Synthesis and spectral characteristics of cyclohexylmethoxy-substituted phthalocyanines of rare-earth elements

Article abstract of DOI:10.1007/s11172-007-0385-5

New symmetrical metal complexes of the rare-earth element phthalocyanines were synthesized by the reaction of 4,5-bis(cyclohexylmethoxy)phthalonitrile, obtained for the first time, with the rare-earth element salts, as well as starting from the corresponding free phthalocyanine. A correlation between method of the synthesis and the reaction product compositions was studied. Structures of the complexes obtained were confirmed by mass spectrometry, X-ray crystallography, and electronic absorption spectroscopy. All the metal complexes are well soluble in organic solvents.

Full text of DOI:10.1007/s11172-007-0385-5

Russian Chemical Bulletin, International Edition, Vol. 56, No. 12, pp. 2426—2432, December, 2007
2426
Synthesis and spectral characteristics of cyclohexylmethoxyꢀsubstituted
phthalocyanines of rareꢀearth elements
a
I. P. Kalashnikova,a S. E. Nefedov,b L. G. Tomilova,a and N. S. Zefirov

aInstitute of Physiologically Active Compounds, Russian Academy of Sciences,
142432 Chernogolovka, Moscow Region, Russian Federation.
Fax: +7 (496) 524 9508. Eꢀmail: tom@org.chem.msu.su
bN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation
New symmetrical metal complexes of the rareꢀearth element phthalocyanines were syntheꢀ
sized by the reaction of 4,5ꢀbis(cyclohexylmethoxy)phthalonitrile, obtained for the first time,
with the rareꢀearth element salts, as well as starting from the corresponding free phthalocyaꢀ
nine. A correlation between method of the synthesis and the reaction product compositions was
studied. Structures of the complexes obtained were confirmed by mass spectrometry, Xꢀray
crystallography, and electronic absorption spectroscopy. All the metal complexes are well
soluble in organic solvents.
Key words: phthalocyanines, rareꢀearth elements, electronic absorption spectra, mass specꢀ
trometry, Xꢀray analysis.
Scheme 1
Phthalocyanine metal complexes, including phthaloꢀ
cyanines of the rareꢀearth elements (REE), belong to the
unique class of macrocyclic compounds, which nowadays
are widely applied as the pigments,1,2 components of
chemical sensors,3—5 electrochromic devices,6 photoconꢀ
ducting materials,1,7 and semiꢀconductors.8,9 Due to their
properties and characteristics, phthalocyanines can be
widely used in diverse fields such as catalysis,10,11 nonlinꢀ
ear optics,12 peptide synthesis,13 and photodynamic therꢀ
apy.14,15
Physical and chemical characteristics of phthalocyaꢀ
nines depend on the complex structures, including the
number of macrocycles in the molecule, the nature of the
central metal ion, and peripheral substituents.
Benzyloxyꢀsubstituted REE diphthalocyanines, studꢀ
ied by us earlier,16,17 had electrochromic properties and
showed high efficiency in limitation of powerful laser raꢀ
diation. In order to study the influence of the peripheral
substituents, we synthesized hydrogenated analogs of the
benzyloxyꢀsubstituted phthalocyanines, viz., symmetrical
cyclohexylmethoxyꢀsubstituted phthalocyanine complexꢀ
es of Lu, Dy, Er, Eu, and Sm.
The synthesis of the starting phthalogene is given in
Scheme 1. The bromination of pyrocatechol was carried
out according to the procedures described earlier.18,19 The
reaction of 4,5ꢀdibromopyrocatechol with cyclohexylmeꢀ
thyl bromide in anhydrous DMSO in the presence of
КОН gave 4,5ꢀbis(cyclohexylmethoxy)ꢀ1,2ꢀdibromobenꢀ
zene (1) in 64% yield, the cyanation of which by the
Rosenmund—Braun method19—21 afforded dinitrile (2)
in 61% yield.
