Synthesis and electronic spectra of dimeric phthalocyanines

Article abstract of DOI:10.1007/s11172-006-0483-9

Dimeric phthalocyanines of a new type with a bridging 9,9,10,10- tetramethyl-9,10-dihydroanthracene fragment were synthesized. On the basis of X-ray diffraction analysis and molecular modeling of 9,9,10,10-tetramethyl-9,10- dihydroanthracene, a nearly pla

Full text of DOI:10.1007/s11172-006-0483-9

Russian Chemical Bulletin, International Edition, Vol. 55, No. 10, pp. 1748—1754, October, 2006
1748
Synthesis and electronic spectra of dimeric phthalocyanines
a
a
a
a
S. G. Makarov,a K. N. Maksimova, E. V. Baranov, G. K. Fukin, O. N. Suvorova,
ꢀ
D. Wöhrle,b and G. A. Domracheva
аG. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831 2) 62 7497. Eꢀmail: makarsg@mail.ru
bInstitute of Organic and Macromolecular Chemistry, University of Bremen,
NW2 Leobenerstrasse, 28334 Bremen, Germany.
Fax: +49 (421) 218 4935
Dimeric phthalocyanines of a new type with a bridging 9,9,10,10ꢀtetramethylꢀ9,10ꢀ
dihydroanthracene fragment were synthesized. On the basis of Xꢀray diffraction analysis and
molecular modeling of 9,9,10,10ꢀtetramethylꢀ9,10ꢀdihydroanthracene, a nearly planar strucꢀ
ture was assumed for these phthalocyanines. The electronic absorption spectra of the obtained
phthalocyanines and their monomeric and conjugated dimeric analogs were compared.
Key words: phthalocyanines, exciton interaction, electronic spectra.
In recent years the interest in the synthesis and study
cyanine aggregates18—20 or crystals21 also induces shifts in
electronic absorption bands depending on the mutual arꢀ
rangement of macrocycles. The design of diꢀ and oligoꢀ
meric structures with various types of interaction of
πꢀsystems is of interest as a way of modification of the
electronic properties of phthalocyanines with outlook to
prepare new molecular materials. Quite a few nonꢀ
conjugated phthalocyanine dimers with relatively flexible
connecting units (bridges) in which one cannot deterꢀ
mine with confidence the mutual positions of the macroꢀ
cycles are known.13,15,16 The hypsochromic shift of the
Q band is indicative of the predominant "faceꢀtoꢀface"
orientation, which is also typical of aggregates in soluꢀ
tions,18,20 crystals,21 and liquid crystals10 of phthalocyaꢀ
nines. There exist dimers with more rigid bridges, which
secure the phthalocyanine fragments in the "faceꢀtoꢀface"
position16 and at an angle of ~100°.17 To our knowledge,
nonconjugated dimers with "edgeꢀtoꢀedge" orientation of
phthalocyanine fragments at an angle of 180° have not yet
been prepared. These dimers are of interest as nonꢀ
conjugated analogs of type 1 and 2 diphthalocyanines
with purely exciton type of interaction of the Pc chroꢀ
mophores, which can be used to estimate the contribuꢀ
tion of the conjugation to the change in the excitation
energy compared to the monomeric analog and to study
the effect of the mutual orientation of the chromophores
on the photophysical properties of oligomeric structures.
According to the exciton interaction theory,22 these should
exhibit a red shift of the absorption bands in the elecꢀ
tronic spectrum. Dimeric phthalocyanines obtained in
this study contain a 9,9,10,10ꢀtetramethylꢀ9,10ꢀdihydroꢀ
anthracene fragment connecting the macrocycles.
