Nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins and pyridazine-fused diazacorrinoids: Metal-template syntheses and peripheral functionalizations

Article abstract of DOI:10.1002/chem.201200463

The present paper reports the first comprehensive study on the synthesis, structures, optical and electrochemical properties, and peripheral functionalizations of nickel(II) and copper(II) complexes of β-unsubstituted 5,15-diazaporphyrins (M-DAP; M=Ni, Cu

Full text of DOI:10.1002/chem.201200463

DOI: 10.1002/chem.201200463
Nickel(II) and Copper(II) Complexes of b-Unsubstituted 5,15-
Diazaporphyrins and Pyridazine-Fused Diazacorrinoids: Metal–Template
Syntheses and Peripheral Functionalizations
Yoshihiro Matano,*[a] Tarou Shibano,[a] Haruyuki Nakano,[b] and Hiroshi Imahori[a, c, d]
Abstract: The present paper reports
the first comprehensive study on the
synthesis, structures, optical and elec-
trochemical properties, and peripheral
functionalizations of nickel(II) and
copper(II) complexes of b-unsubstitut-
ed 5,15-diazaporphyrins (M-DAP; M=
Ni, Cu) and pyridazine-fused diazacor-
rinoids (Ni-DACX; X=N, O). These
two classes of compounds were con-
structed starting from mesityldipyrro-
methane by a metal–template method.
Ni-DAP and Cu-DAP were prepared
in high yields by the reaction of the re-
by the reaction with NaN3. In both
cases, the metal centers change their
geometry from tetrahedral to square
planar during the aza-annulation; X-
ray crystallographic analyses of M-
DAPs showed highly planar diazapor-
phyrin p planes. The Q band of Ni-
DAP was redshifted and intensified
compared with that of a nickel–porphy-
rin reference, due to the involvement
of electronegative nitrogen atoms at
the meso positions. It was found that
the peripheral bromination of Ni-DAP
and Ni-DACO occurred regioselective-
ly to afford Ni-DAP-Br4 and Ni-
DACO-Br, respectively. These bromi-
nated derivatives underwent Stille re-
actions with tributylACTHNUGRTNEUNG(phenyl)stannane
to give the corresponding phenylated
derivatives, Ni-DAP-Ph4 and Ni-
DACO-Ph. On the basis of the absorp-
tion spectra and X-ray analysis, it has
been concluded that the attached
phenyl groups efficiently conjugate
with the diazaporphyrin p system. The
present results unambiguously corrobo-
rate that the b-unsubstituted DAPs and
DACXs are promising platforms for
the development of a new class of p-
conjugated azaporphyrin-based materi-
als.
spective
metal–bis(dibromodipyrrin)
Keywords: diazo compounds · mac-
rocycles · porphyrinoids · template
synthesis
complexes with NaN3–CuX (X=I, Br),
whereas Ni-DACN and Ni-DACO
were formed as predominant products
Introduction
rin and tetraazaporphyrin, and the frontier orbital character-
istics of DAP reflect its D2h-symmetric p system. The first
synthesis of DAP by Fischer and co-workers dates back to
1936,[2] and since then, several types of b-substituted deriva-
tives (2,3,7,8,12,13,17,18-octa-alkyl-DAP, tetrabenzo-DAP,
and their relatives) have been reported.[3,4] The preceding
studies have disclosed that the optical, electrochemical, and
coordination properties of DAPs are distinguished from
those of the two parent macrocycles. We envisioned that b-
unsubstituted (b-free) DAP would also be a promising plat-
form for the further development of azaporphyrin-based
materials, because they are diversely tunable at the periph-
ery. To our knowledge, however, very little information is
available about b-free DAP derivatives,[5] and no attempt
has been made to chemically functionalize their p systems.
In this study, we aimed to establish practical methods for
the synthesis and functionalization of b-free DAPs as well as
to reveal the structure–property relationship of the resulting
p systems. Herein, we report a highly efficient metal–tem-
plate synthesis of nickel(II) and copper(II) complexes of b-
free 5,15-diazaporphyrin (M-DAPs; M=Ni, Cu) and the un-
expected formation of pyridazine-fused diazacorrinoids (Ni-
DACX ; X =N, O). The crystal structures, optical and elec-
trochemical properties, and peripheral functionalizations of
these two p systems are also reported.
Recent developments of phthalocyanine-based functional
dyes, pigments, and electronic materials have stimulated the
search for a new azaporphyrin family that is easily accessible
and finely tunable by conventional synthetic methods.[1]
5,15-Diazaporphyrin (DAP) is a structural hybrid of porphy-
[a] Prof. Dr. Y. Matano, T. Shibano, Prof. Dr. H. Imahori
Department of Molecular Engineering
Graduate School of Engineering, Kyoto University
Nishikyo-ku, Kyoto 615-8510 (Japan)
Fax : (+81)75-383-2571
E-mail: matano@scl.kyoto-u.ac.jp
[b] Prof. Dr. H. Nakano
Department of Chemistry, Graduate School of Sciences
Kyushu University
Fukuoka 812-8581 (Japan)
[c] Prof. Dr. H. Imahori
Institute for Integrated Cell-Material Sciences (WPI-iCeMS)
Kyoto University
Nishikyo-ku, Kyoto 615-8510 (Japan)
[d] Prof. Dr. H. Imahori
Fukui Institute for Fundamental Chemistry
Kyoto University
Sakyo-ku, Kyoto 606-8103 (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201200463.
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FULL PAPER
Results and Discussion
6Ni by treatment with an aqueous HCl solution. The yields
and the distribution of 4Ni/5Ni/6Ni varied to some extent
depending on the reaction conditions, although Ni-DACs
(5Ni/6Ni) were always formed predominantly (Table 1, en-
tries 1 and 2). To our surprise, however, the addition of cop-
per(I) salts dramatically changed the reaction outcome.
When NaN3 was treated with CuI (8 equiv each) in DMF
before the addition of 3Ni, Ni-DAP 4Ni was exclusively
formed in 86% yield (Table 1, entry 3). It seemed that CuN3
was generated as an active reagent from CuI and NaN3.[9]
The amounts of NaN3–CuI could be reduced to 4 equiv
without decreasing the yield of 4Ni (Table 1, entry 4). The
use of CuBr was also effective for the synthesis of 4Ni
(Table 1, entry 5). Under the NaN3–CuI condition, 3Cu was
converted to 4Cu[5] in 89% yield (Table 1, entry 6). The
high-yield formation of 4M (M=Ni, Cu; constantly >85%)
in the NaN3–CuI system was reproducible.[10] These results
definitely show that the copper-assisted metal–template
method is promising for the synthesis of b-free diazapor-
phyrin–nickel(II) and copper(II) complexes.[11]
To achieve the first objective, namely the synthesis of M-
DAPs, we applied a metal–template method by using dipyr-
rin–metal complexes and sodium azide (NaN3), which had
been employed for the synthesis of b-substituted DAP–
copper complexes.[6] Scheme 1 and Table 1 summarize the
present results.
The pyridazine-fused diazacorrinoid skeleton in 5Ni and
6Ni is unprecedented, and its formation is worth noting.
Scheme 2 illustrates a plausible reaction pathway leading to
Scheme 1. Synthesis of 4Ni, 4Cu, 5Ni, and 6Ni. R=2,4,6-Me3C6H2.