The use of such a phthalonitrile allowed us to obtain
phthalocyanine complexes with peripheral substituents,
which can exist in various conformational forms of the
chair—boat type, at the same time, being well soluble in
organic solvents.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2343—2349, December, 2007.
1066ꢀ5285/07/5612ꢀ2426 © 2007 Springer Science+Business Media, Inc.

Cyclohexylmethoxyꢀsubstituted phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 12, December, 2007 2427

2428
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 12, December, 2007
Kalashnikova et al.
Phthalocyanine complexes of Lu, Dy, and Sm were
obtained directly from phthalonitrile 2 and the correꢀ
sponding REE salt in nꢀpentanol in the presence of 1,8ꢀ
diazabicyclo[5.4.0]undecꢀ7ꢀene (DBU) under inert atꢀ
mosphere for 7 h (Scheme 2, Table 1).
were challenged by the problem with the low solubility of
phthalocyanine 3 in higher alcohols. On account of this,
attempted synthesis according to the procedure described
earlier22 was no success. On the basis of the electronic
absorption spectra (EAS) data, it was found that
the poorly soluble phthalocyanine 3 does not form
[Pc(OCH2C6H11)8]2– dianion in the presence of such a
strong base as DBU. That is why the metal complexes are
not formed under these conditions even in the presence
of a large excess of a REE salt. The use of the more basic
REE acetylacetonates instead of acetates did not make
any difference.
Scheme 2
The REE metal complexes were successfully syntheꢀ
Ln = Lu (5a), Dy (4, 5b), Sm (5c), Er (5d, 7a), Eu (5e, 7b);
X = OAc, OCHO
sized from free phthalocyanine
3 through the
formation of the intermediate compound, viz., dilithium
derivative Li2[Pc(OCH2C6H11)8] (6), which gives
[Pc(OCH2C6H11)8]2– dianion in the solution. Attempted
preparation of the dilithium complex from free phthaloꢀ
cyanine in the solution of lithium methoxide similarly to
the procedures for naphthalocyanines23,24 gave no result
in our case. Compound 3 is not dissolved in the freshly
prepared MeOLi solution in methanol to form
Li2[Pc(OCH2C6H11)8] complex even under prolonged
heating. The suspended phthalocyanine 3 was gradually
dissolving in MeOН with the formation of compound 6
only when the finely dispersed crushed lithium metal was
added to this suspension. During this, a characteristic
doubleꢀband EAS of free phthalocyanine transforms into
the singleꢀband spectrum corresponding to its dianion.
The EAS data for compounds 3 and 6 are given in Table 2.
Reagents: i. LnX3, nꢀpentanol, DBU; ii. Li (metal), MeOH; iii.
Ln(acac)3, nꢀpentanol.
It was found that in addition to the target diphthalocyꢀ
anine (compounds 5a—c), there is free octacyclohexylꢀ
methoxyphthalocyanine (3) in the reaction mixture
and in case of dysprosium, monophthalocyanine
Dy[Pc(OCH2C6H11)8]OAc (4) is presented as well. Prodꢀ
ucts 3, 4, and 5a—c were isolated from the reaction mixꢀ
tures by column chromatography and characterized by
spectrophotometry and MALDIꢀTOF method. Phthaloꢀ
cyanine 3, being a byꢀproduct, has low solubility in
nꢀpentanol and crystallizes upon cooling of the reaction
mixture, while the sandwich REE complexes remain in
the solution. Due to this, the main portion of compound
3 can be separated by filtration of the reaction mixture.
Chromatographic separation of Dy monoꢀ and diphthaꢀ
locyanines (4 and 5b) is based on the significant differꢀ
ences in their Rf values (0.28 and 0.90, respectively, silica
gel, CHCl3).
