Synthesis and copper(I)-driven disaggregation of a zinc-complexed phthalocyanine bearing four lateral coordinating rings

Article abstract of DOI:10.1002/ejoc.201200944

A new zinc phthalocyaninate, bearing four flexible phenanthroline- containing 30-membered rings was synthesized by template condensation of a macrocyclic phthalonitrile. The resulting phthalocyanine was an insoluble aggregate. However, in the presence of Cu^I ions, the formation of a soluble complex was observed. UV/Vis and DOSY NMR spectroscopic studies showed a monomolecular state for this species in solution. ¹H-¹H ROESY demonstrated that the macrocyclic substituents adopt a folded conformation, giving the complex a globular shape. The folding originates from stacking interactions between the phthalocyanine core and peripheral copper(I)-phenanthroline complexes. Copyright

Full text of DOI:10.1002/ejoc.201200944

FULL PAPER
DOI: 10.1002/ejoc.201200944
Synthesis and Copper(I)-Driven Disaggregation of a Zinc-Complexed
Phthalocyanine Bearing Four Lateral Coordinating Rings
Alexander G. Martynov,*[a,b,c] Yulia G. Gorbunova[a,b] Sergey E. Nefedov[b]
Aslan Y. Tsivadze,[a,b] and Jean-Pierre Sauvage*[c]
Keywords: Macrocyclic ligands / Phthalocyanines / Template synthesis / Conformation analysis / Copper
A new zinc phthalocyaninate, bearing four flexible phenan- scopic studies showed a monomolecular state for this species
throline-containing 30-membered rings was synthesized by
template condensation of a macrocyclic phthalonitrile. The
resulting phthalocyanine was an insoluble aggregate. How-
ever, in the presence of CuI ions, the formation of a soluble
complex was observed. UV/Vis and DOSY NMR spectro-
in solution. 1H-1H ROESY demonstrated that the macrocyclic
substituents adopt a folded conformation, giving the complex
a globular shape. The folding originates from stacking inter-
actions between the phthalocyanine core and peripheral cop-
per(I)–phenanthroline complexes.
efficient synthesis of new phthalocyanine 1, bearing four
lateral 1,10-phenanthroline (phen) containing coordinating
rings. Compound 1 was synthesized with the aim of using
it as a building block for multicatenanes and rotaxanes,
prototypes of new molecular machines and receptors.[23]
Introduction
Over the course of the last two decades, comprehensive
studies of phthalocyanines bearing lateral macrocyclic sub-
stituents have been carried out. By taking advantage of the
complexing properties of their peripheral binding sites, it is
possible to efficiently control the assembly of these func-
tionalized phthalocyanines.[1–5] For example, interaction of
crown–phthalocyanines with alkali metal ions afforded
multideck species,[6–11] conducting mesophases,[12,13] and
biomimetic models of photosynthesis.[14,15] Interaction be-
tween the crown-ether components and secondary ammo-
nium ions afforded pseudo-rotaxanes and rotaxanes.[16–19]
Much less attention was paid to phthalocyanines bearing
macrocyclic units capable of peripheral transition metal
binding. Interaction of transition metal ions with macro-
cyclic ligands is one of the most powerful approaches for
assembling catenanes and rotaxanes.[20] This approach has
been widely used to construct interlocking-ring compounds
containing porphyrins,[21,22] but it has never been applied in
phthalocyanine chemistry. We would now like to report the
Results and Discussion
Synthesis of the Phthalonitrile Precursor
Previously reported (dicyanobenzo)crown ethers contain-
ing additional aromatic functional groups, which are pre-
cursors to functionalized phthalocyanines, were synthesized
by cycloalkylation of aromatic bis(phenols) with open-chain
o-dibromo derivatives followed by Rosenmund–Braun cy-
anation.[24–26] This reaction resulted in only moderate yields
of macrocyclic phthalonitriles, probably owing to the harsh
reaction conditions, which can promote the formation of
copper phthalocyaninate, as well as other side reactions.
Herein, we report the proposal and successful implementa-
tion of a reorganised reaction sequence, introducing cyano
groups before formation of the macrocycle (Scheme 1),
which avoids the formation of complexes of copper cations
with chelating phenanthroline units.
