Synthesis and characterization of soluble octaaryl- and octaaryloxy-substituted metal-naphthalocyanines

Article abstract of DOI:10.1002/ejoc.200300062

An easy route for the synthesis of vanadium, zinc, magnesium, etc. complexes of new soluble symmetrical octa(m-trifluoromethylphenyl) or octa(m-trifluoromethylphenoxy) substituted 2,3-naphthalocyanines {[(m-CF₃Ph)₈NcM] or [(m-CF₃PhO)₈NcM]} in good yields is described in detail. The structures of the synthesized compounds were verified by UV/Vis and ¹H and ¹³C NMR spectroscopy, as well as by mass spectrometry. The good solubilities of the prepared compounds in toluene and coordinating solvents (e.g., THF), was explained in terms of the nonplanar arrangements of eight m-CF₃Ph substituents in relation to the Nc macrocycle, preventing aggregation of the molecules. The Q-bands in the UV/Vis spectra of the [(m-CF₃Ph)₈NcM] species are each bathochromically shifted by ca. 13 nm in relation to [(m-CF₃PhO)₈NcM] species, appearing at 817 nm for [(m-CF₃Ph)₈NcVO] in toluene. All NcMs prepared exhibit very high molar extinction coefficients for the Q-band {1g(ε) ≈ 5.6} in THF. Some of prepared Nc complexes appeared to be very unstable on exposure to daylight. In addition, a nickel-catalyzed Kumada cross-coupling synthesis of substituted o-terphenyls, intermediate compounds for the preparation of octaaryl-substituted Ncs, is described. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejoc.200300062

FULL PAPER
Synthesis and Characterization of Soluble Octaaryl- and Octaaryloxy-
Substituted Metal-Naphthalocyanines
Sergei Vagin[b] and Michael Hanack*[a]
Keywords: Metal complexes / Phthalocyanines / Naphthalocyanines / o-Terphenyls
An easy route for the synthesis of vanadium, zinc, magnes-
ium, etc. complexes of new soluble symmetrical octa(m-tri-
fluoromethylphenyl) or octa(m-trifluoromethylphenoxy) sub-
UV/Vis spectra of the [(m-CF3Ph)8NcM] species are each
bathochromically shifted by ca. 13 nm in relation to [(m-
CF3PhO)8NcM] species, appearing at 817 nm for [(m-
stituted 2,3-naphthalocyanines {[(m-CF3Ph)8NcM] or [(m- CF3Ph)8NcVO] in toluene. All NcMs prepared exhibit very
CF3PhO)8NcM]} in good yields is described in detail. The
structures of the synthesized compounds were verified by
UV/Vis and 1H and 13C NMR spectroscopy, as well as by
mass spectrometry. The good solubilities of the prepared
compounds in toluene and coordinating solvents (e.g., THF),
was explained in terms of the nonplanar arrangements of
eight m-CF3Ph substituents in relation to the Nc macrocycle,
preventing aggregation of the molecules. The Q-bands in the
high molar extinction coefficients for the Q-band {lg(ε) ഠ 5.6}
in THF. Some of prepared Nc complexes appeared to be very
unstable on exposure to daylight. In addition, a nickel-cata-
lyzed Kumada cross-coupling synthesis of substituted o-ter-
phenyls, intermediate compounds for the preparation of oc-
taaryl-substituted Ncs, is described.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
this respect were obtained in our previous work on indium
naphthalocyanines, octa-substituted either with tert-butyl
or with 2-ethylhexyloxy groups, or both, at the peripheral
positions and bearing axial substituents (e.g., chloro, p-tri-
fluoromethylphenyl, or pentafluorophenyl).[6] The highest
solubility was observed for 3,(4)-tetra-tert-butyl-2,(5)-tetra-
kis(2-ethylhexyloxy)-substituted indium Nc. This unsym-
metrical substitution pattern results in a mixture of four
isomers and effectively hinders the aggregation of the Nc
macrocycles even at high concentrations.[7a] The introduc-
tion of only four tert-butyl groups also results in the readily
soluble tetra-tert-butylnaphthalocyanine and its metal com-
plexes, including dimeric (tBuNcGa)2O species.[7b] Poly-
fluorination of the Nc macrocycle also results in the
solubilization of Nc species, so soluble hexadecafluorinated
(chloro)(naphthalocyanine)gallium and its µ-oxo-dimer
were recently synthesized by our group.[7c] The preparation
of tetraaryloxy-substituted naphthalocyanines as isomeric
mixtures in which aryloxy substituents bear different bulky
groups has also been reported.[8] These naphthalocyanines
show good solubility in common organic solvents, due to
the particular mutual arrangement of peripheral substitu-
ents and Nc-macrocycle, hindering self-association of the
molecules.
Despite the interesting properties of phthalocyanines
(Pcs) and their analogues for different applications in mate-
rials science, including as semiconductors, gas sensors, non-
linear optical limiters, liquid crystals, sensitizers for photo-
dynamic therapy of cancer, and others,[1,2] naphthalocyan-
ines (Ncs) have received less attention, which is partially
due to the greater difficulties involved in their preparation.
Another disadvantage of naphthalocyanines is their poor
solubility in organic solvents. The solubility can be in-
creased by introduction of peripheral substituents (mainly
alkyl, alkylthio, or alkoxy) and/or axial ligands in their
metal complexes. An additional effect that has to be re-
duced for better performance of Ncs and their metal com-
plexes Ϫ in various nonlinear optical devices such as optical
limiters,[3] for example Ϫ is their strong tendency to form
aggregates in solution,[4,5] because of the strong van-der-
Waals interactions between different rings due to the mostly
planar structures of the molecules and their extended con-
jugated π-electron systems. Introduction of bulky substitu-
ents at the peripheries of Nc macrocycles should prevent
these cofacial interactions of the Nc molecules and thus
increase the solubility of the compounds. Good results in
In addition, we have recently found[9] that the introduc-
tion of eight meta-trifluoromethylphenyl (m-CF3Ph) groups
into the porphyrazine macrocycle produces greatly en-
hanced solubility in relation to octaphenylporphyrazine.
The CF3 substituents in the meta positions of the eight phe-
nyl groups cause nonplanar arrangements of the m-CF3Ph
[a]
Universität Tübingen, Institut für Organische Chemie,
Auf der Morgenstelle 18, 72076 Tübingen, Germany
E-mail: hanack@uni-tuebingen.de
[b]
On sabbatical leave from Ivanovo State University of Chemistry
and Technology, Organic Chemistry Department,
153460 Ivanovo, F. Engels 7, Russia
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S. Vagin, M. Hanack
FULL PAPER
groups in relation to the porphyrazine ring, which prevents ladium compounds (Kumada cross-coupling),[11Ϫ14] but
aggregation of the molecules in solution. We also found this method had not previously been applied in the prep-
high solubilities for unsymmetrically benzo-annulated por- aration of ortho-terphenyls (e.g., 4,5-diaryl-o-xylenes). The
phyrazines bearing six to four m-CF3Ph groups,[10a] such as few convenient reported methods for the preparation of
2,3,7,8,12,13-hexakis(m-trifluoromethylphenyl)benzo[q]- substituted ortho-terphenyls are the treatment of ortho-di-
porphyrazine,
2,3,7,8-tetrakis(m-trifluoromethylphenyl)- halogenated benzenes (e.g., 1,2-diiodobenzene or 3,4-di-
benzo-[l,q]porphyrazine and 2,3,12,13-tetrakis(m-trifluoro- bromotoluene) with arylzinc compounds with catalysis by
methylphenyl)benzo[g,q]porphyrazine and their magnesium tetrakis(triphenylphosphane)palladium(0),[15] Suzuki cross-
and indium complexes. The large conjugated π-electron sys- coupling reactions involving phenylboronic acids,[16a] and
tems of these compounds, together with their low aggre- the Ullman coupling reaction.[16b] The first method gives
gation in solutions, met conditions for their behavior as op- fairly high yields, but requires working with butyllithium at
tical limiters.[9][10b] It is known that naphthalocyanines, hav- Ϫ78 °C under inert atmosphere and gives several by-prod-
ing more extended π-electron systems, display especially ucts that have to be separated by column chromatography.