Table 2. MALDIꢀTOF spectra and EAS of phthalocyanines
Compound
MALDIꢀTOF,
M
λ
max/nm
m/z
(calculated) (CHCl3)
C88H114N8O8
1412
1631
2995
2982
2974
2987
2972
—
1411.90
1631.42
2994.73
2982.26
2970.12
2987.02
2971.72
1423.76
4564.16
4533.57
354, 414,
663, 702
352, 620,
686
After purification with hot methanol in a Soxhlet exꢀ
tractor, phthalocyanine 3 was used for the synthesis of Er
and Eu metal complexes (compounds 5d,e). Here, we
(3)
C90H115DyN8O11
(4)
C176H224LuN16O16
(5a)
C176H224DyN16O16
(5b)
C176H224N16O16Sm
(5c)
C176H224ErN16O16
(5d)
C176H224EuN16O16
(5e)
C88H112Li2N8O8
(6)
C264H336Er2N24O24
(7а)
C264H336Eu2N24O24
368, 481,
603, 673
369, 489,
613, 679
371, 495,
619, 685
369, 485,
609, 676
371, 495,
617, 683
360, 592,
635, 662*
345, 415,
635, 657
346, 405,
579, 663
Table 1. Reaction conditions, reaction product composition,
and yields of diphthalocyanines*
Starting
reagent
REE salt
τ/h Reaction
Yield of
diphthaloꢀ
cyanine (%)
products
1
Lu(OCHO)3•2Н2О
Dy (OAc)3•4 Н2О
Sm(OAc)3•4 Н2О
Er(OAc)3•4 Н2О
Er(acac)3
7
7
7
7
7
5
5
3, 5a
3, 4, 5b
3, 5c
—
5d
5d, 7a
5e, 7b
20
16
28
—
Traces
34
37
3
6
4561
Er(acac)3
Eu(acac)3
4529
(7b)
* DBU was used as the base, in case of the starting compound 6,
a base was not used.
* EAS value in acetone.

Cyclohexylmethoxyꢀsubstituted phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 12, December, 2007 2429
N(3)
N(1)
N(5)
a
N(7)
Er(1)
N(9)
N(9A)
Er(1)
N(11)
N(13)
Er(1A)
Er(1A)
N(3A)
N(1A)
N(5A)
N(7A)
Fig. 2. Immediate coordinate environment of Er atoms in moleꢀ
cule 7а.
b
Er(1)
is 2.322(9) Å, Er—N(3) is 2.329(9) Å, Er—N(5) is
2.336(9) Å, Er—N(7) is 2.329(9) Å) with turn the angle
between the internal and external decker of 26.1° (Fig. 2).
In the crystal unit, there are two solvate molecules of
pentanꢀ2ꢀol, a small amount of which is presented in
nꢀpentanol used as the solvent in this synthesis, as well as
six solvate molecules of water, the H atoms of four of
them having the contacts with the O atoms of the oxocyꢀ
clohexane substituents (О...Н is 2.01 Å), while the other
two, with the N atoms of the external deckers.
Er(1A)
Fig. 1. Horizontal (a) and front (b) projections of molecule 7a.