Table 1. The metal–template aza-annulation of 3M (M=Ni, Cu).[a]
Entry
3M
Reagents
Products (Yields [%])[b]
1
2
3
4
5
6
3Ni
3Ni
3Ni
3Ni
3Ni
3Cu
NaN3 (7 equiv)
NaN3 (4 equiv)
NaN3–CuI (8 equiv)
NaN3–CuI (4 equiv)
NaN3–CuBr (4 equiv)
NaN3–CuI (4 equiv)
4Ni (5), 5Ni (13), 6Ni (15)
4Ni (12), 5Ni (13), 6Ni (20)
4Ni (86)
4Ni (88)
4Ni (82)
Scheme 2. A plausible reaction pathway for the formation of 5Ni in the
NaN3 system. R=2,4,6-Me3C6H2.
4Cu (89)
5Ni. In the absence of CuI, the azido moiety in species A
(X=N3 or NH2) may add to the N=C(a) bond of the adja-
cent pyrrole ring accompanied by evolution of N2 to gener-
ate species B or its tautomer. The subsequent skeletal rear-
[a] [3M]=0.5–1.5 mm. [b] Isolated yields based on 3M.
Consecutive treatment of mesityldipyrromethane 1 (mesi-
tyl=2,4,6-Me3C6H2) with N-bromosuccinimide (NBS) and
2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) gave dibro-
modipyrrin 2 in 80% yield. Complexation between 2 and
rangement of the diazabicycloACTHNGUETRNNU[G 3.1.0]hexene ring in B leads
to 5Ni. In the NaN3–CuI system, the copper is likely to en-
hance the leaving ability of X (X=Br) in A through the co-
ordination or oxidative addition, which results in the exclu-
sive formation of 4Ni. In both systems, the high affinity of
nickel(II) to adopt a square-planar geometry plays a crucial
role in promoting the aza-annulation steps.
NiACHTUNGTRENNUNG(OAc)2 proceeded smoothly to give bis(dibromodipyrrin)-
nickel(II) complex 3Ni in 95% yield. Compound 3Ni was
also obtained in 79% yield (based on 1) without isolation of
2. Heating a mixture of 3Ni, NaN3 (7 equiv), and DMF at
1108C for a few hours afforded three major products, which
were separable from one another by silica-gel column chro-
matography. The purple solid (Rf =0.6; hexane/EtOAc 5:1)
was an expected product, Ni-DAP (4Ni), whereas the green
solids (Rf =0.3 and 0.2) were found to be unexpected prod-
ucts, Ni-DACN (5Ni) and Ni-DACO (6Ni).[7] The structures
of these products were determined on the basis of the spec-
tral data, elemental analyses, and X-ray diffraction analyses
(see below).[8] Compound 6Ni was formed via hydrolysis of
the imine moiety of 5Ni during the reaction or column chro-
matography. In fact, 5Ni was quantitatively transformed to
The 1H NMR spectrum of 4Ni in CD2Cl2 showed two
kinds of pyrrole-b protons at d=8.78 and 9.14 ppm (each, d,
4H), whereas the 1H NMR spectra of 5Ni and 6Ni
(Figure 1) displayed six kinds of pyrrole-b protons (each,
1H, d, J=4.3–5.1 Hz) and two olefinic protons (each, d, 1H,
J=9.7–9.9 Hz). All the peripheral protons of 5Ni and 6Ni
1
were assigned by H–1H COSY and NOESY techniques. In
the IR spectrum of 6Ni (KBr pellet), the C=O stretching vi-
bration mode was detected at 1682 cmÀ1. The structures of
3M, 4M, and 5Ni were further elucidated by X-ray crystal-
lography.[12] The ORTEP diagrams are shown in Figures 2, 3,
4, and 5 together with selected bond lengths and angles. As
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Y. Matano et al.
Figure 4. Crystal structure of 4Cu (30% probability ellipsoids); hydrogen
atoms are omitted for clarity. a) Top view and b) side view. Selected bond
Figure 1. 1H NMR spectrum (aromatic region) of 6Ni in CD2Cl2.
À
À
À
lengths (ꢁ) and angles (8): Cu N1 1.953(2); Cu N2 1.945(3); N3 C1
À
1.321(4); N3 C9 1.329(4); N1-Cu-N2 89.42(10); N1’-Cu-N2 90.58(10);
C1-N3-C9 122.2(3).
Figure 5. Crystal structure of 5Ni (30% probability ellipsoids); hydrogen
atoms are omitted for clarity. a) Top view and b) side view. Selected bond
Figure 2. Crystal structures of a) 3Ni and b) 3Cu (30% probability ellip-
soids). Hydrogen atoms are omitted for clarity. a) Selected bond lengths
À
À
À
lengths (ꢁ) and angles (8): Ni N1 1.832(7); Ni N2 1.855(7); Ni N3
À
À
À
(ꢁ) and angles (8): Ni N1 1.950(4); Ni N2 1.963(4); Ni N3 1.973(3);
À
À
À
À
1.832(7); Ni N4 1.875(6); N4 N5 1.414(10); N5 C1 1.438(11); N5 C18
À
Ni N4 1.946(3); N1-Ni-N2 92.04(15); N1-Ni-N3 113.43(14); N1-Ni-N4
À
À
À
1.357(14); N6 C9 1.357(10); N6 C10 1.294(11); N7 C18 1.314(14); N1-
Ni-N2 92.1(3); N2-Ni-N3 90.3(3); N3-Ni-N4 93.2(3); N1-Ni-N4 84.4(3);
N1-C1-N5 110.7(8); C1-N5-N4 114.5(7); C1-N5-C18 121.5(8); N5-C18-N7
115.9(9); C9-N6-C10 115.8(8).
136.72(14); N2-Ni-N3 110.61(15); N2-Ni-N4 111.42(14); N3-Ni-N4
92.32(14). b) Selected bond lengths (ꢁ) and angles (8) of one of the two
À
À
À
independent molecules: Cu2 N5 1.954(4); Cu2 N6 1.948(4); Cu2 N7
À
1.964(4); Cu2 N8 1.946(4); N5-Cu2-N6 94.29(18); N5-Cu2-N7
129.02(18); N5-Cu2-N8 104.21(18); N6-Cu2-N7 104.18(17); N6-Cu2-N8
136.29(19); N7-Cu2-N8 94.34(18).
shown in Figure 1a, the nickel center in 3Ni adopts a distort-
À
ed tetrahedral geometry with Ni N bond lengths of
1.950(4)–1.973(3) ꢁ and endocyclic N-Ni-N bond angles of
92.04(15)–92.32(14)8. The dihedral angle between two N-Ni-
N planes of 3Ni (83.68) is considerably larger than that of
a,a’-unsubstituted analogue (38.58) reported by Scott and
co-workers.[13] This is attributable to the electrostatic repul-
sion between the facing bromine atoms in 3Ni. In sharp
contrast, each nickel center in 4Ni and 5Ni adopts a square-
planar geometry at the core (Figures 3 and 5). The DAP p
plane of 4Ni is highly planar (root mean square of devia-
tions of the 24 atoms from the mean p plane (DdRMS
0.018 ꢁ) compared with the DAC p plane of 5Ni (DdRMS
=
=
À
0.042 ꢁ; Figure S1 in the Supporting Information). The Ni
N distances of 4Ni and 5Ni are 1.913(2)–1.915(2) ꢁ and
1.832(7)–1.875(6) ꢁ, respectively, indicating that the N4-co-
ordination sphere differs slightly between these two macro-
cycles. The structures of 3Cu and 4Cu were also elucidated
by X-ray crystallography (Figures 2b and 4).
Figure 3. Crystal structure of 4Ni (30% probability ellipsoids); hydrogen
atoms are omitted for clarity. a) Top view and b) side view. Selected bond
À
À
À
lengths (ꢁ) and angles (8): Ni N1 1.9145(16); Ni N2 1.9131(16); N3 C1
À
1.325(3); N3 C9 1.321(3); N1-Ni-N2 89.33(7); N1’-Ni-N2 90.67(7); C1-
N3-C9 120.14(18).