high optical limiting effects in solutions, if soluble.[3]
We have found that the reactions between 4,5-dibromo-or-
Here we have tried to utilize the solubilizing effect of m- tho-xylene (1) and excesses of aryl-Grignard reagents de-
CF3-substituted aryls in order to prepare soluble naphtha- rived from 3-bromobenzotrifluoride or 4-bromoveratrol,
locyanines with eight meta-trifluoromethylphenyl or meta- with catalysis by nickel() acetylacetonate in the presence
trifluoromethylphenoxy groups as peripheral substituents of 1,3-bis(2,6-diisopropyl-phenyl)imidazolium chloride,[14]
and to compare their properties in solutions qualitatively.
also provide the corresponding ortho-terphenyls {4,5-
bis[(m-trifluoromethyl)phenyl]-o-xylene (3a) and 4,5-
bis[3,4-dimethoxyphenyl]-o-xylene (3b)} in one step and
represent a good alternative to the method involving or-
ganozinc compounds. The reaction is easy to carry out and
proceeds with good yields (e.g., 62% for 3a). The only by-
product formed in noticeable amounts in this case was
bis[3,3Ј-(trifluoromethyl)biphenyl], which could easily be
separated by column chromatography. In the case of 3b,
3,3Ј,4,4Ј-tetramethoxybiphenyl and veratrol were formed as
Results and Discussion
Synthesis of Precursors: The synthesis of the meta-trifluo-
romethylphenyl-substituted naphthalocyanine complexes
9aϪ13a was carried out as shown in Scheme 1. Reactions
between aryl-Grignard reagents and halogenated benzene
derivatives are known to be catalyzed by nickel or pal-
Scheme 1. Synthesis and numbering of the compounds
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Octaaryl- and Octaaryloxy Substituted Metal-Naphthalocyanines
FULL PAPER
by-products but were easily separated from the desired packings or the presence of different crystalline forms for
product (see Exp. Sect.). The polar, dark-brown by-prod- both compounds in the solid state.
ucts, which stayed on top of the column, were formed in
Synthesis of Naphthalocyanine Compounds: The dinitriles
higher amounts only when the reaction mixture was ov- 5 and 8 were used for the template cyclotetramerization to
erheated because of the strong exothermic effect of the reac- form the Ncs either directly (preparation of 9a, 11aϪ13a,
tion during the addition of the Grignard reagent.
9bϪ13b) or by transformation of 5 into the isoindole-1,3-
diylidenediamine derivative 6 (preparation of 10a) followed
by cyclotetramerization. Satisfactory to good yields were
obtained for the magnesium, zinc, and vanadyl Ncs. Naph-
thalocyanine complexes with Mg (9a, 9b) were prepared by
treatment of dinitriles 5 and 8, respectively, with magnesium
alkoxide in pentanol/octanol mixtures. Complexes 9a and
9b appeared to be unstable in solution and degraded notice-
ably on exposure to daylight. For this reason these com-
pounds could not be purified by column chromatography
and were prepared in their pure states by several fast recrys-
tallizations, the amount of impurities formed during cyclo-
tetramerization in high-boiling alcohols not being as high
as in the cases of the reactions in quinoline or 1-chloro-
naphthalene. The complexes with V (10a, 10b) and Zn (11a,
11b), obtained by reactions in these last two solvents and
possessing higher stabilities, were purified by column chro-
matography on silica gel. It was noticed that the metal-
naphthalocyanines 10a, 10b, 11a, and 11b slowly decom-
pose in solution in the crude state, but are more stable after
purification. Solutions of purified 10a, 10b, 11a, or 11b in
toluene or THF can be kept in a closed quartz cuvette for
several days without noticeable degradation. In general, the
prepared Ncs with aryloxy substituents show better stability
in solution than the analogous octaaryl derivatives. For ex-
ample, the degradation of 9a in THF or toluene proceeds
visually more rapidly than that of 9b in daylight. However,
both compounds were stable in complete darkness, which
made it possible to measure their 13C NMR spectra with
long scan accumulations.
We have also found that condensation of dinitriles 5 or 8
with VCl3 in 1-chloronaphthalene results in the formation
of monochlorinated macrocycles. These were observed as
peaks of 15Ϫ20% intensity in the FD-mass spectra of the
reaction products, together with the 100% intensity Mϩ or
[M ϩ H]ϩ peaks of 10a or 10b. No chlorination of the
macrocycles was observed when the isoindole-1,3-diylidene-
diamine derivative 6 was used for the reaction with VCl3
(synthesis of 10a) or when three equivalents KI to one
equivalent VCl3 were added (synthesis of 10b). The forma-
tion of molecular iodine vapor was observed in the latter
case, the addition of KI not affecting the yield of 10b. It
should be noted that the crude complexes of vanadium Ncs
have to be treated with THF in order to become soluble in
other solvents. The solubilization of the crude products was
very slow if they had been dissolved directly in other sol-
Compound 3a readily undergoes α,αЈ-tetrabromination
in CCl4 in the presence of four equivalents of NBS under
UV irradiation conditions, to give 4. Use of an excess of
NBS under these conditions results in the formation of an
α,αЈ-pentabrominated product, which can be isolated by
column chromatography on silica gel. These products were
also described in cases of radical bromination of similar
compounds.[17,18] NBS-bromination of 3a in CCl4 at reflux
in the presence of catalytic amounts of AIBN without ir-
radiation was not effective enough, requiring a much longer
reaction time and affording a mixture of di-, tri-, and tetra-
brominated products even in the presence of excess NBS.
The recorded 1H and 13C NMR spectra of 4 revealed strong
through-space influence of the bromines of the dibromo-
methyl groups on the resonances of neighboring C and H
atoms. Probably, several different conformations of 4 be-
come considerably stabilized due to the hindered rotation
of the CHBr2 groups, and the signals of several C and H
atoms at room temperature are significantly broadened (see
Exp. Sect.).
Dinitrile 5 was obtained by the standard procedure,
through a DielsϪAlder reaction between fumaronitrile and
the ortho-quinodimethene generated in situ from 4.
The analogous diaryloxy-substituted dicyanonaphthalene
8 was obtained by aromatic nucleophilic substitution of the
bromines in 7 by 3-hydroxybenzotrifluoride in the presence
of K2CO3 in DMF at 130 °C. Although a similar reaction
with 4,5-dihalo-phthalonitriles proceeds readily at 70Ϫ90
°C,[19] the influence of the cyano groups on substitution of
the bromine in 6,7-dibromo-2,3-dicyanonaphthalene (7) is
less strong, and substitution requires a higher temperature
and a longer reaction time. Nevertheless, the yield of 8 is
fairly satisfactory (49%). Compound 8 can be purified
either by recrystallization or by column chromatography,
depending on the purity of the starting material 7. Use of
less pure 7 results in the formation of polar dark-brown by-
products, which usually stay at the top of the column during
chromatography, but they may also substantially disturb the
reaction, lowering the yield. Although the preparation of
6,7-diphenylthio-
or
6,7-dialkylthio-2,3-dicyanonaph-
thalene by treatment of 7 with thiolate ions, catalyzed by
Cu2O, has already been described,[4] the above route for the
preparation of 6,7-diaryloxy-substituted 2,3-dicyanonaph-
thalene (e.g., 8) is presented here for the first time.