[a] A. N. Frumkin Institute of Physical Chemistry and Electro-
chemistry of the Russian Academy of Sciences,
Leninskiy pr., 31, bdg. 4, 119071 Moscow, Russia
E-mail: Martynov.Alexandre@gmail.com
Implementation of this strategy required preparation of
[b] N. S. Kurnakov Institute of General and Inorganic Chemistry a phthalonitrile bearing two diethylene glycol (DEG) chains
Homepage: http://eng.phyche.ac.ru/
of the Russian Academy of Sciences,
(4 in Scheme 1). Previous attempts to prepare 4 either by
Leninskiy pr., 31, 119991 Moscow, Russia
alkylation of 4,5-dicyanocatechol with chloroethoxy-
ethanol[27] or by Pd/C-catalysed hydrogenolysis of bis{2Ј-
[2ЈЈ-(benzyloxy)ethoxy]ethoxy}phthalonitrile[28] were un-
successful. So, we decided to study the cyanation of the o-
dibromide, which already contains the required DEG
chains. Catechol was first alkylated with 2-(2-chloro-
ethoxy)ethanol yielding diol 2,[29] which was then bromin-
E-mail: yulia@igic.ras.ru
Homepage: http://www.igic.ras.ru/
[c] Institut de Science et d’Ingénierie Supramoléculaires, Université
de Strasbourg,
8 allée Gaspard Monge, 67000 Strasbourg, France,
E-mail: jpsauvage@unistra.fr
Homepage: http://wwwchimie.u-strasbg.fr/~lcom/
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201200944.
6888
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Disaggregation of a Zinc-Complexed Phthalocyanine Derivative
Scheme 1. (i): NBS, DMF, room temp. (yield 75%); (ii): Zn(CN)2, Pd2(dba)3, dppf, DMAA, 120 °C (yield 85%); (iii): TsCl, K2CO3,
DMAP, 0Ǟ20 °C (yield 63%); (iv): 6, Cs2CO3, DMF, 65 °C (yield 69%); (v): Zn(OAc)2, DBU, iAmOH, o-DCB, reflux (yield 56%).
ated with N-bromosuccinimide (NBS) in N,N-dimethyl- X-ray Crystallography of Macrocyclic Phthalonitrile 7
formamide (DMF) providing dibromide 3. However,
Slow concentration of a saturated solution of 7 in a mix-
ture of dichloromethane and methanol afforded yellow
Rosenmund–Braun cyanation of 3 with CuCN in refluxing
DMF failed to convert it into dinitrile 4. For this reason,
crystals suitable for X-ray diffraction analysis. Analysis re-
we took note of a Pd-catalysed cyanation reaction – an ap-
vealed that 7 adopts a chair-like conformation with almost
proach widely used to synthesize aromatic mononitriles,[30]
coplanar phenanthroline and phthalonitrile units (angle
2.9°, Figure 1). The 2,9-diarylphenanthroline unit of the
but quite rarely used to prepare o-dinitriles.[31–33]
Recently, Hanack et al. proposed a general procedure for
macrocycle is almost flat with dihedral angles between aryl
the preparation of phthalonitriles under mild conditions,[33]
and phenanthroline units equal to 6.0 and 4.6°.
which tolerate various functional groups. This method im-
plies cyanation of o-dibromides by Zn(CN)2 in the presence
of tris(dibenzylideneacetone)dipalladium [Pd2(dba)3] and
1,1Ј-bis(diphenylphosphanyl)ferrocene (dppf) in N,N-di-
methylacetamide (DMAA) at 110–120 °C. The addition of
polymethylhydrosiloxane (PMHS)[34] made it possible to
avoid the use of an inert gas.
Performing this reaction under the proposed condi-
tions[33] in air resulted in a low yield of nitrile 4. Chromato-
graphic monitoring of the reaction course showed that the
conversion of 3 into 4 occurs during the first 15 min, but
then the reaction terminates, leaving most of the starting
dibromide 3 unreacted. However, when the same reaction
was performed under argon, the desired phthalonitrile 4
was obtained in excellent yield (85%).