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Nickel(II) and Copper(II) Complexes of 5,15-Diazaporphyrins
FULL PAPER
The copper center in 3Cu adopts a tetrahedral geometry
shifted and largely intensified compared with that of 7. This
is deeply related to the nondegenerate frontier orbitals of
the DAP p systems[4d,e] (see below). The Ni-DAC derivatives
5Ni and 6Ni displayed broad and split absorption bands
reaching l=700 nm due to their unsymmetrical structures.
À
with Cu N bond lengths of 1.946(5)–1.964(5) ꢁ, whereas
À
that in 4Cu adopts a square-planar geometry with Cu N
bond lengths of 1.945(3)–1.953(2) ꢁ. It is evident that the
aza-annulation from 3Cu also produces a completely planar
À
Cu–DAP p plane (DdRMS =0.019 ꢁ) in 4Cu. The N
C(a) bond lengths of 4Ni and 4Cu are almost identical,
G
whereas the C(a)-NACHTUNGTRENNUNG(meso)-C(a) bond angle of 4Cu is slight-
ly wider than that of 4Ni. This reflects the difference in the
À
respective M N bond lengths (1.953(2) and 1.945(3) ꢁ for
4Cu; 1.9145(16) and 1.9131(16) ꢁ for 4Ni).
To reveal the optical and electrochemical properties of
the present b-free DAP and DAC p systems, UV/Vis ab-
sorption spectra and redox potentials of 4m, 5Ni, and 6Ni
as well as porphyrin reference 7 were recorded in CH2Cl2
(Table 2, Figure 6). In the absorption spectra of 4m, Soret
and Q bands appeared at lmax =373–397 and 571–577 nm, re-
spectively. It should be noted that the Q band of 4Ni is red-
The incorporation of two nitrogen atoms into the meso
positions induced anodic shifts for both oxidation and reduc-
tion potentials (Eox and Ered) of the porphyrin p system; in
cyclic voltammetry (CV) measurements, 4Ni showed rever-
sible redox processes at Ered,1 =À1.40 and Eox,1 = +0.80 V,
whereas 7 showed the respective processes at Ered,1 =À1.77
and Eox,1 = +0.59 V vs. Fc/Fc+ (Figure S2 in the Supporting
Information). These results indicate that 4Ni is harder to
oxidize and easier to reduce than 7. The Ni-DACO 6Ni also
showed reversible redox processes at Ered,1 =À1.56 V and
Table 2. Optical and electrochemical data for 4–12.[a]
lmax [nm] (loge)
Eredox [V][b]
4Ni
4Cu
5Ni
6Ni
7
373 (4.8), 390 (4.9), 571 (4.8)
384 (5.0), 397 (5.0), 577 (4.9)
406 (4.8), 556 (4.2), 592 (4.2), 638 (4.6)
386 (4.7), 580 (4.2), 623 (4.5)
398 (5.4), 514 (4.2), 547 (3.9)
401 (5.0), 587 (4.9)
+0.80, À1.40, À2.02
+0.77, À1.37, À1.95
N.m.
+0.54, À1.56, À2.00
+1.00, +0.59, À1.77
N.m.
E
ox,1 = +0.54 V. Accordingly, the energy gap (Eox–Ered) de-
creases in the order: (2.36 V)>4Ni (2.20 V)>6Ni
7
(2.10 V), which correlates well with the order of the lowest
excitation energies observed in their absorption spectra.
DFT calculations on the meso-phenyl-substituted models
4Nim (R=Ph) and 7m shed light on the character of their
frontier orbitals (Figure 7). The replacement of two meso
8
9
374 (4.9), 420 (5.1), 612 (4.8)
385 (4.7), 589 (4.2), 626 (2.8)
389 (4.7), 576 (4.2), 632 (4.4)
389 (4.8), 591 (4.3), 635 (4.5)
+0.68, À1.33, À2.01
10
11
12
N.m.
N.m.
+0.50, À1.54, À2.02
[a] Recorded in CH2Cl2; N.m.=not measured. [b] Redox potentials (vs.
ferrocene/ferrocenium couple; with Bu4N+PF6À; Ag/Ag+).
Figure 7. Molecular orbitals (HOMOÀ1, HOMO, LUMO, and LUMO+
1) of 4Nim and 7m, and their energies (in eV) calculated by the B3LYP
method.
carbons by nitrogens (from 7m to 4Nim) breaks the near
degeneracy of the frontier orbitals and stabilizes LUMO
(from À2.31 to À2.89 eV) larger than HOMO (from À5.39
to À5.61 eV). As a result, the HOMO–LUMO gap of 4Nim
becomes narrow compared with that of 7m. This is in good
accordance with a trend of the redox potentials observed for
the corresponding p systems, 4Ni and 7.
Furthermore, we examined peripheral functionalizations
of the b-free DAP and DAC p systems by using a bromina-
tion–cross-coupling strategy (Scheme 3). The Ni-DAP 4Ni
Figure 6. Absorption spectra of a) 4Ni (blue), 7Ni (red), 9 (green) and
b) 5Ni (green), 6Ni (purple), 12 (blue) in CH2Cl2.
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Y. Matano et al.
Figure 9. Crystal structure of 11 (30% probability ellipsoids); hydrogen
atoms are omitted for clarity. a) Top view and b) side view. Selected bond
À
À
À
lengths (ꢁ) and angles (8): Ni N1 1.857(5); Ni N2 1.825(5); Ni N3
À
À
À
À
1.898(5); Ni N4 1.847(5); N3 N6 1.385(6); N5 C1 1.342(7); N5 C18
À
À
À
1.322(7); N6 C9 1.392(8); N6 C10 1.418(7); C10 O 1.217(7); N1-Ni-N2
90.7(2); N2-Ni-N3 83.2(2); N3-Ni-N4 93.6(2); N4-Ni-N1 92.5(2); N2-C9-
N6 114.4(5); C9-N6-N3 112.7(5); C9-N6-C10 121.9(5); N6-C10-O
119.6(6); C1-N5-C18 119.6(5).
Scheme 3. Functionalizations of 4Ni and 6Ni. R=2,4,6-Me3C6H2.
reacted with excess NBS in CHCl3 to give Ni-DAP-Br4 8 in
90% yield. It is of interest that the bromination of 4Ni oc-
curred regioselectively at the pyrrole-b carbons apart from
the meso-mesityl groups, probably due to the steric reason.
possess mostly planar p planes (DdRMS =0.045 ꢁ for 9,
0.059 ꢁ for 11). It is noteworthy that dihedral angles be-
tween the b-phenyl rings and the mean DAP p plane in 9
(16.2–34.68) are much narrower than those between the b-
xylyl rings and the mean porphyrin p plane in nickel por-
phyrin P1 (48.0–53.48) reported by Osuka and co-workers.[12]
This is attributable to the different steric effects of the meso
bridges, nitrogen atom (in 9) and CH (in P1); because 9 has
no substituent on the meso nitrogen atoms, the b-phenyl
rings can lean to the DAP p plane to a large extent.
The Stille coupling of 8 with tributyl
ACHTUNGTRENNUNG
ceeded smoothly in the presence of [PdAHCUTNGTRENNUNG
give Ni-DAP-Ph4 9. According to a similar protocol, the Ni-
DACO 6Ni was also converted to DACO-Ph 12 via Ni-
DACO-Br 10 (main product in bromination).