of porphyrin oligomers as potential molecular conducꢀ
tors, nonlinear optical materials, and systems that simuꢀ
late photosynthesis has markedly increased.1 The oligoꢀ
mers of phthalocyanines, the most wellꢀknown porphyrin
analogs, remain much less studied. Phthalocyanines have
been extensively used for many years as dyes and pigꢀ
ments,2 catalysts and photocatalysts,3—5 photoconductors
in xerography,6 and photosensitizers in photodynamic tuꢀ
mor therapy.7 The enhanced attention to new phthaloꢀ
cyanine systems is due to a number of interesting properꢀ
ties such as conduction in a broad range,8 electroꢀ
chromism,9 and mesogenic10 and nonlinear optical11
properties most of which are due to specific features of the
aromatic πꢀsystem of the phthalocyanine macrocycle,
which is also responsible for exceptional thermal and
chemical stabilities of these compounds. A possible way
of modification of the electronic structures of conjugated
systems is to extend the conjugation system. For phthaloꢀ
cyanines, this may be attained by fusing additional benꢀ
zene rings at the macrocycle periphery12 and by conꢀ
structing conjugated oligomers.13 The former approach
results in a pronounced decrease in the stability, whereas
the conjugated systems of types 1 and 2 incorporating two
phthalocyanine fragments, which we obtained previꢀ
ously,14 are rather stable.
The extension of the system of conjugation is typically
accompanied by color deepening. In solutions, most
phthalocyanines exhibit a strong absorption band around
680 nm (Q band), which shifts to the near IR region
(840 nm) on going to dimers 1 and 2.14 The exciton interꢀ
action in nonconjugated dimers13,15—17 and in phthaloꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1686—1692, October, 2006.
1066ꢀ5285/06/5510ꢀ1748 © 2006 Springer Science+Business Media, Inc.

Synthesis of dimeric phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
1749
R = 2,6ꢀMe2C6H3
Results and Discussion
ene—hexane (metalꢀfree phthalocyanines) afforded
monomers 7 and 9 and dimers 8 and 10. The yields of
compounds 8 and 10 were 0.3 and 2.0%, respectively.
Note that dimeric phthalocyanine 2 was prepared in 71%
yield by standard metallation of monomer 1 with zinc
acetate in a toluene—DMF mixture.14 A solubility of the
resulting phthalocyanines sufficient for chromatographic
separation and for the subsequent study is provided by the
bulky 2,6ꢀdimethylphenoxyl substituents R.
Phthalocyanine dimers were synthesized according to
Scheme 1. The reductive methylation of anthracene by a
known procedure afforded 9,9,10,10ꢀtetramethylꢀ9,10ꢀ
dihydroanthracene (3)23 whose tetracyano derivative was
prepared in two steps via the intermediate 2,3,6,7ꢀtetraꢀ
iodoꢀ9,9,10,10ꢀtetramethylꢀ9,10ꢀdihydroanthracene (4)
by analogy with the procedure described previously24 for a
fenestrindane derivative. The yield of product 5 was 17%
based on anthracene. A mixture of tetracyano derivative 5
with excess 4,5ꢀbis(2,6ꢀdimethylphenoxy)phthalonitrile
(6) was heated in nꢀbutanol in the presence of a base
(magnesium butoxide or DBU). For the synthesis of zinc
phthalocyanines, zinc acetate was also added. Metalꢀfree
phthalocyanines were prepared by demetallation of magꢀ
nesium phthalocyanines with trifluoroacetic acid. Mixed
condensation gave a mixture of phthalocyanines, mainly,
monomers 7 and 9 and dimers 8 and 10. Chromatography
of the obtained mixtures on silica gel with gradient eluꢀ
tion by toluene—ether (Zn phthalocyanines) or toluꢀ
All compounds prepared in this work were characterꢀ
ized by electrospray ionization (ESI) mass spectrometry.
Molecular or pseudomolecular ions without pronounced
fragmentation were present in all cases.
1
The H NMR data are summarized in Table 1. The
shielding/deshielding effects typical of phthalocyanines
caused by the ring current of the phthalocyanine aromatic
πꢀsystem, which induced significant shifts of the proton
signals depending on the proton position with respect to
the macrocycle, are even more pronounced in phthaloꢀ
cyanine dimers of type 1,14 where the shifts of the signals
are determined by two macrocycles. The protons located

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Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
Makarov et al.