The complexes obtained are characterized by spectroꢀ
photometry. The EAS data attest that diphthalocyanines
5а—е are the freeꢀradical neutral forms [Pc•–Ln3+Pc2–]:
in the spectra of these compounds, there is a Qꢀband at
673—685 nm characteristic of phthalocyanines and a band
Diphthalocyanine complexes of Er and Eu were obtained
by the reaction of dilithium complex 6 with REE salts in
nꢀpentanol. Acetylacetonates of Er and Eu were used as
the source of the REE cations. It was found that the
reaction takes place in the absence of DBU, giving a small
amount of tripleꢀdecker REE phthalocyanines (7a,b) as
the byꢀproducts. Products 7a,b were isolated in pure form
by column chromatography and characterized by specꢀ
trophotometry and MALDIꢀTOF method. In addition,
erbium tripleꢀdecker complex 7a was isolated in the crysꢀ
talline form from the THF solution and characterized by
Xꢀray method. According to the Xꢀray data, in the tripleꢀ
decker sandwich complex 7а, two ErIII atoms, being on
the nonꢀbonding metal—metal distance of 3.4866(12) Å
in length, are bound with four N atoms, belonging to the
bridged phthalocyanine fragment (Er—N(9) is 2.607(9) Å,
Er—N(11) is 2.580(9) Å, Er—N(13) is 2.593(9) Å). Moꢀ
lecular structure of 7a is given in Figure 1, a, b. The
coordinate environment of each metal atom, viz., a disꢀ
torted square antiprism, is supplemented with four N atꢀ
oms of the peripheral phthalocyanine ligand (Er—N(1)
–
at 481—495 nm on account of the presence of the Pc•
freeꢀradical fragment in the molecule. The Soretꢀband
has the maximum in the region 368—371 nm. Analysis of
the EAS also demonstrates such features characteristic of
this class of compounds as bathochromic shift of the
Qꢀband and wiggle satellite from 673 and 603 nm for Lu
diphthalocyanine to 685 and 619 nm for Sm diphthalocyꢀ
anine, respectively, which is caused by an increase in
ionic radius of a lanthanide. There is also a bathochromic
shift of the band corresponding to the freeꢀradical fragꢀ
ment, while there is only a slight change in position of the
Soretꢀband. In the spectrum of Dy monophthalocyanine
(4), there is no band at 489 nm characteristic only of
diphthalocyanines, while a bathochromic shift of the
Qꢀband and wiggle satellite by 7 nm for Dy monophthaꢀ
locyanine relatively to the corresponding Dy diphthaloꢀ
cyanine could be seen. The Soretꢀband here has a hypsoꢀ

2430
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 12, December, 2007
Kalashnikova et al.
A
I (arb. units)
2995
1.5
1.0
0.5
a
8
6
4
2
1
2
400
500
600
700
λ/nm
Fig. 3. Electronic absorption spectra of dysprosium monoꢀ (4)
and diphthalocyanine (5b) (1 and 2, respectively).
A
1.0
1
0.8
2
0.6
0.4
0.2
0
1000
2000
3000
m/z
I (arb. units)
2995
400
500
600
700
λ/nm
2996
8
Fig. 4. Electronic absorption spectra of europium diꢀ (5е) and
triphthalocyanine (7b) (1 and 2, respectively).
2994
b
2997
6
4
2
chromic shift. The spectra of cyclohexylmethoxyꢀsubstiꢀ
tuted Dy monoꢀ and diphthalocyanines are given in Fig. 3;
there is a distinction between the EAS of tripleꢀdecker
phthalocyanines and diphthalocyanines. Positions of the
Soretꢀband and Qꢀband maxima are close, while the
Qꢀband of the tripleꢀdecker complex is considerably
broadened and has a profound shoulder, which can be,
apparently, explained by the sterical hindrance caused by
bulky substituents.22 The EAS of Eu diꢀ and tripleꢀdecker
phthalocyanines are given in Fig. 4.
2998
2993
2985
2990
2995
3000
m/z
From the data published by us earlier, it follows that
position of the Qꢀband virtually does not change for аcyꢀ
clic hexadecaalkoxyꢀsubstituted diphthalocyanines with
Fig. 5. MALDIꢀTOF spectrum of diphthalocyanine 5а (a) and
the molecular ion peak (b).
the alkoxy substituents of different length and it is at
~664—669 and 674—680 nm for Lu and Sm diphthalocyꢀ
anines, respectively.19,25 Close values were observed for
diphthalocyanines with aromatic benzyloxy substituents.16
From the data in Table 3 it follows that for alicyclic peꢀ
ripheral substituents, the Qꢀband bathochromically shifts
by ~10 nm.