It is interesting to note that both dinitriles 5 and 8 exhibit vents such as toluene. This observation is probably connec-
slight splitting of their -CϵN stretching vibrations in their ted with the hydrolysis of the crude materials to give the
IR spectra recorded in KBr, whereas in the 13C NMR spec- vanadium() oxides 10a or 10b, which proceeds much more
tra of 5 and 8 in solution both of their CN groups are rapidly in THF.
equivalent and give only one 13C resonance: at δ ϭ
In order to obtain more information about the properties
115.7 ppm for 5 and at δ ϭ 115.6 ppm for 8. This unusual of the new substituted naphthalocyanines of series a
effect can be explained in terms of the dinitriles’ crystal {octa(m-trifluoromethylphenyl-substituted Ncs} and series
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S. Vagin, M. Hanack
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b {octa(m-trifluoromethylphenoxy-substituted Ncs}, we 9b) are even more aggregated in noncoordinating solvents
tried to prepare their complexes with indium and copper by such as chloroform or toluene, although they are highly sol-
a route similar to that used for the synthesis of vanadium uble in THF, showing very low aggregation even at high
compounds 10a and 10b. Treatment of dinitriles 5 and 8 concentrations, as can be seen from their 1H and 13C
with InCl3 in chloronaphthalene yielded the corresponding NMR spectra.
(chloro)indium() complexes 12a and 12b, respectively,
To compare the solubility of 10a with those of Ncs pos-
though these appeared to be very unstable in solution (e.g., sessing only four peripheral meta-trifluoromethylphenyl
in THF or toluene) and for this reason could not be isolated substituents, we prepared the corresponding vanadyl
in their pure states. The copper() complexes 13a and 13b tetra(m-trifluoromethylphenyl)naphthalocyanine (14, see
were also prepared by treatment of dinitriles 5 and 8 with Scheme 2) by a route similar to that used for 10a, starting
anhydrous CuCl2 in chloronaphthalene. Although they from 4-bromo- or 4-iodo-o-xylene. As expected, 14 shows a
were stable in solution, they did not possess high solubility strong tendency to aggregate even in THF and is practically
and were heavily aggregated even in THF, which is due to insoluble in toluene, in contrast to the octasubstituted de-
the square-planar coordination geometry of NcCu com- rivative 10a, and so was not further investigated. Its prep-
plexes and their low ability to coordinate axial ligands. aration was also complicated by the formation of two prod-
These compounds were also not isolated in their pure states. ucts, namely the desired 3,4-dimethyl-3Ј-trifluoromethyl bi-
It is remarkable that the (m-CF3Ph)8NcM complexes phenyl and the by-product 3,3Ј-bis(trifluoromethyl)bi-
9aϪ11a cannot be crystallized by addition of methanol, phenyl (see Scheme 2) during the first step, and by these not
since they are soluble in this solvent, although showing very being separable by column chromatography. It was possible
strong aggregation. For this reason we had to use hexane to remove this by-product only after partial NBS-bromin-
to precipitate them from concentrated CH2Cl2, toluene, or ation of the mixture. For these reasons we do not describe
THF solutions. In contrast, the (m-CF3PhO)8NcM com- the detailed preparation of 14 in the Exp. Sect.
plexes 9bϪ11b crystallize easily upon addition of methanol.
We conclude that the presence of eight meta-trifluorome-
The vanadium (10a, 10b) and indium (12a, 12b) com- thylphenyl substituents in the 3-, 4-, 12-, 13-, 21-, 22-, 30-,
pounds, in which the central metal with the axial ligand and 31-positions of 2,3-naphthalocyanine effectively pre-
(oxygen or chlorine) is located out of the Nc plane, show vents aggregation of the Nc metal complexes 9aϪ12a, but
good solubilities in coordinating solvents and moderate only in the presence of an axial ligand or ligands (e.g.
solubilities in some noncoordinating solvents. According to ϪCl, ϭO, or THF) bound to the central metal atom (va-
their UV/Vis spectra, they virtually do not aggregate in nadium, indium, zinc, or magnesium). The square-planar
THF at concentrations of ca. 1 ϫ 10Ϫ4 , as well as in copper complex 13a is poorly soluble and strongly aggre-
toluene at concentrations lower 5 ϫ 10Ϫ5  for 10a and gated even in coordinating solvents, due to its weak ability
1 ϫ 10Ϫ5  for 10b, but are already displaying noticeable to form penta- or hexacoordinate species. The presence of
aggregation in CHCl3 or CH2Cl2 at 1 ϫ 10Ϫ6 . Complexes only four meta-trifluoromethylphenyl groups in positions
of zinc() (11a, 11b) and, especially, of magnesium() (9a, 3(4), 12(13), 21(22), and 30(31) does not solubilize naphtha-
Scheme 2. Preparation of tetrakis(m-trifluoromethylphenyl)-substituted Nc complex of vanadium
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Octaaryl- and Octaaryloxy Substituted Metal-Naphthalocyanines
Table 1. UV/Vis data for naphthalocyanine complexes
FULL PAPER
Compound
Q-band, λ [nm] (lgε)
B-band and others
λ [nm] (lgε)
Solvent
Q
Q
Q
2,0
0,0
1,0
[(m-CF3Ph)8NcMg] (9a)
770 (5.63)
757 (5.66)
807 (5.59)
817
796 (5.57)
805
771 (5.58)
779
758 (5.59)
767
808
812
796
800
733 (4.78)
721 (4.80)
765 (4.77)
773
754 (4.77)
763
733 (4.79)
739
721 (4.81)
729
769 sh.
771
757
760
687 (4.82)
677 (4.85)
718 (4.81)
725
708 (4.80)
715
688 (4.80)
694
678 (4.83)
684
719
720
709
711
351 (5.15)
357 (5.07)
364 (5.16), 346 (5.16)
446; 368; 325
362 (5.07), 334 (5.06)
440 sh., 369, 327
344 (5.16)
422, 350
351 (5.13), 330 (5.16)
351
367, 346
457, 370, 348
366, 337
THF
THF
THF
Toluene
THF
Toluene
THF
Toluene
THF
Toluene
THF
Toluene
THF
[(m-CF3PhO)8NcMg] (9b)
[(m-CF3Ph)8NcVO] (10a)
[(m-CF3Ph)8NcVO] (10a)
[(m-CF3PhO)8NcVO] (10b)
[(m-CF3PhO)8NcVO] (10b)
[(m-CF3Ph)8NcZn] (11a)
[(m-CF3Ph)8NcZn] (11a)
[(m-CF3PhO)8NcZn] (11b)
[(m-CF3PhO)8NcZn] (11b)
[(m-CF3Ph)8NcIn(Cl)] (12a)[a]
[(m-CF3Ph)8NcIn(Cl)] (12a)[a]
[(m-CF3PhO)8NcIn(Cl)] (12b)[a]
[(m-CF3PhO)8NcIn(Cl)] (12b)[a]
[(m-CF3Ph)8NcCu] (13a)[a]
[(m-CF3PhO)8NcCu] (13b)[a]
[(m-CF3Ph)4NcVO] (14)[a]
448 sh., 373, 339
Toluene
THF
THF
THF
THF
777, 733, 435 sh., 338
761, 715, 326
796 sh., 736
741 (4.90)
[4]
[(PhS)8NcZn]
779 (5.67)
694 (4.92)
353 (5.16)
[a]
Not isolated in pure state.
locyanines even in the case of the square-pyramidal com- THF at low concentrations are typical of non-aggregated
plex [(m-CF3Ph)4NcVO] 14. The key point determining the naphthalocyanines and consist of an intense sharp Q-band
solubilities of the prepared substituted naphthalocyanines in the red or near-infrared region (750Ϫ820 nm) with two
is the presence of meta-substituted aryls in neighboring posi- vibronic satellites on the blue side. The B-band in the UV
tions at the periphery of the macrocycle, resulting in their region is very broad and in some cases has several maxima
nonplanar arrangement relative to the Nc plane.