Tosylation of 4 with TsCl with 4-(dimethylamino)pyr-
idine (DMAP) and excess of K2CO3 in acetonitrile afforded
open-chain precursor 5. It was further used for cycloalkyl-
ation of 2,9-bis(p-hydroxyphenyl)-1,10-phenanthroline (6)
Figure 1. Molecular structure of 7 with thermal ellipsoids drawn at
the 50% probability level.
[35]
in the presence of Cs2CO3 under high-dilution condi-
Macrocycle 7 crystallizes with 3 solvate molecules of
tions to afford macrocyclic phthalonitrile 7 in 65% yield.
dichloromethane (Figure 2), in which the hydrogen atoms
Therefore, successful completion of steps (iii) and (iv) form weak contacts with the oxygen atoms of the DEG
showed that the phthalonitrile fragment is robust enough chains as well as the nitrile nitrogen atoms. The molecules
to withstand the conditions of both tosylation and cyclo- in the crystal form head-to-tail dimers with fairly short π–
alkylation. Thus, this approach looks promising for the π stacking contacts (C···C 3.519–3.801 Å). In turn, these
preparation of other macrocyclic phthalonitriles bearing la- dimers form layers, inclined at 74.6° with respect to each
bile or coordinating functional groups.
other (Supporting Information, Figure S8).
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Figure 3. UV/Vis spectra of 1 (suspension) in CHCl3/CH3CN (1:1,
v/v) before (dashed line) and after treatment with [Cu(CH3CN)4]-
(PF6) (solid line).
Figure 2. Hydrogen bonds [Å] in the crystal lattice of compound
7: O(1)···C(41) 3.471, O(2)···C(42) 3.448, O(3)···C(42) 3.258, O(4)···
C(42) 3.227, O(5)···C(42) 3.460, N(4)···C(43) 3.247.
onance signals became sharper, may suggest some dynamic
conformational process involving the phen part of the mole-
cule only.
Synthesis and Investigation of Phthalocyanine 1
When starting macrocyclic precursor 7 was treated with
[Cu(CH3CN)4](PF6) in a mixture of CDCl3/CD3CN (1:1,
v/v), a small but significant downfield shift of the resonance
signals of the phen protons was observed owing to the weak
electron-withdrawing effect of the CuI centre (Figure 4).
The condensation leading to phthalocyaninate 1 was car-
ried out by treating 7 with zinc acetate and 1,8-diazabicy-
clo[5.4.0]undecene-7 (DBU) in a refluxing mixture of
isoamyl alcohol/1,2-dichlorobenzene (o-DCB) (1:1). The re-
sulting compound was found to be almost insoluble in com-
mon organic solvents, apparently because of strong aggre-
gation. Therefore, purification and isolation of 1 could not
be performed by chromatography. Thus, 1 was purified first
by treatment of the reaction mixture with an aqueous ethyl-
enediaminetetraacetic acid (EDTA) solution to remove ex-
cess ZnII ions. Then, the soluble organic impurities were
extracted with toluene in a Soxhlet apparatus, yielding 1 as
a bluish-green insoluble powder.
1
However, the H NMR spectra of complexes [7·Cu+] and
[1·4Cu+] differed, and it was noticed that the resonance sig-
nals of the phen protons in [1·4Cu+] were significantly
shifted upfield relatively to the spectrum of [7·Cu+]. This
upfield shift is particularly large for protons 5 and 6 located
at the rear of the phen nucleus.
To overcome the low solubility of 1, a suspension of 1 in
CHCl3/CH3CN (1:1) was treated with 4 equiv. of
[Cu(CH3CN)4](PF6), which resulted in rapid formation of
a transparent green solution. UV/Vis monitoring of this
process demonstrated significant changes (Figure 3). The
broad structureless band of 1 (mostly in suspension) van-
ished, and a narrow Q-band at 680 nm with a well-resolved
vibration overtone at 612 nm, typical for monophthalocy-
aninates, was observed, suggesting the monomeric state of
the resulting Pc species [1·4Cu+]. Notably, addition of ZnII
and AgI salts did not result in dissolution of 1.