The MALDIꢀTOF method was used for the mass specꢀ
trometry study. In the mass spectra of the compounds,
singleꢀcharged peaks with the weights corresponding to
the molecular ions were observed. The spectrophotometꢀ
ric and mass spectrometric data are given in Table 2. The
MALDIꢀTOF spectra and molecular ion peak of Lu diꢀ
phthalocyanine are given in Fig. 5.
Table 3. Position of Qꢀband maximum of some hexadecaꢀsubstiꢀ
tuted diphthalocyanines Ln[Pc(OR)8]2 (Ln = Lu, Sm)
Ln
Lu
R
λ
max/nm (CHCl3)
Pr
C5H11
CH2Ph
CH2C6H11
Pr
C5H11
CH2Ph
CH2C6H11
660 19
669 25
662 16
673*
680 19
675 25
675 16
685*
Sm
* Determined in the present work.

Cyclohexylmethoxyꢀsubstituted phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 12, December, 2007 2431
MgSO4. The solvent was evaporated at reduced pressure to obꢀ
tain additional crop of the product (0.3 g). The combined prodꢀ
uct was recrystallized from ethanol and sublimated in vacuo to
obtain white crystals (3.21 g, 61%), m.p. 131—133 °С. Found
(%): С, 75.00; Н, 8.07; N, 7.90. C22H28N2O2. Calculated (%):
С, 74.96; Н, 8.01; N, 7.95. 1H NMR (CDCl3), δ: 10.98—1.43
(m, 10 Н, С6Н11); 1.60—1.95 (m, 12 Н, С6Н11); 3.80 (d, 4 Н,
OСН2, J = 5.8 Hz); 7.04 (s, 2 Н, С6Н2).
Experimental
nꢀPentanꢀ1ꢀol (pure grade) was used after distillation, DMF
(pure for analysis grade) and DMSO (chemically pure) were
distilled in vacuo and dried with barium oxide. For the synthesis
of compound 1, КОH (pure for analysis grade) was used. Cycloꢀ
hexylmethyl bromide (Lancaster, 98%) was used without addiꢀ
tional purification. For the synthesis of phthalocyanines, forꢀ
mates, acetates, and acetylacetonates of the corresponding lanꢀ
thanides (pure for analysis grade) were used. NMR spectra were
recorded on a Bruker DPXꢀ200 spectrometer (200 MHz, relaꢀ
tively to Me4Si). EAS spectra were recorded on a Specord UV—
Vis spectrophotometer (Carl Zeiss), mass spectra were recorded
on a VISIONꢀ2000 instrument (MALDIꢀTOF).
Lutetium(III) 2,2´,3,3´,9,9´,10,10´,16,16´,17,17´,23,23´,
24,24´ꢀhexadeca(cyclohexylmethoxy)diphthalocyanine (5а). A
mixture of phthalonitrile
2
(400 mg, 1.13 mmol),
Lu(OCHO)3•2Н2О (49 mg, 0.14 mmol), and DBU (128 mg,
0.84 mmol) was refluxed for 7 h in nꢀpentanol (25 mL) under
argon atmosphere. After cooling, the formed precipitate of phthaꢀ
locyanine 3 was filtered off and washed with aq. methanol. The
filtrate was concentrated, ethyl acetate (15 mL) was added to it,
and the mixture was refluxed for 15 min and cooled. An addiꢀ
tional amount of phthalocyanine 3, undissolved in ethyl acetate,
was filtered off. The solution of the diphthalocyanine 5a in ethyl
acetate was concentrated, the residue was dissolved in CHCl3
and subjected to column chromatography on silica gel (eluent,
benzene—МеОН, 10 : 1). After evaporation of the solvent, comꢀ
pound 5a as a dark green powder was obtained (83 mg, 20%).
Phthalocyanine 3 was placed in the Soxhlet apparatus, extracted
with methanol from tars and admixture of the starting phthaꢀ
lonitrile 2, and dried in vacuo.