(see Figure 1). The measured molar extinction coefficients
The unusual instability of some Nc-metal complexes un- of 9a,b-11a,b in THF are high, which also indicates no ag-
der irradiation, especially in solution, might result from the gregation at least at low concentrations (Ͻ 10Ϫ5 ). The
photocatalytic generation of singlet oxygen, destroying the lg(ε) values for the Q-bands of V, Zn, and Mg compounds
Nc macrocycle. Complexes of Ncs with vanadium appeared in THF are in the range of 5.57Ϫ5.66, similar to that seen
to be more stable to light exposure than those with zinc or, in [(PhS)8NcZn][4] and higher than those found for alkyl-
especially, with magnesium and indium.
thio-, alkyl-, and alkoxynaphthalocyanine complexes.[4,20]
A
Spectroscopic Characterization of the Nc Complexes change in the solvent from THF to toluene shifts the ab-
9؊14: The structures of the prepared Ncs were verified by sorption bands bathochromically, by up to 10 nm for the
mass spectrometry and UV/Vis and NMR spectroscopy, as Q-band (see Table 1). The naphthalocyanines with m-tri-
well as by elemental analysis. The EA results are satisfac- fluoromethylphenoxy (m-CF3PhO) substituents (series b)
tory to good for carbon and nitrogen, but less exact for show a blue-shifted Q-band relative to the octakis(m-tri-
hydrogen, due to the high fluorine contents in the mol- fluoromethylphenyl) derivatives (series a) and the phe-
ecules, which, as we have also observed in our previous nylthio-, alkyl-, alkoxy-, and alkylthio-substituted metal-
work,[10a] disturb the determination of hydrogen.
The IR spectra do not contain much additional infor-
mation on the structures of the prepared compounds
9aϪ11a or 9bϪ11b. The presence of CF3 groups and aryls
gives rise to intense and medium-strength vibrations, which
dominate in the regions 1060Ϫ1340 cmϪ1 (ϪCF3) and
600Ϫ930 cmϪ1 (aryls), as we have described earlier,[9,10a]
the positions of which do not depend on the nature of the
central metal. The Nc complexes of the series a and b have
fairly similar spectral patterns. They differ mainly in the
positions and intensities of several vibrations in the
1350Ϫ1600 cmϪ1 region (more intense vibrations were ob-
served for 9bϪ11b), and an additional band at ca. 1284
cmϪ1 appears in the spectra of compounds of series b.
The UV/Vis data for 9؊14 are collected in Table 1, and
Figure 1. UV/Vis spectra of (m-CF3Ph)8NcVO (10a, solid line), (m-
the spectra of some selected compounds are shown in Fig-
CF3Ph)8NcZn (11a, dashed line), and (m-CF3Ph)8NcCu (dotted
ure 1. The spectra of In-, V-, Zn-, and Mg-Nc complexes in line) in THF at concentrations lower than 1 ϫ 10Ϫ5

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FULL PAPER
naphthalocyanines with the same substitution pattern, as
well as the unsubstituted NcMs.[4,20] The difference in the
absorption maxima of the Q-band between (m-
CF3Ph)8NcM and (m-CF3PhO)8NcM reaches 13 nm for Zn
and Mg complexes, respectively, even though substituents
at the most distant peripheral positions of Nc macrocycle
possess the weakest abilities to shift the Q-band.[20] This is
due to the weaker conjugation of the oxygen in the aryloxy
substituents with the Nc macrocycle in (m-CF3PhO)8NcM
9bϪ12b, caused by competitive delocalization of oxygen
electron pairs onto the trifluoromethylphenyl groups. This
can affect even the electron-withdrawing properties for m-
CF3PhO substituents in contrast to alkyloxy groups. In
contrast, the m-CF3Ph groups are in partial conjugation
with the macrocycle, donating π-electrons and shifting the
Q-band slightly towards the red. However, the ‘‘shifting’’
effect of m-CF3Ph substituents in the Nc unit is much
weaker than their effect in the porphyrazine unit.[9,10a]
The high solubilities of the Zn and Mg complexes 9a, 9b,
11a, and 11b in THF allowed well resolved 1H and 13C
Scheme 3. Numbering of H and C atoms of naphthalocyanines 9a,
9b, 11a, and 11b used for describing their NMR spectroscopic data
1
NMR spectra to be recorded for these compounds. The H
NMR spectra each show two singlets for the macrocyclic α
and β protons (see Scheme 3), shifted downfield in relation
to the protons of the corresponding dinitriles 5 and 8 due to
the ring current effect, and the multiplets of aryl or aryloxy
substituents (see Exp. Sect. and Figure 2). Signals of small
amounts of co-crystallized or coordinated solvents such as
methanol, THF, hexane, or toluene, which were replaced
by [D8]THF upon dissolving, were also observed. All 13
nonequivalent carbons signals were observed in the
110Ϫ160 ppm region in the 13C NMR spectra of 9a, 9b,
11a, and 11b and were assigned (see Exp. Sect. and Fig-
ure 2). The assignment was carried out in the light of our
previous results on aryl-substituted porphyrazines,[9,10a]
with analysis of the numerous data obtained in this work
for precursors and Nc complexes, and also by consideration
of nuclear Overhauser effects and the influence of fluorine
1
nuclei. The H and 13C spectra of (m-CF3PhO)8NcMg 9b
are shown as an example in Figure 2, demonstrating the
1
resolution of H and 13C signals and their assignment. The
1H NMR spectrum of [(m-CF3Ph)8NcVO] 10a in [D8]THF
was also recorded. Because of the paramagnetism of VIV,
the signals of Nc-macrocycle protons were not observed in
the δ ϭ Ϫ6 to δ ϭ 18 ppm region, the signals of the m-
CF3Ph substituents appearing in their usual region as a
broadened multiplet. Along with the paramagnetism of the
central metal, the broadening of these signals is also caused
by aggregation of the compound at concentrations close to
saturation. The solubility of 10a was not high enough for
its 13C NMR spectrum to be recorded.
1
Figure 2. H (a) and 13C (b) NMR spectra of (m-CF3PhO)8NcMg
(9b) in [D8]THF (the signal assignment is given in Scheme 3)
additional purification. THF for Grignard reactions was dried over
sodium and distilled, and the other solvents were used without ad-
ditional purification.