R = 2,6ꢀMe2C6H3
more closely to the center of the system are deshielded to
a greater extent. This effect promotes signal resolution in
the spectrum. The greatest chemical shifts are observed
for the signals of the benzene type phthalocyanine proꢀ
tons, especially for the bridging benzene rings (δ >11 (1, 2)
and ~9.5 (8, 10)). The broad signals of the methyl protons
of the bridge in compounds 8 and 10 (δ ~3) are also
considerably shifted downfield compared to compound 3
(δ 1.65). Generally, the signals of dimers 8 and 10 are
somewhat broadened compared to the signals of dimers 1
and 2, which is apparently due to less rigid structure. The
positions of signals for the internal pyrrole protons
(δ 0—–1) are due to the influence of the adjacent
macrocycle, which decreases shielding, as opposed to
dimeric phthalocyanines of the "faceꢀtoꢀface" type in
which further upfield shifts are observed for these protons
(up to δ –8).20
It was shown by Xꢀray diffraction that compound 3
(Fig. 1, Table 2) is planar. The average deviation of the
carbon atoms of the anthracene fragment from the plane

Synthesis of dimeric phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
1751
Scheme 1
R = 2,6ꢀMe2C6H3
1
Table 1. H NMR spectra of phthalocyanines 1, 2, 7—10
Compound
δ
(solvent)
phthalocyanine
R
bridge H
pyrrole H
H arom.
H arom.
Me
1 (CDCl3)14
11.14 (s, 2 H);
9.06, 8.29, 8.15
(all s, 4 H each)
11.67 (s, 2 H);
9.69 (s, 4 H);
8.67—8.72
7.32—7.44
(br.s, 36 H)
2.62, 2.48, 2.38
(all s, 24 H each)
—
—
–0.04 (br.s, 4 H)
—
2 (C6D6,
60 °C)
7.25—7.49
(br.s, 36 H)
2.66, 2.37, 2.29
(all s, 24 H each)
(br.s, 8 H)
8.18 (s, 8 H)
7 (CDCl3)14
8 (CDCl3)
7.30—7.41
(br.s, 24 H)
7.33—7.62
(br.s, 36 H)
2.43 (s, 48 H)
—
–0.76 (br.s, 2 H)
–0.43 (br.s, 4 H)
9.66, 8.63,
8.34, 8.19
2.60 (s, 24 H);
2.45—2.56
3.30—3.78
(br.s, 12 H)
(all s, 4 H each)
8.19 (s, 8 H)
(br.s, 48 H)
2.43 (s, 48 H)
9 (CDCl3)
7.30—7.41
(br.s, 24 H)
7.45—7.73
(br.s, 36 Н)
—
—
—
10 (DMSOꢀd6
+ KCN**)
9.49, 8.38,
7.93, 7.88
2.30—2.45
(br.s, 48 H)*
3.00 (br.s)*
(all s, 4 H each)
* A part of the signal is covered by the band of the residual DMSOꢀd6 (δ 2.50) or water (δ 3.33) protons.
** ~10 mmol L–1
.
is 0.008 Å. Apparently, the 9,10ꢀdihydroanthracene fragꢀ
ment in compounds 8 and 10 is also planar.
C(8)
C(7)
C(9A)
C(5A)
C(4A)
C(1)
C(3A)
C(2)
C(3)
C(6)
Table 2. Selected geometric parameters (bond lengths (d) and
bond angles (ω)) of compound 3
C(6A)
C(1A)
C(5)
C(2A)
C(7A)
C(4)
Bond
d/Å
Angle
ω/deg
C(9)
C(8A)
С(5)—С(6) 1.397(2)
С(6)—С(7) 1.526(2)
С(7)—С(8) 1.545(2)
С(5)—С(6)—С(7)
С(6)—С(7)—С(5А) 113.00(9)
С(8)—С(7)—С(9) 109.16(9)
123.5(1)
Fig. 1. Crystal structure of compound 3.

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Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
Makarov et al.
ε•10–5/L mol–1 cm–1
Obviously, the deviation from the planar structure gives
rise to steric hindrance as the Me groups approach each
other and the hydrogen atoms in positions 1, 4, 5, and 8.