The crystal structures of 9 and Ni-DACO-Br2 11 (minor
product in bromination) were elucidated by X-ray crystal-
lography. As shown in Figures 8 and 9, compounds 9 and 11
In the absorption spectra, both Soret and Q bands of 9
are redshifted by l=30 and 41 nm, respectively, relative to
the corresponding absorption bands of 4Ni (Figure 6). The
degree of b-substitution-induced redshifts observed for the
NiDAP derivatives 9 versus 4Ni is appreciably larger than
that observed for the Ni-porphyrin counterparts P1[14] versus
P2[15] with the same meso-aryl groups (DlSoret =19 nm;
DlQ =16 nm). Obviously, the b-phenyl groups in 9 are conju-
gated with the porphyrin p system more efficiently than are
the b-xylyl groups in P1, which agrees well with the results
on the X-ray diffraction analyses. The effective p conjuga-
tion was also observed for 12, which exhibited a redshift of
12 nm for the longest Q band relative to 6Ni (Figure 6).
Conclusion
We successfully established an efficient metal–template syn-
thesis of b-free 5,15-diazaporphyrin-nickel and -copper com-
plexes by using the NaN3–CuX reagents. In addition, we un-
expectedly found that a new azaporphyrin family, the pyrid-
azine-fused diazacorrinoides, was produced predominantly
under the classical condition (NaN3/DMF). Furthermore, we
demonstrated for the first time that the successive bromina-
tion–Stille coupling reactions could be utilized for the regio-
Figure 8. Crystal structure of 9 (30% probability ellipsoids); hydrogen
atoms are omitted for clarity. a) Top view and b) side view. Selected bond
À
À
À
lengths (ꢁ) and angles (8): Ni N1 1.923(2); Ni N2 1.920(2); N3 C1
À
À
À
1.322(3); N3 C9 1.319(3); C2 C19 1.487(3); C8 C25 1.485(3); N1-Ni-N2
89.12(9); N1’-Ni-N2 90.88(9), C1-N3-C9 121.4(2); C1-C2-C19 128.6(2);
C9-C8-C25 127.5(2).
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Nickel(II) and Copper(II) Complexes of 5,15-Diazaporphyrins
FULL PAPER
Synthesis of 3Cu: To a solution of 2 (35.4 mg, 0.0843 mmol) in MeOH
(20 mL) was added CuACTHNUTRGNEUNG(OAc)2 (7.2 mg, 0.040 mmol). After 1 h of stirring
selective functionalizations of the DAP and DAC p systems
at the periphery. The newly constructed diazaporphyrin de-
rivatives exhibited the characteristic properties owing to the
electronic and steric effects of the meso nitrogen atoms. The
present results unambiguously corroborate that the b-free
DAPs and DACs are promising platforms for the develop-
ment of a new class of p-conjugated azaporphyrin-based ma-
terials.
at RT, the mixture was evaporated under reduced pressure, and a solid
residue was recrystallized from CH2Cl2/MeOH to give 3Cu as a green
solid (34.3 mg, 90%). M.p. >3008C; HRMS (ESI): m/z calcd for
C36H31Br4CuN4: 897.8573 [M+H]+; found: 897.8567; UV/Vis (CH2Cl2):
lmax (e)=462 (35000), 515 nm (48000mÀ1 cmÀ1); elemental analysis calcd
(%) for C36H30Br4CuN4 (Mw): C 47.95, H 3.35, N 6.21, Br 35.44; found: C
47.72, H 3.33, N 6.08, Br 35.34.
Reaction of 3Ni with NaN3 (typical procedure): A mixture of 3Ni
(500 mg, 0.557 mmol), sodium azide (157 mg, 2.42 mmol), and DMF
(500 mL) was stirred at 1108C. After 1 h, toluene and brine were added,
and the organic phase was washed with brine several times. The toluene
layer was separated, washed with water twice, and evaporated under re-
duced pressure to leave a solid residue, which was then subjected on
silica-gel column chromatography (hexane/EtOAc 5:1). The major three
products, 4Ni (Rf =0.6; 39.9 mg, 12%), 5Ni (Rf =0.3; 43.4 mg, 13%), and
6Ni (Rf =0.2; 68.1 mg, 20%) were isolated separately. The yields and the
distribution of 4Ni/5Ni/6Ni varied to some extent depending on the re-
action conditions employed. 4Ni: m.p. >3008C; 1H NMR (400 MHz,
CD2Cl2): d=1.79 (s, 12H; para-Me), 2.61 (s, 6H; ortho-Me), 7.29 (s, 4H;
Ar-meta), 8.78 (d, J=4.8 Hz, 4H; pyrrole-b), 9.14 ppm (d, J=4.8 Hz, 4H;
pyrrole-b); 13C{1H} NMR (100 MHz, CD2Cl2): d=151.0, 144.5, 139.3,
139.0, 135.5, 134.5, 133.8, 128.3, 121.2, 30.1, 21.5 ppm; HRMS (ESI): m/z
calcd for C36H30N6Ni: 604.1885 [M]+; found: 604.1847; UV/Vis (CH2Cl2):
lmax (e)=373 (62000), 390 (78000), 571 nm (60000mÀ1 cmÀ1); elemental
analysis calcd (%) for C36H30N6Ni (Mw): C 71.43, H 5.00, N, 13.88; found:
C 69.76, H 5.07, N 13.09. 5Ni: m.p. >3008C; 1H NMR (400 MHz,
CDCl3): d=1.82 (s, 6H; ortho-Me), 1.91 (s, 6H; ortho-Me), 2.53 (s, 3H;
para-Me), 2.54 (s, 3H; para-Me), 7.18 (s, 4H; Ar-meta), 7.43 (d, J=
9.8 Hz, 1H; vinyl), 7.91 (d, J=9.8 Hz, 1H; vinyl), 7.99 (d, J=5.0 Hz, 1H;
pyrrole-b), 8.02 (d, J=4.4 Hz, 1H; pyrrole-b), 8.24 (d, J=4.8 Hz, 1H;
pyrrole-b), 8.27 (br-s, 1H; NH), 8.40 (d, J=4.8 Hz, 1H; pyrrole-b), 8.49
(d, J=5.0 Hz, 1H; pyrrole-b), 9.06 ppm (br-s, 1H; pyrrole-b); 1H NMR
(400 MHz, CD2Cl2): d=1.82 (s, 6H; ortho-Me), 1.91 (s, 6H; ortho-Me),
2.53 (s, 3H; para-Me), 2.54 (s, 3H; para-Me), 7.20 (s, 4H; Ar-meta), 7.46
(d, J=9.7 Hz, 1H; vinyl), 7.88 (d, J=9.7 Hz, 1H; vinyl), 7.99 (2ꢂd, J=
4.8 Hz, each 1H; pyrrole-b), 8.20 (d, J=4.4 Hz, 1H; pyrrole-b), 8.34 (d,
J=4.8 Hz, 1H; pyrrole-b), 8.34 (s, 1H; NH), 8.44 (d, J=4.8 Hz, 1H; pyr-
role-b), 9.06 ppm (d, J=4.8 Hz, 1H; pyrrole-b); HRMS (ESI): m/z calcd
for C36H32N7Ni: 620.2067 [M+H]+; found: 620.2061; UV/Vis (CH2Cl2):
Experimental Section
All melting points were recorded on a Yanagimoto micromelting point
apparatus and are uncorrected. 1H and 13C{1H} NMR spectra were re-
corded on a JEOL EX400, AL300, or ECA-600P spectrometers. Chemi-
cal shifts are reported in ppm as the relative values versus tetramethylsi-
lane. Selected 1H NMR spectra are shown in Figures S3–S12 in the Sup-
porting Information. 1H–1H COSY and NOESY spectra were recorded
on JEOL ECA-600P and JEOL ECS-400 spectrometers, respectively.