Experimental Section
General: 4,5-Dibromo-o-xylene (1),[21] 6,7-dibromo-2,3-dicyano- The following equipment was used for characterization: UV/Vis:
1
naphthalene (7),[22] and 1,3-bis(2,6-diisopropylphenyl)imidazolium
Schimadzu UV-365. FT-IR: Bruker Tensor 27; H and 13C NMR:
chloride (2)[11] were synthesized according to the literature. 3- Bruker AC 250 (1H: 250.131 MHz. 13C: 62.902 MHz). MS:
Bromobenzotrifluoride (98% pure), 4-bromo-o-xylene, 4-iodo-o-xy- Finnigan TSQ 70 MAT (EI), Varian Mat 711 (FD), G2025A
lene, 4-bromoveratrol, and 3-hydroxybenzotrifluoride were pur- Hewlett Packard (MALDI-TOF). Elemental analyses: CarloϪErba
chased from Lancaster, Avocado, or Aldrich and were used without
Elemental Analyzer 1104, 1106.
2666
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Org. Chem. 2003, 2661Ϫ2669

Octaaryl- and Octaaryloxy Substituted Metal-Naphthalocyanines
FULL PAPER
4,5-Bis[m-(trifluoromethyl)phenyl]-o-xylene (3a): A mixture of 1
(11 g, 41.7 mmol), 2 (0.7 g, 1.64 mmol), and nickel() acetylaceton-
ate [Ni(Acac)2] (0.2 g, 0.74 mmol, 95% pure, Aldrich) in dry THF
(30 mL) was stirred for 20 min under inert atmosphere. A solution
mixture was filtered, the solvent was removed from the filtrate, and
the obtained viscous residue was recrystallized from methanol to
yield 1.3 g (72%) of 4 as a white powder. M.p. 147Ϫ150 °C. 1H
NMR (CDCl3): δ ϭ 7.18Ϫ7.75 (m, 12 H, CHBr2 ϩ HPh ϩ HBenz
)
of the Grignard reagent prepared from 3-bromobenzotrifluoride ppm. 13C NMR (CDCl3, the atom-numbering is according to no-
(34 g, 151 mmol) and magnesium turnings (3.7 g, 152 mmol) in dry
THF (150 mL) was then added dropwise to the obtained light-
greenish suspension, over a period of 1 h, the reaction mixture im-
mediately turning dark brown. To avoid a vigorous exothermic pro-
cess, the reaction mixture had to be cooled in a ice/water bath dur-
ing the addition. It was kept overnight at room temperature, and
menclature): δ ϭ 35.5 (s, CHBr2), 123.7 (q, 1J ഠ 273 Hz, CF3),
3
3
124.5 (q, J ഠ 3.7 Hz, CPh-4), 126.5 (q, J ഠ 3.7 Hz, CPh-2), 129.0
(s, CPh-5), 130.9 (q, 2J ഠ 32.8 Hz, CPh-3), 131.4 (s, very broad,
CBenz-3,6), 132.8 (s, CPh-6), 137.6 (s, very broad, CBenz-1,2), 139.4
(s, CPh-1), 141.2 (s, broadened, CBenz-4,5) ppm. MS (FD): m/z ϭ
709.5 (100), quint, [Mϩ]. C22H12Br4F6 (709.95): calcd. C 37.22, H
the formation of MgBr2 precipitate was observed. The obtained 1.70, Br 45.02, F 16.06; found C 36.74, H 1.12, Br 41.08.
mixture was quenched with ice/water/dilute HCl solution and ex-
tracted with diethyl ether (2 ϫ 100 mL). The obtained organic solu-
2,3-Dicyano-6,7-bis[m-(trifluoromethyl)phenyl]naphthalene (5):
A
mixture of 4 (4 g, 5.63 mmol), fumaronitrile (0.6 g, 7.7 mmol), and
NaI (5.5 g, 36.7 mmol) in DMF (30 mL) was heated on the oil bath
at 60Ϫ70 °C for 6 h and then left at room temperature for 10 h. A
saturated NaHSO3 solution was then added to the formed dark
brown, half-solidified mass until the dark color of the solution had
disappeared. The precipitated yellowish substance was filtered off,
washed thoroughly with NaHSO3 solution and then with water,
and dried under vacuum at 80 °C. The obtained powder was dis-
solved in CH2Cl2 to give a saturated solution, which was slowly
diluted with an excess of hexane. The formed off-white crystalline
precipitate was filtered off and dried. Yield 1.8 g (67%) of 5. M.p
215Ϫ217 °C. FT-IR (KBr): ν˜ ϭ 3072 cmϪ1 vw, 2235 m, 2229 m,
1630 vw, 1593 vw, 1558 vw, 1490 vw, 1481 vw, 1444 w, 1431 m,
1404 vw, 1388 vw, 1330 vs, 1287 vw, 1258 m, 1216 m, 1167 s, 1124
s, 1098 m, 1075 m, 1050 m, 1002 vw, 984 vw, 922 m, 905 m, 856
w, 814 m, 805 m, 739 w, 709 m, 691 w, 659 m, 554 vw, 534 w, 475
tion was washed with brine and dried over anhydrous MgSO4, and
the solvent and other volatile compounds were rotary evaporated
off to yield a brown, viscous oil, which was chromatographed with
n-hexane on silica gel. The second UV-active large fraction was
collected, the solvent was removed in a rotary evaporator, and the
colorless, viscous residue was dissolved in 100 mL of hot methanol.
After having been kept at Ϫ20 °C overnight, the methanol solution
gave 10.2 g (62%) of 3a as a pure white, crystalline substance. M.p.
1
68Ϫ70 °C. H NMR (CDCl3): δ ϭ 2.40 (s, 6 H, CH3), 7.20Ϫ7.50
(m, 10 H, HPh ϩ HXy) ppm, where Ph ϭ 3-CF3-phenyl ring, Xy ϭ
xylene ring. 13C NMR (CDCl3, the atom numbering is according
3
to nomenclature): δ ϭ 19.4 (s, CH3), 123.2 (q, J ഠ 3.9 Hz, CPh
-
4), 124.0 (q, 1J ഠ 272 Hz, CF3), 126.7 (q, 3J ഠ 3.9 Hz, CPh-2),
128.4 (s, CPh-5), 130.5 (q, J ഠ 32.4 Hz, CPh-3), 131.7 (s, CXy-3,6),
2
133.1 (s, CPh-6), 136.7 (s, CPh-1), 137.0 (s, CXy-1,2), 141.7 (s, CXy
-
4,5) ppm. C22H16F6 (394.36): calcd. C 67.01, H 4.09, F 28.90; found
C 67.27, H 3.66.
1
m. H NMR (CDCl3, the atom-numbering is according to IUPAC
nomenclature): δ ϭ 7.35Ϫ7.58 (m, 8 H, HPh), 8.08 (s, 2 H, HNaph
-
5,8), 8.42 (s, 2 H, HNaph-1,4) ppm. 13C NMR (CDCl3): δ ϭ 111.0
4,5-Bis(3,4-dimethoxyphenyl)-o-xylene (3b): Compounds 1 (16 g,
60.6 mmol), 2 (1.1 g, 2.6 mmol), and [Ni(Acac)2] (0.34 g, 1.3 mmol)
in 30 mL of THF, and 4-bromoveratrol (46 g, 212 mmol) and Mg
(5.15 g, 212 mmol) in 210 mL of THF were used for the same pro-
cedure as described for the preparation of 3a. The reaction mixture
was quenched with ice/water/NH4Cl solution and extracted with
diethyl ether. The organic phase was dried and the solvent was
rotary evaporated. The residue was chromatographed on silica gel
with CH2Cl2. The first fraction, probably containing veratrol, was
removed. The second fraction, containing 3b in admixture with
3,3Ј,4,4Ј-tetramethoxybiphenyl, was collected, the solvent was re-
moved, and the solid was recrystallized from hexane. After drying,
the obtained material was additionally recrystallized from meth-
anol, giving a white powder. Yield 10 g (44%) after drying in vacuo.