An analog of compound 3, 9,9,10,10ꢀtetrachloroꢀ9,10ꢀ
dihydroanthracene, also has a planar structure,25 whereas
unsubstituted 9,10ꢀdihydroanthracene exists in a boat conꢀ
formation with a dihedral angle between the benzene rings
of 145°.26 The molecular modeling of compound 3
(MM+ molecular mechanics method) also predicts a plaꢀ
nar geometry. A deviation from the plane by rotation of
one benzene ring through 30° around the C(7)—C(7А)
axis followed by partial geometry optimization (with fixed
coordinates of the carbon atoms of the benzene rings)
entails an increase in energy by 25 kJ mol–1. The fraction
of molecules with an energy of ≥25 kJ mol–1 per degree of
freedom at 298 K is 0.004%, which suggests an essentially
planar conformation of the bridge and dimers 8 and 10 as
a whole.
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
1
2
400
500
600
700
λ/nm
Fig. 3. Electronic spectra of phthalocyanines 7 (1) and 8 (2, ×0.5)
in chloroform.
Q band is observed, and in the case of metalꢀfree phthaloꢀ
cyanines, minor differences between the Soret bands
(300—450 nm) can be noted. The extinction coefficients
for compounds 8 and 10 are almost twice as high as those
for compounds 7 and 9. Hence, in this case, the phthaloꢀ
cyanine fragments behave as almost independent chroꢀ
mophores, unlike those in conjugated dimers 1 and 2.
Nonconjugated phthalocyanine dimers of the "faceꢀtoꢀ
face" type15,16 and aggregates18,20 tend to exhibit a fairly
broad absorption band at about 630 nm, which is shifted
hypsochromically compared to that for monomer analogs
by ~50 nm. The relatively weak interaction of the phthaloꢀ
cyanine chromophores in dimers 8 and 10 can be attribꢀ
uted to considerably weaker overlap of the πꢀorbitals comꢀ
pared to the "faceꢀtoꢀface" dimers.
The electronic absorption spectra of the dimeric
phthalocyanine 1 in comparison with those of monomer 7
have been analyzed in detail previously.14 The spectra of
compounds 2, 9, and 10 in THF are presented in Fig. 2
and those of compounds 7 and 8 in chloroform are in
Fig. 3. As in the case of dimer 1,14 the longꢀwavelength
absorption band of dimer 2 is shifted bathochromically by
~150 nm with respect to the monomeric analog, the exꢀ
tinction coefficient for compound 1 or 2 is higher than
that for 7 or 9 but less than twice higher. Apart from the
band at about 850 nm, the spectrum exhibits a number of
lowꢀintensity bands in the range of 500—800 nm associꢀ
ated with the higher excited states of the dimeric system
and with the vibronic components of the longꢀwavelength
band. Unlike these significant changes in the spectrum
taking place on going from monomeric phthalocyanines 7
and 9 to conjugated dimers 1 and 2, the electronic spectra
of dimers 8 and 10 almost do not differ from the spectra of
monomers 7 and 9 (Table 3): only a slight red shift of the
Thus, we prepared newꢀtype phthalocyanine dimers
with the 9,9,10,10ꢀtetramethylꢀ9,10ꢀdihydroanthracene
bridge, presumably having a planar structure (based on
Xꢀray diffraction data for the bridging fragment 3). These
compounds are nonconjugated analogs of type 1 and 2
dimers. The electronic spectra of dimers 8 and 10 indicate
ε•10–5/L mol–1 cm–1
Table 3. Electronic spectra of phthalocyanines 2, 7—10
3.0
Comꢀ
pound
λ
max/nm (ε•10–5
)
2.5
2
Q band
Soret band
2.0
1.5
1.0
0.5
1
2
840 (4.70), 794 (0.61),
748 (0.93), 722 (1.08)
704 (1.65), 667 (1.39),
648 (0.47), 605 (0.28)
708 (3.22), 675 (2.57),
654 (0.93), 611 (0.50)
674 (3.38), 644 (0,42),
608 (0.47)
363 (1.87)
3
7
420 (0.41),
350 (0.86)
394 (0.72),
349 (1.57)
355 (1.06)
8
9
400
500
600
700
800
λ/nm
10
682 (6.9), 652 (0.85),
615 (0.83)
356 (2.2)
Fig. 2. Electronic spectra of phthalocyanines 2 (1), 9 (2) and
10 (3) in THF (×0.5 (1, 3)).