HRMS were obtained on a Thermo EXACTIVE spectrometer. IR spec-
tra were obtained on a JASCO FT/IR-470 Plus spectrometer. UV/Vis ab-
sorption spectra were obtained on a PerkinElmer Lambda 900 UV/Vis/
NIR spectrometer. Electrochemical measurements were performed on
a CH Instruments model 660 A electrochemical workstation by using
a glassy carbon working electrode, a platinum wire counter electrode,
and an Ag/Ag+ [0.01m AgNO3, 0.1m nBu4NPF6 (MeCN)] reference elec-
trode. The potentials were calibrated with ferrocene/ferrocenium [Emid
=
+0.20 V vs Ag/AgNO3]. Elemental analyses were performed at the Mi-
croanalytical Laboratory of Kyoto University. Mesityldipyrromethane
1 was prepared according to the reported procedure.[16] Sodium azide
(>98%), copper iodide (>99.5%), copper bromide (>95%), and dehy-
drated DMF (water content <0.005%) were purchased from Wako Pure
Chemical Industries. All chemicals and solvents were of reagent-grade
quality and used without further purification. TLC was performed with
Alt. 5554 DC-Alufolien Kieselgel 60 F254 (Merck), and preparative
column chromatography was performed by using UltraPure SilicaGel
(230–400 mesh; SiliCycle Inc.) or silica gel 60 (spherical, neutrality; Na-
calai tesque). All the reactions were performed under an argon atmos-
phere.
lmax (e)=406
(64000),
556
(17000),
592
(15000),
638 nm
(37000mÀ1 cmÀ1); IR (KBr): n˜max =3303 (NH) cmÀ1; elemental analysis
calcd (%) for C36H31N7Ni (Mw): C 69.70, H 5.04, N 15.80; found: C 69.26,
Synthesis of 2: Compound 1 (3.0 g, 11 mmol) was taken in dry THF
(150 mL) and cooled to À788C. NBS (4.0 g, 22 mmol) was added in two
portions over 1 h. After NBS dissolved completely, a THF solution
(15 mL) of DDQ (2.60 g, 11.4 mmol) was added dropwise over 10 min.
The reaction mixture was warmed to RT and then evaporated under re-
duced pressure to give a solid residue, which was washed with hexane/
CH2Cl2. The residue was then immediately subjected to silica-gel column
chromatography (hexane as an eluent) to give 2 (Rf =0.7) as a yellow
solid (3.8 g, 80%). M.p. 1378C; 1H NMR (400 MHz, CD2Cl2): d=2.05 (s,
6H; ortho-Me), 2.33 (s, 3H; para-Me), 6.26 (d, J=4.4 Hz, 2H; pyrrole-
b), 6.29 (d, J=4.4 Hz, 2H; pyrrole-b), 6.92 ppm (s, 2H; ArH);
13C{1H} NMR (CD2Cl2): d=140.6, 138.6, 137.1, 129.1, 128.3, 120.9, 21.2,
19.9 ppm; HRMS (ESI): m/z calcd for C18H17N2Br2: 418.9758 [M+H]+
(78Br,78Br); found: 418.9753; UV/Vis (CH2Cl2): lmax (e)=445 nm
(21000mÀ1 cmÀ1); elemental analysis calcd (%) for C18H16Br2N2 (Mw): C
51.46, H 3.84, N 6.67, Br 38.01; found: C 51.47, H 3.70, N 6.57, Br 38.11.
1
H 5.19, N 15.70%. 6Ni: m.p. >3008C; H NMR (400 MHz, CD2Cl2): d=
1.82 (s, 6H; ortho-Me), 1.92 (s, 6H; ortho-Me), 2.55 (s, 3H; para-Me),
2.56 (s, 3H; para-Me), 7.19 (s, 2H; Ar-meta), 7.22 (s, 2H; Ar-meta), 7.83
(d, J=9.9 Hz, 1H; vinyl), 8.02 (d, J=4.4 Hz, 1H; pyrrole-b), 8.05 (d, J=
5.1 Hz, 1H; pyrrole-b), 8.26 (d, J=4.8 Hz, 1H; pyrrole-b), 8.39 (d, J=
4.8 Hz, 1H; pyrrole-b), 8.50 (d, J=5.1 Hz, 1H; pyrrole-b), 8.63 (d, J=
9.9 Hz, 1H; vinyl), 8.91 ppm (d, J=4.4 Hz, 1H; pyrrole-b); HRMS
(ESI): m/z calcd for C36H31N6NiO: 621.1907 [M+H]+; found: 621.1899;
UV/Vis (CH2Cl2): lmax (e)=386 (46000), 580 (16000), 623 nm
(29000mÀ1 cmÀ1); IR (KBr): n˜max =1682 cmÀ1 (C=O).
Reaction of 3Ni with NaN3–CuI: A mixture of CuI (501 mg, 2.64 mmol),
sodium azide (171 mg, 2.63 mmol), and DMF (200 mL) was stirred at RT
for 10 min, during which the color of the solution changed to black. Com-
pound 3Ni (300 mg, 0.334 mmol) was then added in one portion, and the
resulting mixture was heated to 1108C. After 1 h, toluene and brine were
added, and the organic phase was washed with water several times. The
organic phase was dried over Na2SO4 and evaporated under reduced
pressure to leave a solid residue, which was then subjected on silica-gel
column chromatography (hexane/EtOAc 5:1) followed by reprecipitation
from CH2Cl2/MeOH. The major product, 4Ni was obtained as a purple
solid (173 mg, 86%). In this reaction, 5Ni and 6Ni were not produced in
detectable amounts. When 4 equiv of NaN3 and CuI were used, 4Ni was
obtained in 88% yield. If CuBr was used instead of CuI, 4Ni was isolated
in 82% yield.
Synthesis of 3Ni: To a solution of 2 (2.0 g, 4.8 mmol) in CH2Cl2 (45 mL)
and MeOH (30 mL) was added NiACHTNUTRGNE(NUG OAc)2·4H2O (0.59 g, 2.4 mmol). After
1 h of stirring at RT, the mixture was evaporated under reduced pressure,
and a solid residue was recrystallized from MeOH/CH2Cl2 to give 3Ni as
a green solid (2.03 g, 95%). Compound 3Ni could be prepared in 79%
yield (based on 1) without isolating 2. M.p. >3008C; HRMS (ESI): m/z
calcd for C36H31Br4N4Ni: 892.8636 [M+H]+; found: 892.8619; UV/Vis
(CH2Cl2): lmax (e)=352 (20000), 447 (34000), 518 nm (81000mÀ1 cmÀ1);
elemental analysis calcd (%) for C36H30Br4N4Ni (Mw): C 48.21, H 3.37, N
6.25, Br 35.63; found: C 47.95, H 3.09, N 6.26, Br 35.54.
Chem. Eur. J. 2012, 18, 6208 – 6216
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6213

Y. Matano et al.
Reaction of 3Cu with NaN3–CuI: A mixture of CuI (95 mg, 0.50 mmol),
sodium azide (33 mg, 0.51 mmol), and DMF (300 mL) was stirred at RT
for 1 h. Compound 3Cu (100 mg, 0.111 mmol) was then added in one
portion, and the resulting mixture was heated to 1108C. After 1 h, tolu-
ene and brine were added, and the organic phase was washed with brine
several times. The organic phase was dried over Na2SO4 and evaporated
under reduced pressure to leave a solid residue, which was then subjected
on silica-gel column chromatography (hexane/ethyl acetate 5:1) followed
by reprecipitation from CH2Cl2/MeOH. The major product, 4Cu (Rf =
0.5) was obtained as a purple solid (60.3 mg, 89%). M.p. >3008C;
HRMS (ESI): m/z calcd for C36H31CuN6: 610.1901 [M+H]+; found:
610.1888; UV/Vis (CH2Cl2): lmax (e)=384 (95000), 397 (93000), 577 nm
(88000mÀ1 cmÀ1). Although this compound was described in a patent,[5]
the yield and the spectral data were not reported.