M.p. 138Ϫ139 °C. 1H NMR (CDCl3, Ph ϭ 3,4-dimethoxyphenyl
ring, numbering according to IUPAC nomenclature): δ ϭ 2.33 (s,
6 H, CH3), 3.59 (s, 6 H, OCH3), 3.83 (s, 6 H, OCH3), 6.59 (s,
broadened, 2 H, HPh-2), 6.74Ϫ6.75 (m, 4 H, HPh-5,6), 7.20 (s, 2 H,
HXy-3,6) ppm. 13C NMR (CDCl3, the atom-numbering is accord-
ing to IUPAC nomenclature): δ ϭ 19.3 (s, CH3), 55.6, 55.8 (s ϩ s,
3-OCH3 and 4-OCH3), 110.8 (s, CPh-2), 113.6 (s, CPh-5), 121.8 (s,
CPh-6), 131.6 (s, CXy-3,6), 134.4 (s, CPh-1), 135.6 (s, CXy-1,2), 137.7
(s, CXy-4,5), 147.6, 148.2 (s ϩ s, CPh-3 and CPh-4) ppm. MS (EI):
m/z ϭ 378.1 (100), [Mϩ]. C24H26O4 (378.47): calcd. C 76.17, H
6.92; found C 75.79, H 7.55.
(s, CNaph-2,3), 115.7 (s, CN), 123.6 (q, 1J ഠ 273 Hz, CF3), 124.7
3
3
(q, Jഠ 3.8 Hz, CPh-4), 126.5 (q, Jഠ 3.8 Hz, CPh-2), 129.1 (s, CPh
5), 130.1 (s, CNaph-1,4), 131.0 (q, 2J ഠ 32.4 Hz, CPh-3), 132.6 (s,
CNaph-9,10), 132.9 (s, CPh-6), 135.7 (s, CNaph-5,8), 139.6 (s, CNaph
-
-
6,7), 142.5 (s, CPh-1) ppm. MS (EI): m/z ϭ 466.0 (100) [Mϩ], 397.1
(50) [M Ϫ CF3]ϩ], 328.1 (40), [M Ϫ 2CF3]ϩ, and other fragments
with the peaks of lower intensity. C26H12F6N2 (466.39): calcd. C
66.96, H 2.59, N 6.01, F 24.44; found C 67.24, H 2.18, N 6.11.
6,7-Bis[m-(trifluoromethyl)phenyl]benzo[f]isoindole-1,3-diylidene-
diamine (6): Compound 5 (1 g, 2.15 mmol) was suspended in a
methanol (25 mL) solution of Na (55 mg, 2.4 mmol) for 20 h with
bubbling of a stream of dry ammonia through the reaction mixture
at room temperature. The reaction was monitored by TLC until
complete disappearance of the starting material. The formed yel-
lowish suspension was diluted with water (ca. 10 mL) and filtered,
and the obtained precipitate was washed thoroughly with water and
dried at 70 °C under vacuum. Yield 1 g (96%) of white-yellowish
poor soluble powder. FT-IR (KBr): ν˜ ϭ 3270 cmϪ1 vw, 3216 w,
broad, 3038 m, broad, 1701 w, 1641 m, 1597 w, 1538 m, 1475 m,
1453 m, 1392 w, 1336 vs, 1301 m, 1274 w, 1256 m, 1168 s, 1120 s,
1098 m, 1076 m, 1047 w, 911 m, 863 w, 807 m, 709 m, 660 w, 610
w, 480 w. C26H15F6N3 (483.42): calcd. C 64.60, H 3.13, N 8.69, F
23.58; found C 64.41, H 2.78, N 8.07.
2,3-Dicyano-6,7-bis[m-(trifluoromethyl)phenyloxy]naphthalene (8):
Compound 7 (2.5 g, 7.4 mmol), 3-hydroxybenzotrifluoride (8 g,
49.4 mmol), and anhydrous K2CO3 (10 g, 72.5 mmol) in DMF
(50 mL) were heated at 130 °C for 15 h. After cooling, the reaction
1,2-Bis(dibromomethyl)-4,5-bis[m-(trifluoromethyl)phenyl]benzene
(4): A mixture of 3a (1 g, 2.54 mmol) and N-bromosuccinimide
(NBS, 1.8 g, 10.1 mmol) in tetrachloromethane (40 mL) was heated
at reflux under UV irradiation (mercury lamp) for 10 h until all the mixture was slowly diluted with water (200Ϫ300 mL) and the
NBS had been converted into succinimide, floating on the surface
of the tetrachloromethane solution. After cooling, the reaction
formed precipitate was filtered off, thoroughly washed with water,
and dried at 80 °C under vacuum. This crude product was purified
Eur. J. Org. Chem. 2003, 2661Ϫ2669
www.eurjoc.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2667

S. Vagin, M. Hanack
FULL PAPER
further either by column chromatography (silica gel, CH2Cl2), or
by crystallization as follows: the crude material was dissolved in
boiling toluene, and hexane or heptane was added dropwise after
the solution had been allowed to cool down slightly, in order to
initiate the crystallization process. After the formation of the first
crystals, the addition was stopped and the solution was left to cool
to room temperature. The formed precipitate was filtered off and
dried at 80 °C under vacuum. Yield (after purification by column
3675 cmϪ1 vw, 3072 vw, 1615 w, 1594 m, 1491 m, 1449 s, 1356 m,
1328 vs, 1284 m, 1253 s, 1219 m, 1172 m, 1125 s, 1091 m, 1081 m,
1064 m, 1034 m, 1001 vw, 925 m, 908 m, 881 w, 793 w, 764 vw, 745
w, 724 vw, 696 m, 655 w, 626 vw, 538 vw, 475 w, 452 vw. 1H NMR
([D8]THF): δ ϭ 7.48Ϫ7.68 (m, 32 H, HPh), 8.07 (s, 8 H, HNc-β),
9.22 (s, 8 H, HNc-α) ppm. 13C NMR ([D8]THF): δ ϭ 115.7 (q, 3J ഠ
3.7 Hz, CPh-2), 120.6 (s, CPh-6), 121.1 (q, 3J ഠ 4.1 Hz, CPh-4), 121.6
1
(s, CPh-5), 122.6 (s, CNc-3), 125.0 (q, J ഠ 272 Hz, CF3), 131.8 (s,
2
chromatography) 1.8 g (49%) of white-yellowish powder. M.p. CNc-5), 132.2 (s, CNc-4), 133.0 (q, J ഠ 32.4 Hz, CPh-3), 136.9 (s,
203Ϫ205 °C. FT-IR (KBr): ν˜ ϭ 3074 cmϪ1 vw, 2238 m, 2233 m,
1630 w, 1597 m, 1492 s, 1464 s, 1450 s, 1420 w, 1395 m, 1324 vs, (MALDI-TOF): m/z
CNc-2), 148.0 (s, CNc-6), 153.4 (s, CNc-1), 158.8 (s, CPh-1) ppm. MS
ϭ
2018.9 (100) [M
ϩ
H]ϩ.