Synthesis of dimeric phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
1753
1
C, 29.22; H, 2.18. H NMR (DMSOꢀd6), δ: 8.01 (s, 4 H); 1.53
(s, 12 H). MS (EI, 70 eV), m/z (Irel (%)): 740 [M]+ (31), 725
[M – CH3]+ (100), 710 [M – 2 CH3]+ (20), 598 [M – CH3 – I]+
(11), 471 [M – CH3 – 2 I]+ (12), 456 [M – 2 CH3 – 2 I]+ (15),
329 [M – 2 CH3 – 3 I]+ (7), 299 [M – CH3 – I]2+ (10), 243
[M – 2 I]2+ (11), 202 [M – 2 CH3 – 4 I]+ (20), 101 [M –
2 CH3 – 4 I]2+ (25).
the absence of exciton interaction between the phthaloꢀ
cyanine chromophores, which attests to a crucial role of
conjugation in their interaction in dimers 1 and 2. Weaker
interaction compared to that in the "faceꢀtoꢀface" type
dimers may be due to insignificant overlap of the macroꢀ
cycle πꢀorbitals.
9,9,10,10ꢀTetramethylꢀ9,10ꢀdihydroanthraceneꢀ2,3,6,7ꢀ
tetracarbonitrile (5). A mixture of compound 4 (1.85 g, 2.5 mmol)
and CuCN (9.90 g, 110 mmol) in pyridine (0.5 L) was heated for
20 h at 115 °C, concentrated to a small volume, and diluted with
excess 25% aq. ammonia. The precipitate was washed with
25% aq. ammonia and water, dried, and extracted with acetone,
the solution was concentrated, and the residue was extracted
again with acetone. The extract was passed through a short
column with silica gel and concentrated, and the residue was
washed with methanol and dried in vacuo. Yield 0.50 g (59%),
colorless crystals. Found (%): C, 78.22; H, 4.64; N, 16.94.
C22H16N4. Calculated (%): C, 78.55; H, 4.79; N, 16.66.
Experimental
IR spectra were recorded on a Perkin—Elmer Spectrum
1000 spectrometer for KBr pellets, the electronic spectra were
measured on a Perkin—Elmer Lambda 25 spectrometer, and
NMR spectra were obtained on a Bruker Avance DPX 200 inꢀ
strument (200 MHz (1H); CDCl3, acetoneꢀd6, and DMSOꢀd6
as solvents; sample concentrations <1 mmol L–1; the chemical
shifts were referred to Me4Si based on the residual proton signals
of the solvent). EI mass spectra (70 eV) were recorded on a
Finnigan MAT 95 mass spectrometer and ESI mass spectra were
run on a Bruker Esquire LC instrument.
Commercial solvents (Fluka, analytically pure grade) were
used as received for recording the spectra and dried by standard
methods for the syntheses. Column chromatography was carried
out using silica gel 60 (Merck) with a particle size of 40—63 µm.
Sulfuric acid, periodic acid, potassium iodide, copper(I) cyaꢀ
nide, DBU, magnesium turnings, and trifluoroacetic acid (Fluka)
were used as received. Zinc acetate dihydrate (Fluka) was dried
in vacuo at 110 °C over P2O5 (drying is accompanied by partial
hydrolysis, which is not important in this case). 9,9,10,10ꢀTetraꢀ
methylꢀ9,10ꢀdihydroanthracene (3),23 4,5ꢀbis(2,6ꢀdimethylꢀ
phenoxy)phthalonitrile (6), and phthalocyanines 1 and 7 were
synthesized using previously described procedures.14
1
IR (KBr), ν/cm–1: 2229 (C≡N). H NMR (acetoneꢀd6), δ: 8.45
(s, 4 H); 1.86 (s, 12 H). MS (EI, 70 eV), m/z (Irel (%)): 336 [M]+
(2), 321 [M – CH3]+ (100), 306 [M – 2 CH3]+ (36), 291
[M – 3 CH3]+ (10).