1H; vinyl), 8.85 ppm (d, J=4.4 Hz, 1H, pyrrole-b); HRMS (ESI): m/z
calcd for C36H30BrN6NiO: 699.1012 [M+H]+; found: 699.0982; UV/Vis
(CH2Cl2): lmax (e)=385 (45000), 589 (17000), 626 nm (26000mÀ1 cmÀ1);
1
IR (KBr): n˜max =1690 cmÀ1 (C=O). 11: m.p. >3008C; H NMR (600 MHz,
CD2Cl2): d=1.83 (s, 6H, ortho-Me), 1.86 (s, 6H, ortho-Me), 2.54 (s, 3H,
para-Me), 2.55(s, 3H, para-Me), 7.19 (s, 2H, Ar-meta), 7.23 (s, 2H, Ar-
meta), 7.79 (d, J=9.9 Hz, 1H, vinyl), 8.04 (d, J=5.4 Hz, 1H, pyrrole-b),
8.21 (s, 1H, pyrrole-b), 8.50 (d, J=5.4 Hz, 1H, pyrrole-b), 8.58 (d, J=
9.9 Hz, 1H, vinyl), 8.95 ppm (s, 1H, pyrrole-b); HRMS (ESI): m/z calcd
for C36H29Br2N6NiO: 777.0118 [M+H]+; found: 777.0087; UV/Vis
(CH2Cl2): lmax (e)=389 (49000), 576 (17000), 632 nm (27000mÀ1 cmÀ1);
IR (KBr): n˜max =1690 cmÀ1 (C=O).
Synthesis of 12:
A
A
mixture 10 (38 mg, 0.054 mmol), tributyl-
(PPh3)4] (6 mg, 0.005 mmol),
and DMF (40 mL) was stirred at 1208C. After 1 h, toluene and water
were added. The toluene layer was separated, washed with water, and
evaporated under reduced pressure to leave a solid residue, which was
then subjected on silica-gel column chromatography (hexane/EtOAc
5:1). Compound 12 (Rf =0.5) was isolated as a green solid (25 mg, 66%)
after recrystallization from CH2Cl2/MeOH. M.p. >3008C; 1H NMR
(400 MHz, CD2Cl2): d=1.84 (s, 6H, ortho-Me), 1.95 (s, 6H, ortho-Me),
2.55 (s, 6H, para-Me), 7.24 (s, 2H, Ar-meta), 7.23 (s, 2H, Ar-meta), 7.45
(t, J=7.7 Hz, 1H, Ph-para), 7.60 (dd, J=7.7, 7.1 Hz, 2H, Ph-meta),7.80
(d, J=9.8 Hz, 1H, vinyl), 7.98 (d, J=4.3 Hz, 1H, pyrrole-b), 8.06 (d, J=
4.9 Hz, 1H, pyrrole-b), 8.38 (s, 1H, pyrrole-b), 8.53 (d, J=4.9 Hz, 1H,
pyrrole-b), 8.56 (d, J=7.1 Hz, 2H, Ph-ortho), 8.63 (d, J=9.8 Hz, 1H,
vinyl), 8.87 ppm (d, J=4.3 Hz, 1H, pyrrole-b); HRMS (ESI): m/z calcd
for C42H35N6NiO: 697.2220 [M+H]+; found: 697.2218; UV/Vis (CH2Cl2):
lmax (e)=389 (62000), 591 (21000), 635 nm (30000mÀ1 cmÀ1); IR (KBr):
n˜max =1691 cmÀ1 (C=O).
Synthesis of 7:
A
mixture of 5,15-dimesitylporphyrin (30 mg,
0.055 mmol), NiCl2 (7.7 mg, 0.059 mmol), and DMF (5 mL) was stirred at
1008C for 10 h. After cooling to RT, CH2Cl2 was added, and the resulting
solution was washed with an aqueous NaHCO3 solution and brine, dried
over Na2SO4, and evaporated under reduced pressure. The solid residue
was then subjected on silica-gel column chromatography (CH2Cl2/hexane
1:1). Compound 7 (Rf =0.8) was isolated as a purple solid (18.9 mg,
57%). M.p. >3008C; 1H NMR (400 MHz, CD2Cl2): d=1.77 (s, 12H;
para-Me), 2.60 (s, 6H; ortho-Me), 7.27 (s, 4H; Ar-H), 8.76 (d, J=4.9 Hz,
4H; pyrrole-b), 9.18 (d, J=4.9 Hz, 4H; pyrrole-b), 9.94 ppm (s, 2H;
meso-H); 13C{1H} NMR (100 MHz, CD2Cl2): d=21.46, 21.56, 105.12,
117.17, 128.18, 131.59, 132.83, 137.60, 138.35, 139.38, 143.16 ppm; HRMS
(ESI): m/z calcd for C38H33N4Ni: 603.2059 [M+H]+; found: 603.2054;
UV/Vis (CH2Cl2): lmax (e)=398 (230000), 514 (16000), 547 nm
(8800mÀ1 cmÀ1).
Synthesis of 8: To a solution of 4Ni (44 mg, 0.073 mmol) in CHCl3
(10 mL) was added NBS (174 mg, 0.98 mmol), and the resulting mixture
was heated at reflux. After 10 h, the solvent was removed under reduced
pressure, and a solid residue was purified by column chromatography on
silica gel (CH2Cl2/hexane 1:1 as eluents) to give 8 (Rf =0.8) as a purple
X-ray crystallographic analyses: Single crystals of 3Ni, 3Cu, 4Ni, 4Cu,
5Ni, 9, and 11 were grown from CH2Cl2/MeOH at RT. X-ray crystallo-
graphic measurements were made on a Rigaku Saturn CCD area detec-
tor with graphite monochromated MoKa radiation (0.71070 ꢁ) at
À1308C. The data were corrected for Lorentz and polarization effects.
The structures were solved by using a direct method[17] and refined by
full-matrix least squares techniques against F2 by using SHELXL-97.[18]
The nonhydrogen atoms were refined anisotropically, and hydrogen
atoms were refined by using the rigid model. All calculations were per-
formed by using CrystalStructure crystallographic software package,[19]
except for the refinement. CCDC-860204 (3Ni), CCDC-860205 (3Cu),
CCDC-860206 (4Ni), CCDC-860207 (4Cu), CCDC-861350 (5Ni),
CCDC-860209 (9), and CCDC-860208 (11) 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.
1
solid (60 mg, 90%). M.p. >3008C; H NMR (400 MHz, CD2Cl2): d=1.79
(s, 12H; para-Me), 2.60 (s, 6H; ortho-Me), 7.29 (s, 4H; Ar-H), 8.82 ppm
(s, 4H; pyrrole-b); HRMS (ESI): m/z calcd for C36H27Br4N6Ni: 916.8384
[M+H]+; found: 916.8361; UV/Vis (CH2Cl2): lmax (e)=364 (61000), 401
(97000), 587 nm (77000mÀ1 cmÀ1).
