Z. Gross, Chem. Eur. J.
2001, 7, 4259–4265.
[34] COLLECT Program, Data Collection Software, Nonius, Delft,
The Netherlands, 1998.
[35] Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307–
326.
[7] R. Guilard, S. Brandès, A. Tabard, N. Bouhmaida, C. Lecomte,
P. Richard, J. M. Latour, J. Am. Chem. Soc. 1994, 116, 10202–
10211.
[8] R. Guilard, S. Brandès, C. Tardieux, A. Tabard, M. L’Her, C.
Miry, P. Gouerec, Y. Knop, J. P. Collman, J. Am. Chem. Soc.
1995, 117, 11721–11729.
[36] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.
Giacovazzo, A. Guagliardi, A. G. Moliterni, G. Polidori, R.
Spagna, J. Appl. Crystallogr. 1999, 32, 115–119.
[37] SHELXL97 Program, Program for the Refinement of the Crys-
tal Structures, University of Göttingen, Germany, 1997.
Received September 13, 2004
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1041