2,3,9,10,16,17,37,38,42,43,47,48ꢀDodeca(2,6ꢀdimethylꢀ
phenyloxy)ꢀ33,33,66,66ꢀtetramethylꢀ33,66ꢀdihydrobenꢀ
zo[1,2ꢀb;3,4ꢀb´]ꢀ29H,31Hꢀbisphthalocyanine (8). Magnesium
turnings (0.15 g) were dissolved in boiling butanol (40 mL)
(~2 h). The resulting suspension was cooled, and compound 5
(0.17 g, 0.5 mmol) and compound 6 (1.47 g, 4 mmol) were
added. The mixture was refluxed for 48 h, cooled, and diluted
with methanol (200 mL). The precipitate formed was separated
by centrifugation, washed with methanol, dried, and extracted
with toluene. Toluene was evaporated under reduced pressure,
and the residue was dissolved in CF3COOH (25 mL). The soluꢀ
tion was stirred in the dark for 1 h at ~20 °C and poured in ice
water (~100 mL). The precipitate was separated by centrifugaꢀ
tion, washed with water, a 5% solution of NaHCO3 and again
water, dried, and extracted with a toluene—hexane mixture (15%
hexane, v/v). The solution of a phthalocyanine mixture thus
formed was chromatographed on silica gel with a toluene—hexꢀ
ane mixture as the eluent (the hexane content was gradually
decreased from 15 to 5%). The second fraction was collected,
the solvent was removed under reduced pressure, and the resiꢀ
due was recrystallized from toluene and dried in vacuo at 60 °C.
Yield 3.7 mg (0.3%), green flakes. Found (%): C, 78.08; H, 5.82;
N, 8.48. C166H140N16O12. Calculated (%): C, 78.16; H, 5.53,
N, 8.79. IR (KBr), ν/cm–1: 3305 (N—H). ESI MS (CH2Cl2—pyꢀ
ridine (1 : 100), negative ion mode), m/z: 2548 [M]–.
Zinc complex of 2,3,9,10,16,17,23,24ꢀocta(2,6ꢀdimethylꢀ
phenyloxy)ꢀ29H,31Hꢀphthalocyanine (9) and zinc complex of
2,3,9,10,16,17,37,38,42,43,47,48ꢀdodeca(2,6ꢀdimethylꢀ
phenyloxy)ꢀ33,33,66,66ꢀtetramethylꢀ33,66ꢀdihydrobenꢀ
zo[1,2ꢀb;3,4ꢀb´]ꢀ29H,31Hꢀbisphthalocyanine (10). A mixture of
compound 5 (55 mg, 0.16 mmol), compound 6 (0.6 g, 1.6 mmol),
zinc acetate (70 mg), and DBU (0.4 mL) in nꢀbutanol (4 mL)
was refluxed for 15 h, cooled, and diluted with methanol (20 mL).
The resulting precipitate was separated by centrifugation, washed
with methanol, dried, extracted with toluene, and chromatoꢀ
graphed on silica gel with a toluene—ether mixture as the eluꢀ
ent, the ether content being gradually increased to 9%. The first
and second fractions containing products 9 and 10, respectively,
Zinc complex of 2,3,7,8,12,13,19,20,24,25,29,30ꢀdoꢀ
deca(2,6ꢀdimethylphenyloxy)tribenzo[b,g,l]ꢀ21H,23Hꢀ
5,10,15,20ꢀtetraazaporphyno[2,3ꢀb]ꢀ29H,31Hꢀphthalocyanine
(2). A solution of zinc acetate dihydrate (44 mg, 0.2 mmol) in
DMF (1 mL) was added to a solution of compound 1 (24 mg,
10 µmol) in toluene (2 mL). The mixture was refluxed for 15 h,
cooled, and diluted with methanol (10 mL). The resulting preꢀ
cipitate was separated by centrifugation, washed with methanol,
dried, and dissolved in toluene. The solution was chromatoꢀ
graphed on silica gel with a toluene—ether mixture as the eluent
(8% ether v/v). A blue violet fraction was collected, the solvents
were evaporated under reduced pressure, and the residue was
reprecipitated by hexane from toluene and dried in vacuo at 60 °C.
Yield 18 mg (71%), a black powder. Found (%): C, 73.05;
H, 4.86; N, 9.13. C154H122N16O12Zn2. Calculated (%): C, 73.41;
H, 4.88; N, 8.89. MS ESI (CH2Cl2—DMF (1 : 10), positive ion
mode), m/z: 1258 [M + 2 H]2+
.