1285 s, 1263 s, 1233 m, 1213 s, 1187 vs, 1122 vs, 1094 m, 1064 m,
1003 vw, 925 s, 917 m, 903 m, 880 m, 801 m, 744 w, 698 m, 656 w,
532 w, 473 w. H NMR (CDCl3, the atom-numbering is according
C104H48F24MgN8O8 ϫ H2O (2017.9 ϩ18.0): calcd. C 61.36, H 2.48,
N 5.50, F 22.60; found C 61.42, H 2.31, N 5.65.
1
{3,4,12,13,21,22,30,31-Octakis[m-(trifluoromethyl)phenyl]-2,3-
naphthalocyaninato}oxovanadium (10a): A small flask containing 6
(0.5 g, 1.04 mmol), VCl3 (85 mg, 0.54 mmol), and 1-chloronaph-
thalene (1 mL) was placed in an oil bath (200 °C) and heated for
1 h. After cooling, the reaction mixture was thoroughly washed
with hexane and dissolved in THF. The solvent was rapidly re-
moved by rotary evaporation, and the solid material was chromato-
graphed on silica gel with toluene/CHCl3 (1:1). The first colored
fraction was collected, concentrated on a rotary evaporator, and
precipitated with hexane. The product was centrifuged and dried
under vacuum at 70 °C. Yield 0.34 g (68%) of light green, fine pow-
der. UV/Vis (THF): λ (lgε) ϭ 807 (5.59), 765 (4.77), 718 (4.81), 364
(5.16), 346 (5.16) nm. FT-IR (KBr): ν˜ ϭ 1613 cmϪ1 vw, 1591 vw,
1470 vw, 1425 w, 1376 m, 1332 vs, 1256 m, 1237 w, 1168 s, 1128 s,
1090 s, 1077 s, 1044 m, 1007 w, 981 vw, 906 m, 885 w, 850 vw, 805
to IUPAC nomenclature, Ph ϭ 3-CF3-phenoxy group): δ ϭ
7.21Ϫ7.28 (m, 4 H, HPh), 7.40 (s, 2 H, HNaph-5,8), 7.46Ϫ7.57 (m,
4 H, HPh), 8.15 (s, 2 H, HNaph-1,4) ppm. 13C NMR (CDCl3): δ ϭ
3
110.0 (s, CNaph-2,3), 115.6 (s, CN), 116.1 (q, J ഠ 3.8 Hz, CPh-2),
116.4 (s, CPh-6), 121.8 (q, 3J ഠ 3.8 Hz, CPh-4), 122.4 (s, CPh-5),
123.4 (q, 1J ഠ 272 Hz, CF3), 130.7 (s, CNaph-9,10), 130.9 (s, CNaph
-
2
5,8), 132.9 (q, J ഠ 32.8 Hz, CPh-3), 134.4 (s, CNaph-1,4), 150.8 (s,
CNaph-6,7), 155.5 (s, CPh-1) ppm. MS (EI): m/z ϭ 498.0 (100) [Mϩ],
336.0 (30) [M Ϫ OC7H4F3 Ϫ H]ϩ, 317.0 (50) [M Ϫ OC7H4F3
Ϫ
HF]ϩ, 268.1 (30) [M Ϫ OC7H4F3 Ϫ CF3]ϩ and other fragments
with the peaks of lower intensity. C26H12F6N2O2 (498.39): calcd. C
62.66, H 2.43, N 5.62, F 22.87; found C 62.65, H 2.08, N 5.60.
{3,4,12,13,21,22,30,31-Octakis[m-(trifluoromethyl)phenyl]-2,3-
naphthalocyaninato}magnesium (9a): Mg turnings (40 mg,
1.65 mmol) were dissolved in a pentanol/octanol mixture (1:1,
7 mL) at 160 °C, and compound 5 (0.7 g, 1.50 mmol) was added.
The reaction mixture was stirred at 160 °C for 2.5 h, cooled down,
and transferred into methanol (50 mL). Water was added dropwise
to the obtained mixture in order to complete the precipitation of
product, followed by centrifugation. The solid material was again
washed several times with methanol and water and was dried in
vacuo at 60 °C. After drying, the compound was dissolved in a
CH2Cl2/THF mixture (1:1) and rapidly filtered into hexane, the
formed precipitate being centrifuged and dried. Yield 0.28 g (40%)
of green powder. UV/Vis (THF): λ (lgε) ϭ 770 (5.63), 733 (4.78),
687 (4.82), 351 (5.15) nm. FT-IR (KBr): ν˜ ϭ 1613 cmϪ1 vw, 1592
vw, 1490 vw, 1474 vw, 1441 vw, 1422 w, 1372 m, 1332 vs, 1257 m,
1238 w, 1167 s, 1128 s, 1095 s, 1077 s, 1046 w, 1034 m, 1002 vw,
981 vw, 906 m, 879 w, 848 vw, 804 m, 745 w, 736 vw, 702 s, 659 w,
1
m, 773 vw, 750 w, 737 w, 702 s, 659 w, 565 vw, 476 w. H NMR
([D8]THF): δ ϭ 7.50Ϫ7.75 (m, broadened, HPh) ppm. MS (FD):
m/z ϭ 1933.5 (100) [M ϩ H]ϩ]. C104H48F24N8OV (1932.5): calcd.
C 64.64, H 2.50, N 5.80, F 23.59; found C 64.90, H 3.02, N 5.99.
{3,4,12,13,21,22,30,31-Octakis[m-(trifluoromethyl)phenoxy]-2,3-
naphthalocyaninato}oxovanadium
(10b):
1-Chloronaphthalene
(0.2 mL) was added by syringe at 195 °C to a mixture of 8 (200 mg,
0.40 mmol), VCl3 (20 mg, 0.13 mmol), and NaI (60 mg,
0.40 mmol), and the reaction mixture was heated at this tempera-
ture for 30 min. The evolution of I2 was observed during the reac-
tion. After cooling, the mixture was thoroughly washed with hex-
ane to remove chloronaphthalene and iodine, and the purification
was carried out as in the case of 10a, including the treatment with
THF. Yield 75 mg (37%) of green powder. UV/Vis (THF): λ (lgε) ϭ
796 (5.57), 754 (4.77), 708 )4.80), 362 (5.07) 334 (5.06) nm. FT-IR
(KBr): ν˜ ϭ 1616 cmϪ1 vw, 1594 m, 1490 s, 1449 s, 1359 s, 1328 vs,
1284 s, 1254 s, 1220 m, 1171 s, 1125 s, 1088 s, 1064 m, 1044 vw,
1003 w, 926 m, 909 m, 884 m, 793 w, 750 w, 696 m, 654 vw, 477
vw. MS (FD): m/z ϭ 2060.9 (100) [Mϩ]. C104H48F24N8O9V
(2060.5): calcd. C 60.62, H 2.35, N 5.44, F 22.13; found C 60.72,
H 2.57, N 5.57.
1
564 vw, 476 w. H NMR ([D8]THF, for numbering see Scheme 3):
δ ϭ 7.50Ϫ7.80 (m, 32 H, HPh), 8.53 (s, 8 H, HNc-β), 9.40 (s, 8 H,
HNc-α) ppm. 13C NMR ([D8]THF): δ ϭ 122.5 (s, CNc-3), 124.6 (q,
low resolved, CPh-4), 125.3 (q, 1J ഠ 272 Hz, CF3), 128.0 (q, low
2
resolved, CPh-2), 130.0 (s, CPh-5), 131.4 (q, J ഠ 32.4 Hz, CPh-3),
132.5 (s, CPh-6), 134.0 (s, CNc-4), 134.6 (s, CNc-5), 137.7 (s, CNc-2),
138.6 (s, CNc-6), 142.9 (s, CPh-1), 153.9 (s, CNc-1) ppm.