Column chromatography was performed on Lancaster Siliꢀ
ca Gel 60 (0.060—0.200 mm) and on polymeric BioꢀBeads SꢀX1
packing material.
Xꢀray
analysis
of
compound
7а•6Н2О•
•Me(СН2)2СН(ОН)Me was performed on a SMART APEX
diffractometer, CCD detector (λ(MoꢀKα) = 0.71073 Å, graphꢀ
ite monochromator, ωꢀscanning technique, 2θ
= 46°);
max
C274H348N24O32Er2, M = 4824.28, monoclinic syngonia, space
group C2/c, a = 46.883(9) Å, b = 26.394(5) Å, c = 22.847(4) Å,
α = 114.117(2)°, V = 25804(8) Å3 (120 К), Z = 4, dcalc = 1.242
g cm–3, 17887 measured reflections, 8508 independent reflecꢀ
tions with F2 > 2σ(I), µ = 0.717 mm–1, R1 = 0.0874, wR2
=
0.1827. The peripheral cyclohexylmethoxy fragments are disorꢀ
dered over few positions, the multiplicity of which was not preꢀ
cisely detected. Hydrogen atoms were geometrically generated
and refined using a riding model. All the calculations were carꢀ
ried out with the use of SAINT26 and SHELXTLꢀ97 program
packages.27
Dysprosium(III) 2,3,9,10,16,17,23,24ꢀocta(cyclohexylꢀ
methoxy)phthalocyanine monoacetate (4) and dysprosium(III)
2,2´,3,3´,9,9´,10,10´,16,16´,17,17´,23,23´,24,24´ꢀhexadecaꢀ
(cyclohexylmethoxy)diphthalocyanine (5b). The synthesis was carꢀ
ried out similarly to the procedure for compound 5а from
phthalonitrile 2 (400 mg, 1.13 mmol) and Dy(OAc)3•4Н2О
(58 mg, 0.14 mmol). A byꢀproduct, phthalocyanine 3, was isoꢀ
lated as in the procedure for 5а. A mixture of soluble products 4
and 5b was separated by column chromatography (SiO2, CHCl3),
with diphthalocyanine 5b being the first to elute and monoꢀ
phthalocyanine 4 being the second. Compounds 4 (67 mg, 29%)
and 5b (80 g, 16%) were obtained.
Samarium(III) 2,2´,3,3´,9,9´,10,10´,16,16´,17,17´,23,23´,
24,24´ꢀhexadeca(cyclohexylmethoxy)diphthalocyanine (5с) was
obtained similarly to compound 5а from phthalonitrile 2
(400 mg, 1.13 mmol) and Sm(OAc)3•4 Н2О (56 mg, 0.14 mmol)
in the presence of DBU (128 mg, 0.84 mmol). The yield was
116 mg (28%).
Dilithium 2,3,9,10,16,17,23,24ꢀocta(cyclohexylmethoxy)ꢀ
phthalocyanine (6). Finely dispersed lithium metal (4.5 mg,
0.63 mmol) was added to a suspension of phthalocyanine 3
(300 mg, 0.21 mmol) in methanol (40 mL) and the reaction
mixture was refluxed for 4 h under inert atmosphere. After coolꢀ
ing, the solvent was evaporated, the residue was placed in the
Soxhlet apparatus to extract the product 6 with anhydrous aceꢀ
tone, filtering off the insoluble in acetone LiOH and unreacted
phthalocyanine 3. The solvent was evaporated to obtain 250 mg
of dilithium derivative 6 as the dark green solid substance, which
was further used without additional purification. The EAS data
of product 6 are given in Table 2.