Synthesis of 9:
(phenyl)stannane
A
mixture of
(64.8 mg,
8
(20.1 mg, 0.0218 mmol), tributyl-
T
0.176 mmol), [Pd(PPh3)4] (2.3 mg,
ACHTUNGTRENNUNG
0.0020 mmol), and DMF (5 mL) was stirred at 1208C. After 3 h, toluene
and water were added. The toluene layer was separated, washed with
water, and evaporated under reduced pressure to leave a solid residue,
which was then subjected on silica-gel column chromatography (hexane/
CH2Cl2 4:1). Compound
9 (Rf =0.7) was isolated as a green solid
Computational details: The structures of model compounds 4Nim and
7m were optimized by using DFT. The basis sets used were 6–311GACHTUNGTRENNUNG(d,p)
(11.8 mg, 59%) after recrystallization from CH2Cl2–MeOH. M.p.
>3008C; 1H NMR (400 MHz, CD2Cl2): d=1.90 (s, 12H; para-Me), 2.64
(s, 6H; ortho-Me), 7.33 (s, 4H; Ar-H), 7.56 (t, J=7.3 Hz, 4H; Ph-para),
7.66 (t, J=7.3 Hz, 8H; Ph-meta), 8.75 (d, J=7.3 Hz, 8H; Ph-ortho),
8.88 ppm (s, 4H; pyrrole-b); 13C{1H} NMR (100 MHz, CD2Cl2): d=160.2,
154.9, 152.6, 147.1, 146.0, 133.3, 132.0, 131.2, 129.9, 129.0, 128.3, 121.2,
120.4, 30.1, 21.5 ppm; HRMS (ESI): m/z calcd for C60H47N6Ni: 909.3210
[M+H]+; found: 909.3205; UV/Vis (CH2Cl2): lmax (e)=374 (70000), 420
(120000), 612 nm (64000mÀ1 cmÀ1).
basis set[20] for H, C, and N and the Wachters–Hay all-electron basis
set[21] supplemented with one f-function (exponent: 1.29) for Ni. The
functional of DFT was Becke, three parameter, Lee–Yang–Parr (B3LYP)
exchange–correlation functional.[22] We confirmed that the optimized geo-
metries were not in saddle, but in stable points. As a result, the stable ge-
ometries of 4Nim and 7m became D2h symmetry; in the optimized struc-
tures of model compounds, the meso-phenyl groups are perpendicular to
the (diaza)porphyrin p planes. The Cartesian coordinates are summarized
in Table S1 in the Supporting Information. All the calculations were car-
ried out by using the Gaussian 09 suite of programs.[23] Selected molecu-
lar orbitals and their energies are summarized in Figure 7.
Syntheses of 10 and 11: To a solution of 6Ni (56.3 mg, 0.0905 mmol) in
CHCl3 (10 mL) was added NBS (16.2 mg, 0.0910 mmol), and the resulting
mixture was stirred at RT. After 2 h, the solvent was removed under re-
duced pressure, and a solid residue was purified by column chromatogra-
phy on silica gel (hexane/EtOAc 5:1) to give three major compounds, 11
(Rf =0.6; 2.5 mg, 4%), 10 (Rf =0.5; 38.8 mg, 61%), and 6Ni (Rf =0.3;
7.0 mg, 12%). These compounds are separable, and their structures were
characterized on the basis of NMR spectroscopy and MS. 10: m.p.
>3008C; 1H NMR (600 MHz, CD2Cl2): d=1.83 (s, 6H, ortho-Me), 1.91
(s, 6H, ortho-Me), 2.54 (s, 3H, para-Me), 2.55(s, 3H, para-Me), 7.21 (s,
2H, Ar-meta), 7.24 (s, 2H, Ar-meta), 7.80 (d, J=9.9 Hz, 1H; vinyl), 8.00
(d, J=4.4 Hz, 1H pyrrole-b), 8.06 (d, J=4.9 Hz, 1H, pyrrole-b), 8.29 (s,
1H, pyrrole-b), 8.53 (d, J=4.9 Hz, 1H, pyrrole-b), 8.62 (d, J=9.9 Hz,
Acknowledgements
We thank Dr. Takashi Matsumoto (Rigaku corporation), Dr. Keiko
Kuwata, and Dr. Haruo Fujita (Kyoto University) for the measurements
of X-ray diffraction analysis of 5Ni, HRMS, and 2D-NMR spectra, re-
spectively. We also thank Prof. Hiroshi Shinokubo (Nagoya University)
and Prof. Shigeki Kawabata (Toyama Prefectural University) for fruitful
6214
www.chemeurj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 6208 – 6216

Nickel(II) and Copper(II) Complexes of 5,15-Diazaporphyrins
FULL PAPER
discussion. This work was supported by Grants-in-Aid (p Space, Nos.
21108511 and 23108708) from MEXT, Japan.
[11] All attempts to convert 4Ni and 4Cu to a freebase by treatment
with protic acids (CF3CO2H, conc. H2SO4, conc. H2SO4–CF3CO2H)
have so far failed.
[12] 3Ni: C36H30Br4N4Ni, Mw =896.99 gmolÀ1
;
0.40ꢂ0.15ꢂ0.05 mm;
monoclinic; P21/n; a=10.909(2), b=11.443(3), c=27.564(6) ꢁ; b=
m=
[1] For example, see: a) Phthalocyanines, Properties and Applications,
Vol. I–IV (Eds.: C. C. Leznoff, A. B. P. Lever), Wiley, New York,
1989, 1993, 1993, 1996; b) N. B. McKeown, Phthalocyanine Materi-
als: Synthesis, Structure and Function, Cambridge University Press,
Cambridge, 1998; c) N. Kobayashi in The Porphyrin Handbook,
Vol. 2, (Eds.: K. Kadish, R. M. Smith, R. Guilard), Academic Press,
San Diego, 2000, pp. 301–360; d) G. de La Torre, M. Nicolau, T.
Torres in Supramolecular Photosensitive and Electroactive Materials
(Ed.: H. S. Nalwa) Academic Press, San Diego, 2001, pp. 1–111;
e) M. S. Rodrꢃguez-Morgade, G. de La Torre, T. Torres in The Por-
phyrin Handbook, Vol. 15 (Eds.: K. Kadish, R. M. Smith, R. Gui-
lard), Academic Press, San Diego, 2003, pp. 125–159; f) K. Ishii, N.
Kobayashi in The Porphyrin Handbook, Vol. 16, (Eds.: K. Kadish,
R. M. Smith, R. Guilard), Academic Press, San Diego, 2003, pp. 1–
42; g) J. Mack, M. J. Stillman in The Porphyrin Handbook, Vol. 16,
(Eds.: K. Kadish, R. M. Smith, R. Guilard), Academic Press, San
Diego, 2003, pp. 43–116.