2,3,6,7ꢀTetraiodoꢀ9,9,10,10ꢀtetramethylꢀ9,10ꢀdihydroꢀ
anthracene (4). Periodic acid (H5IO6) (1.09 g, 4.8 mmol) was
dissolved in conc. H2SO4 (48 mL) at 0 °C, and KI (2.39 g,
14.4 mmol) was added with stirring in small portions. Comꢀ
pound 3 (0.28 g, 1.2 mmol) was added to the resulting solution,
cooling was terminated, and the solution was stirred for 14 h.
The mixture was poured into ice water, and the precipitate was
filtered off, washed with water and methanol, dried, dissolved in
chloroform, and passed through a short column with silica gel.
The solvent was evaporated, and the precipitate was washed
with methanol and dried in vacuo. Yield 0.42 g (48%), a pinkish
powder. Found (%): C, 29.38; H, 1.93. C18H16I4. Calculated (%):

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Makarov et al.
were collected. The solvent was removed under reduced presꢀ
sure and the compound was recrystallized from toluene and
dried in vacuo at 60 °C. Compound 9. Yield 0.27 g (43%), green
flakes. Found (%): C, 75.14; H, 5.31; N, 7.29. C96H80N8O8Zn.
Calculated (%): C, 74.92; H, 5.24; N, 7.28. ESI MS
(CH2Cl2—MeOH (1 : 10), negative ion mode), m/z: 1571
[M + Cl]–. Compound 10. Yield 9.0 mg (2.0%), green flakes.
Found (%): C, 74.07; H, 5.09; N, 8.51. C166H136N16O12Zn2.
Calculated (%): C, 74.45; H, 5.12; N, 8.37. MS ESI
(DMF + NaCN (~1 mmol L–1), negative ion mode), m/z: 1362
3. D. Wöhrle, O. Suvorova, R. Gerdes, O. Bartels, L. Lapok,
N. Baziakina, S. Makarov, and A. Slodek, J. Porphyrins
Phthalocyanines, 2004, 8, 1020.
4. J. H. Zagal, Coord. Chem. Rev., 1992, 119, 89.
5. R. Gerdes, O. Bartels, G. Schneider, D. Wöhrle, and
G. SchulzꢀEkloff, Polym. Adv. Technol., 2001, 12, 152.
6. K.ꢀY. Law, Chem. Rev., 1993, 93, 449.
7. E. BenꢀHur and W. Shun Chan, in The Porphyrin Handꢀ
book, Eds K. M. Kadish, K. M. Smith, and R. Guilard,
Academic Press, San Diego, California, 2003, 19, 1.
8. T. Inabe and H. Tajima, Chem. Rev., 2004, 104, 5503.
9. M. M. Nicholson, in Phthalocyanines: Properties and Appliꢀ
cations, Eds C. C. Leznoff and A. B. P. Lever, VCH Publishꢀ
ers, New York, 1993, 3, 71.
[M + 2 CN]2–
.
XꢀRay diffraction analysis of compound 3. The crystals were
prepared by slow evaporation of an acetone solution. XꢀRay
diffraction data were collected at 100 K on a Bruker AXS SMART
APEX diffractometer (ϕ—ω scanning, MoꢀKα radiation, λ =
0.71073 Å, graphite monochromator). Absorption corrections
were applied using the SADABS program.27 The structure was
solved by the direct method using the SHELXS97 software 28
and refined by the fullꢀmatrix least squares method on F 2 using
the SHELXL97 software.29 All nonhyrogen atoms were refined
in the anisotropic approximation. The hydrogen atoms were
found from the difference electron density synthesis and refined
isotropically. Crystal data and Xꢀray diffraction experiment
details: C18H20, M = 236.34, orthorhombic system, space
group Pbca, a = 11.3901(10) Å, b = 8.0274(7) Å, c =
10. C. Piechocki, J. Simon, A. Skoulios, D. Guillon, and
P. Weber, J. Am. Chem. Soc., 1982, 104, 5245.
11. S. Flom, in The Porphyrin Handbook, Eds K. M. Kadish,
K. M. Smith, and R. Guilard, Academic Press, San Diego,
California, 2003, 19, 179.
12. N. Kobayashi, S. Nakajima, H. Ogata, and T. Fukuda, Chem.
Eur. J., 2004, 10, 6294.