Erbium(III) 2,2´,3,3´,9,9´,10,10´,16,16´,17,17´,23,23´,
24,24´ꢀhexadeca(cyclohexylmethoxy)diphthalocyanine (5d) and
dierbium(III) tris[2,3,9,10,16,17,23,24ꢀocta(cyclohexylmethoxy)ꢀ
phthalocyanine] (7а). A mixture of derivative 6 (100 mg,
7.02•10–5 mol) and Er(acac)3 (22 mg, 4.68•10–5 mol) in
4,5ꢀBis(cyclohexylmethoxy)ꢀ1,2ꢀdibromobenzene (1). Powꢀ
dered КОН (10.77 g, 0.192 mol) was added to anhydrous DMSO
(50 mL) with stirring at ~20 °C. After 5 min, dibromopyrocateꢀ
chol (6.52 g, 0.024 mol) and cyclohexylmethyl bromide (17.24 g,
0.097 mol) were sequentially added to the mixture. The reaction
mixture was initially stirred in an ice bath for 30 min and then,
at ~20 °C for 4.5 h. After the reaction was over, the mixture was
poured into ice water (200 mL), extracted with dichloromethane
(4×30 mL), sequentially washed with diluted aqueous NaOH
(2×30 mL) and water, and dried with MgSO4. After the solvent
and excess cyclohexylmethyl bromide were evaporated in vacuo,
a mobile red oil was obtained, which was dissolved in benzene
and subjected to column chromatography on alumina (eluent,
benzene). After the solvent was evaporated, the product was
recrystallized from ethyl acetate—hexаne (1 : 1) to obtain colorꢀ
less crystals (7.04 g, 64%), m.p. 73—74 °С. Found (%): С, 52.13;
Н, 6.09; Br, 34.76. C20H28Br2O2. Calculated (%): С, 52.19;
Н, 6.13; Br, 34.72. 1H NMR (CDCl3), δ: 0.90—1.40 (m,
10 Н, С6Н11); 1.60—1.90 (m, 12 Н, С6Н11); 3.70 (d, 4 Н,
OСН2, J = 5.8 Hz); 7.00 (s, 2 Н, С6Н2).
4,5ꢀBis(cyclohexylmethoxy)phthalonitrile (2). A mixture of
dibromide 1 (7.00 g, 0.015 mol) and CuCN (4.09 g, 0.046 mol)
in anhydrous DMF (90 mL) was refluxed for 7 h. After cooling,
almost all the solvent was evaporated, dichloromethane (50 mL)
and concentrated aq. ammonia (500 mL) were added to the
residue, and the mixture was stirred for 1 day. The precipitate
formed was filtered off, washed with water, and dried. The filꢀ
trate was extracted with dichloromethane (3×15 mL), the comꢀ
bined organic extracts were washed with water and dried with

2432
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 12, December, 2007
Kalashnikova et al.
nꢀpentanol (20 mL) was refluxed for 12 h under inert atmoꢀ
sphere. After cooling, the solvent was evaporated in vacuo, the
residue was dissolved in СНСl3. The tars and the small admixꢀ
ture of the metalꢀfree phthalocyanine were separated off by
column chromatography (SiO2, CHCl3), then, products 5d and
7a were separated by additional chromatography (BioꢀBeads,
THF). The solvent was evaporated to obtain compounds 5d
(35 mg, 34%) and 7a (5 mg, 4.7%).
Europium(III) 2,2´,3,3´,9,9´,10,10´,16,16´,17,17´,23´,23,
24,24´ꢀhexadeca(cyclohexylmethoxy)diphthalocyanine (5e) and
dieuropium(III) tris[2,3,9,10,16,17,23,24ꢀocta(cyclohexylꢀ
methoxy)phthalocyanine] (7b) were obtained from derivative 6
(100 mg, 7.02•10–5 mol) and Eu(acac)3 (21 mg, 4.68•10–5
mol) similarly to the synthesis of 5d. Diphthalocyanine 5e (38 mg,
37%) and tripleꢀdecker complex 7b (3.5 mg, 3.2%) were isolated.
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Received April 25, 2007;
in revised form October 16, 2007