94.261(3)8; V=3431.3(13) ꢁ3; Z=4; 1calcd =1.736 gcmÀ3
;
52.55 cmÀ1; collected reflections 25914; independent 7665; parame-
ters 406; Rw =0.1385, R=0.0521 [I>2.0s(I)]; GOF=1.094. 3Cu:
C36H30Br4CuN4; Mw =901.82 gmolÀ1; 0.40ꢂ0.10ꢂ0.03 mm; triclinic;
P-1; a=11.2953(13), b=12.5757(16), c=26.170(4) ꢁ; a=89.482(5),
b=78.093(5), g=71.624(4)8; V=3445.6(8) ꢁ3; Z=4; 1calcd
=
1.738 gcmÀ3; m=53.04 cmÀ1; collected reflections 27377; indepen-
dent 15074; parameters 811; Rw =0.1238; R=0.0521 [I>2.0s(I)];
GOF=1.113. 4Ni: C36H30N6Ni; Mw =605.37 gmolÀ1
;
0.20ꢂ0.10ꢂ
0.03 mm; monoclinic; P21/c; a=8.400(2), b=23.910(6), c=
7.694(2) ꢁ; b=112.673(3)8; V=1426.0(6) ꢁ3; Z=2; 1calcd
=
1.410 gcmÀ3; m=7.18 cmÀ1; collected reflections 11067; independent
3176; parameters 196; Rw =0.0967; R=0.0388 (I >2.00s(I)); GOF=
1.071. 4Cu: C36H30CuN6; Mw =610.20 gmolÀ1; 0.60ꢂ0.25ꢂ0.02 mm;
monoclinic; P21/c; a=8.285(4), b=24.560(12), c=7.417(4) ꢁ; b=
109.722(5)8; V=1420.8(12) ꢁ3; Z=2; 1calcd =1.426 gcmÀ3
;
m=
8.07 cmÀ1; collected reflections 10312; independent 3241; parame-
ters 196; Rw =0.1305; R=0.0532 [I>2.0s(I)]; GOF=1.074. 5Ni:
C36H31N7Ni; Mw =620.39 gmolÀ1; 0.20ꢂ0.15ꢂ0.05 mm; trigonal; P3;
a,b=15.508(2), c=10.9418(11) ꢁ; g=1208; V=2278.9(5) ꢁ3; Z=3;
1calcd =1.356 gcmÀ3; m=6.77 cmÀ1; collected reflections 10286; inde-
pendent 4479; parameters 406; Rw =0.1476; R=0.0678 [I>2.0s(I)];
[2] H. Fischer, H. Harberland, A. Mꢄller, Justus Liebigs Ann. Chem.
1936, 521, 122.
[3] P. A. Stuzhin, O. G. Khelevina, Coord. Chem. Rev. 1996, 147, 41.
[4] For recent examples, see: a) S. Neya, H. Hori, K. Imai, Y. Kawa-
mura-Konishi, H. Suzuki, Y. Shiro, T. Iizuka, N. Funasaki, J. Bio-
chem. 1997, 121, 654; b) P. A. Stuzhin, M. Goeldner, H. Homborg,
A. S. Semeikin, I. S. Migalova, S. Wolowiec, Mendeleev Commun.
1999, 9, 134; c) P. A. Stuzhin, S. S. Ivanova, I. S. Migalova, Russ. J.
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Fujimura, S. Neya, P. A. Stuzhin, N. Kobayashi, Eur. J. Org. Chem.
2004, 1621; e) N. Pan, Y. Bian, T. Fukuda, M. Yokoyama, R. Li, S.
Neya, J. Jiang, N. Kobayashi, Inorg. Chem. 2004, 43, 8242; f) H.
Shinmori, F. Kodaira, S. Matsugo, S. Kawabata, A. Osuka, Chem.
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Chem. Commun. 2006, 4590; h) N. E. Galanin, L. A. Yakubov, E. V.
Kudrik, G. P. Shaposhnikov, Russ. J. Gen. Chem. 2008, 78, 1436; i) N.
Pan, Y. Bian, M. Yokoyama, R. Li, T. Fukuda, S. Neya, J. Jiang, N.
Kobayashi, Eur. J. Inorg. Chem. 2008, 5519; j) P. A. Stuzhin, S. E.
Nefedov, R. S. Kumeev, A. Ul-Haq, V. V. Minin, S. S. Ivanova,
Inorg. Chem. 2010, 49, 4802; k) T. Okujima, G. Jin, S. Otsubo, S.
Aramaki, N. Ono, H. Yamada, H. Uno, J. Porphyrins Phthalocya-
nines 2011, 15, 697; l) P. A. Stuzhin, A. Ul-Haq, S. E. Nefedov, R. S.
Kumeev, O. I. Koifman, Eur. J. Inorg. Chem. 2011, 2567.
[5] Two b-free DAP–copper complexes including 4Cu were reported in
a patent, although the yields and the spectral data are not described:
A. Ogiso, S. Inoue, T. Nishimoto, H. Tsukahara, T. Misawa, T.
Koike, N. Mihara, S. Murayama, R. Nara, WO-A1–2001047719,
2001.
[6] a) R. L. N. Harris, A. W. Johnson, I. T. Kay, J. Chem. Soc. C 1966,
22; b) O. G. Khelevina, N. V. Chizhova, P. A. Stuzhin, A. S. Semei-
kin, B. D. Berezin, Russ. J. Coord. Chem. 1997, 71, 74.
[7] Modified porphyrins containing a fused pyridinone unit (oxypyripor-
phyrins) were reported by a few research groups: a) T. D. Lash, S. T.
Chaney, Chem. Eur. J. 1996, 2, 944; b) T. Schçnemeier, E. Breitmai-
er, Synthesis 1997, 273; c) T. D. Lash, S. T. Chaney, J. Org. Chem.
1998, 63, 9076; d) H. Eguchi, Y. Ohgo, A. Ikezaki, S. Neya, M. Na-
kamura, Chem. Lett. 2008, 37, 768; e) S. Neya, M. Suzuki, H. Ode,
T. Hoshino, Y. Furutani, H. Kandori, H. Hori, K. Imai, T. Komatsu,
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[8] Shinokubo et al. have independently developed an efficient synthet-
ic procedure for azacorroles by Pd-catalyzed amination of a dichloro-
dipyrrin complex. M. Horie, Y. Hayashi, S. Yamaguchi, H. Shinoku-
bo, Chem. Eur. J. 2012, DOI: 10.1002/chem.201200485.
GOF=1.141. 9: C60H46N6Ni; Mw =909.74 gmolÀ1
0.03 mm; monoclinic; Pbca; a=11.878(2), b=19.174(4), c=
m=
;
0.30ꢂ0.10ꢂ
19.389(4) ꢁ; V=4416.0(14) ꢁ3; Z=4; 1calcd =1.368 gcmÀ3
;
4.90 cmÀ1; collected reflections 33148; independent 5067; parame-
ters 304; Rw =0.1421; R=0.0690 [I>2.0s(I)]; GOF=1.235. 11:
C36H28Br2N6NiO; Mw =779.17 gmolÀ1; 0.25ꢂ0.04ꢂ0.03 mm; mono-
clinic; P21/c; a=8.463(4), b=13.769(7), c=27.102(15) ꢁ; b=
93.889(9)8;
V=3151(3) ꢁ3;
Z=4;
1calcd =1.643 gcmÀ3
;
m=
31.93 cmÀ1; collected reflections 24083; independent 7158; parame-
ters 415; Rw =0.2062; R=0.0787 [I>2.0s(I)]; GOF=1.159.
ˇ
´
[13] H. S. Gill, I. Finger, I. Bozidarevic, F. Szydlo, M. J. Scott, New J.
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of P1 in CH2Cl2 were reported to be 424 and 562 nm, respectively.
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and lQ of P2 in CHCl3 were reported to be 403 and 546 nm, respec-
tively.
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2007, 307.
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carano, C. Giacovazzo, A. Guagliardi, M. Burla, G. Polidori, M. Ca-
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Burla, R. Caliandro, M. Camalli, B. Carrozzini, G. L. Cascarano, L.
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[10] CAUTION! Although we have not experienced it, heavy-metal
azides are believed to be explosive in nature. Therefore, care must
be taken with CuN3 in the reaction procedure.
Chem. Eur. J. 2012, 18, 6208 – 6216
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6215

Y. Matano et al.
J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J.
Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J.
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J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox,
J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.
Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A.
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Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian,
Inc., Wallingford CT, 2009.
Received: February 13, 2012
Published online: March 30, 2012
6216
www.chemeurj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 6208 – 6216