13. N. Kobayashi, Coord. Chem. Rev., 2002, 227, 129.
14. S. Makarov, Ch. Litwinski, E. A. Ermilov, O. Suvorova,
B. Röder, and D. Wöhrle, Chem. Eur. J., 2006, 12, 1468.
15. E. S. Dodsworth, A. B. P. Lever, P. Seymour, and C. C.
Leznoff, J. Phys. Chem., 1985, 89, 5698.
16. N. Kobayashi, H. Lam, W. A. Nevin, P. Janda, C. C.
Leznoff, and A. B. P. Lever, Inorg. Chem., 1990, 29, 3415.
17. Y. Asano and N. Kobayashi, Tetrahedron Lett., 2004,
45, 9577.
18. W. J. Schutte, M. SluytersꢀRehbach, and J. H. Sluyters,
J. Phys. Chem., 1993, 97, 6069.
19. K. Ishii, S. Abiko, M. Fujitsuka, O. Ito, and N. Kobayashi,
J. Chem. Soc., Dalton Trans., 2002, 1735.
14.5761(13) Å, α = 90°, V = 1332.7(2) Å3, Z = 4, dcalc
=
1.178 g cm–3, µ = 0.66 cm–1, the range of θ was 2.79—26.50°,
the number of measured reflections was 7597, the number of
independent reflections (Rint) was 1370 (0.03), the number of
refined parameters was 123, F(000) = 512, R1(I ≥ 2σ(I )) = 0.04,
wR2 (for all reflections) 0.1198, S(F 2) = 0.941.
The geometry of compound 3 was optimized and the
strain energies were calculated by the MM+ method using the
HyperChem 5.02 software.30 The electrostatic interactions were
calculated from the bond dipole moments.
20. N. Kobayashi and A. B. P. Lever, J. Am. Chem. Soc., 1987,
109, 7433.
The authors are grateful to T. Dülks for recording the
mass spectra.
21. D. Wöhrle, L. Kreienhoop, and D. Schlettwein, in Phthaloꢀ
cyanines. Properties and Applications, Eds C. C. Leznoff and
A. B. P. Lever, VCH Publishers, New York, 1996, 4, 219.
22. A. S. Davydov, Teoriya molekulyarnykh eksitonov [Theory of
Molecular Excitons], Nauka, Moscow, 1968, 296 pp. (in
Russian).
This work was supported by the Council on Grants at
Russian Federation President (Program for the State Supꢀ
port of Leading Scientific Schools of the Russian Federaꢀ
tion, NShꢀ8017.2006.3), the Russian Foundation for Baꢀ
sic Research (Project No. 06ꢀ03ꢀ32728ꢀа), the Federal
Target Science and Engineering Program (Contracts
02.442.11.7286 and 02.445.11.7365), and the German Sciꢀ
entific Research Society (Grant WO 237/32ꢀ3).
23. I. Granoth, Y. Segall, H. Leader, and R. Alkabets, J. Org.
Chem., 1976, 41, 3682.
24. J. Tellenbröker and D. Kuck, Eur. J. Org. Chem., 2001, 1483.
25. N. F. Yannoni and J. Silverman, Science, 1964, 148, 231.
26. W. G. Ferrier and J. Iball, Chem. Ind., 1954, 1296.
27. G. M. Sheldrick, Empirical Absorption Correction Program,
Universität Göttingen, Göttingen (Germany), 1996.
28. G. M. Sheldrick, Program for Crystal Structure Solution,
Universität Göttingen, Göttingen (Germany), 1990.
29. G. M. Sheldrick, Program for Crystal Structure Refinement,
Universität Göttingen, Göttingen (Germany), 1997.
30. HyperChem. R. 5.02 Pro, Hypercube Inc., Gainesville
(USA), 1997.
References
1. P. D. Harvey, in The Porphyrin Handbook, Eds K. M. Kadish,
K. M. Smith, and R. Guilard, Academic Press, San Diego,
California, 2003, 18, 63.
2. P. Erk and H. Hengelsberg, in The Porphyrin Handbook,
Eds K. M. Kadish, K. M. Smith, and R. Guilard, Academic
Press, San Diego, California, 2003, 19, 105.
Received July 26, 2006