C104H48F24MgN8 ϫ 2H2O (1889.9 ϩ36.0): calcd. C 64.86, H 2.72,
N 5.82, F 23.68; found C 64.19, H 2.68, N 5.25.
{3,4,12,13,21,22,30,31-Octakis[m-(trifluoromethyl)phenyl]-2,3-
naphthalocyaninato}zinc (11a): Quinoline (0.1 mL) was added by
syringe at 210 °C to a mixture of 5 (100 mg, 0.21 mmol) and ZnCl2
(20 mg, 0.15 mmol), and the temperature was maintained for
30 min. After cooling, the reaction mixture was thoroughly washed
with hexane, dissolved in CH2Cl2, and precipitated with hexane,
{3,4,12,13,21,22,30,31-Octakis[m-(trifluoromethyl)phenoxy]-2,3-
naphthalocyaninato}magnesium (9b): Mg turnings (10 mg,
0.41 mmol) were dissolved in a pentanol/octanol mixture (1:1, 3 ml)
at 160 °C and compound 8 (380 mg, 0.76 mmol) was added. The and the obtained solid was chromatographed on silica gel with
reaction mixture was heated at reflux for 1 h and cooled. The
formed dense mass was washed thoroughly with methanol, dried,
dissolved in THF, and rapidly filtered into methanol. The obtained
precipitate was centrifuged and dried in vacuo at 60 °C. Yield
toluene/THF (3:1). The first colored fraction was collected, concen-
trated, precipitated with hexane, centrifuged, and dried in vacuo at
70 °C. Yield 28 mg (27%) of 11a. UV/Vis (THF): λ (lgε) ϭ 771
(5.58), 733 (4.79), 688 (4.80), 344 (5.16) nm. FT-IR (KBr): ν˜ ϭ
240 mg (62%) of dark green powder. UV/Vis (THF): λ (lgε) ϭ 757 1612 cmϪ1 vw, 1592 vw, 1490 vw, 1471 vw, 1422 w, 1373 m, 1332
(5.66), 721 (4.80), 677 (4.85), 357 (5.07) nm. FT-IR (KBr): ν˜ ϭ
vs, 1256 m, 1237 w, 1167 s, 1127 s, 1095 s, 1075 s, 1046 w, 1035 m,
2668
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2003, 2661Ϫ2669

Octaaryl- and Octaaryloxy Substituted Metal-Naphthalocyanines
FULL PAPER
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M. Hanack, M. Lang, Adv. Mater. 1994, 6, 819Ϫ833. [2b] I.
1001 vw, 981 vw, 905 m, 877 w, 804 m, 739 w, 701 s, 659 w, 561
vw, 475 w. 1H NMR ([D8]THF): δ ϭ 7.54Ϫ7.75 (m, 32 H, HPh),
8.50 (s, 8 H, HNc-β), 9.30 (s, 8 H, HNc-α) ppm. 13C NMR
([D8]THF): δ ϭ 122.4 (s, CNc-3), 124.7 (q, low resolved, CPh-4),
Okura, Photosensitization of Porphyrins and Phthalocyanines,
Kodansha, Tokyo, 2000.
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[3]
1
125.3 (q, J ഠ 272 Hz, CF3), 127.9 (q, low resolved, CPh-2), 130.0
(s, CPh-5), 131.5 (q, 2J ഠ 32.0 Hz, CPh-3), 132.6 (s, CPh-6), 134.0 (s,
CNc-4), 134.6 (s, CNc-5), 136.9 (s, CNc-2), 138.7 (s, CNc-6), 142.8 (s,
CPh-1), 153.6 (s, CNc-1) ppm. C104H48F24N8Zn ϫ 0.5 toluene
(1930.9 ϩ46.07): calcd. C 65.31, H 2.65, N 5.67, F 23.61; found C
65.25, H 2.99, N 5.22.
[4]
[5]
[6]
[7] [7a]
{3,4,12,13,21,22,30,31-Octakis[m-(trifluoromethyl)phenoxy]-2,3-
naphthalocyaninato}zinc (11b): The reaction between 8 (200 mg,
0.40 mmol), ZnCl2 (40 mg, 0.29 mmol), and quinoline (0.2 mL) was
carried out as in the case of 11a (210 °C, 15 min). After cooling,
the product was thoroughly washed with methanol, chromato-
graphed as in case of 11a, concentrated, and precipitated by ad-
dition of methanol. Yield 103 mg (50%) after drying in vacuo at 70
°C. UV/Vis (THF): λ (lgε) ϭ 758 (5.59), 721 (4.81), 678 (4.83), 351
(5.13), 330 (5.16) nm. FT-IR (KBr): ν˜ ϭ 1616 cmϪ1 vw, 1595 m,
1490 m, 1449 s, 1358 m, 1329 vs, 1284 m, 1254 s, 1221 w, 1170 m,
1124 s, 1091 m, 1063 m, 1037 w, 925 m, 909 m, 879 w, 794 w, 739
w, 696 m, 656 vw, 476 vw. 1H NMR ([D8]THF): δ ϭ 7.55Ϫ7.72
M. Hanack, T. Schneider, M. Barthel, J. S. Shirk, S. R.
Flom, R. G. S. Pong, Coord. Chem. Rev. 2001, 219Ϫ221,
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235Ϫ258.
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[11]
(m, 32 H, HPh), 8.02 (s, 8 H, HNc-β), 9.13 (s, 8 H, HNc-α) ppm. 13
C
9889Ϫ9890.
NMR ([D8]THF): δ ϭ 115.9 (q, 3J ഠ 4.1 Hz, CPh-2), 120.2 (s, CPh
-
[12]
[13]
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G. Y. Li, J. Organomet. Chem. 2002, 653, 63Ϫ68.
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3
6), 121.2 (q, J ഠ 4.1 Hz, CPh-4), 121.5 (s, CPh-5), 122.8 (s, CNc-3),
1
125.0 (q, J ഠ 272 Hz, CF3), 131.87 (s, CNc-5), 131.94 (s, CNc-4),
2
133.1 (q, J ഠ 32.4 Hz, CPh-3), 135.9 (s, CNc-2), 148.1 (s, CNc-6),
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152.8 (s, CNc-1), 158.7 (s, CPh-1) ppm. C104H48N8O8F24Zn (2058.9):
calcd. C 60.67, H 2.35, N 5.44, F 22.15; found C 60.77, H 1.95,
N 5.43.
[15b]
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Acknowledgments
[17]
[18]
[19]
[20]
We thank the Deutsche Forschungsgemeinschaft (Phthalocyanine
und Naphthalo-cyanine des Indiums und Titans für Optical
Limiting-Experimente, Project Ha 280/65Ϫ1) and the European
Community (contract HPRN-CT-2000Ϫ00020) for financial
support of this work. We also express our gratitude to Dr. S.
Stevanovic, Tübingen University, for measuring the MALDI-TOF
mass spectrum.
[21]
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[1]
Phthalocyanines: Properties and Applications (Eds.: C. C.
Leznoff, A. B. P. Lever), VCH Publishers, Inc., New York,
1989؊1996, vol. 1Ϫ4.
Received February 4, 2003
Eur. J. Org. Chem. 2003, 2661Ϫ2669
www.eurjoc.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2669