The NMR spectrum of the soluble compound obtained
after addition of copper(I) exhibited the expected number
of signals, which were assigned by 1H-1H COSY and
ROESY experiments. Increasing the temperature to 55 °C
resulted in a small upfield shift and sharpening of the reso-
nance signals attributed to the phen protons, whereas the
aromatic protons of the phthalocyanine (Pc) ring (HPc) did
Figure 4. Aromatic region of 1H NMR spectra of 7, [7·Cu+] and
[1·4Cu+] (CDCl3/CD3CN at 25 °C for 7 and [7·Cu+] and 55 °C for
[1·4Cu+]; for the latter compound, it was checked that the chemical
shifts of the various protons were only slightly temperature-de-
pendent). Proton numbering is given in Scheme 1.
In the ROESY spectrum of [1·4Cu+] cross-peaks between
not change position and breadth (Supporting Information, the o,m-protons of the phenyl groups belonging to the ring
Figure S5). The position of the latter signals is known to and HPc were observed, suggesting that these two sets of
be sensitive to aggregation of Pc molecules, which can be protons are in close proximity in solution (Figure 5).
hindered by increasing temperature.[36] Therefore, the fact
This can be rationalized by assuming that owing to the
that by raising the temperature the chemical shift and the flexibility of DEG chains the phen-incorporating rings are
shape of HPc were not affected, whereas the Hphen res- folded in such a way that the rear of the phen units lie above
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Disaggregation of a Zinc-Complexed Phthalocyanine Derivative
Figure 6. MM+ model of the folded conformation of [1·4Cu+]. The
phthalocyanine ring is coloured in blue, the lateral macrocycles are
coloured in green, the red spheres correspond to copper(I) ions.
in the ZnII coordination sphere, in line with previously re-
ported data.[37] Two acetonitrile molecules are also likely to
form coordination bonds with each CuI ion introduced into
the peripheral macrocycles. Indeed, acetonitrile is a strong
π-acceptor and a weak σ-donor, which fulfils the require-
ments of monovalent copper.
1
Figure 5. Aromatic region of H-1H ROESY spectrum of [1·4Cu+]
(CDCl3/CD3CN at 55 °C). The ovals mark the cross-peaks, which
suggest a folded conformation of the macrocyclic substituents (in-
set).
or below the plane of the Pc nucleus. The phen units will
thus experience the ring-current effect of the Pc group, and
the 4, 5, 6 and 7 protons will undergo a strong upfield shift
(Δδ5,6 = –1.32 and Δδ4,7 = –0.98 ppm, relative to [7·Cu+]).
This is also the case for protons 3 and 8, but to a lesser
extent (Δδ3,8 = –0.50 ppm). Another possibility, which
could account for the observed upfield shift of the HPhen
resonance signals, would be intermolecular stacking be-
tween the phen units of a given molecule and the Pc ring
of another one.
Conclusions
A new phthalocyanine bearing four peripheral coordinat-
ing rings has been synthesised in good yield from relatively
simple precursors. Owing to the presence of phen groups in
the lateral rings, the compound can form stable complexes
with transition metals such as copper(I). Coordination of
this metal centre to the peripheral rings suppresses com-
pletely the aggregation of the phthalocyanines and allows
solution studies to be performed. Addition of copper(I) also
changes dramatically the conformation of the system, lead-
ing to a folded and globular structure. Previously, a similar
folding process driven by π–π interactions was evidenced
in a gold(III) porphyrinate attached to a phen-containing
macrocycle.[38] To the best of our knowledge this type of
interaction has never been observed in the case of phthalo-
cyanines bearing peripheral macrocyclic substituents.
It is expected that the system described herein will pave
the way to new interlocking-ring compounds incorporating
phthalocyanines.
To distinguish between intra- and intermolecular stack-
1
ing, H-DOSY measurements were performed (Supporting
Information, Figure S7). They revealed the presence of a
single molecular species with a diffusion coefficient of
3.6ϫ10–10 m2 s–1. Modelling of [1·4Cu+] with four folded
macrocycles suggested a globular structure with a radius of
ca. 12 Å (Figure 6), in good agreement with the hydrody-
namic radius estimated from the diffusion coefficient
(12.2 Å).
Altogether, the NMR study demonstrates that [1·4Cu+]
is a monomeric species in solution, with folded macrocyclic
units. The folded conformation is likely to be stabilised by
the interaction between the electron-deficient [phen·Cu+]
units and the electron-donating Pc nucleus.
The presence of CD3CN in the samples prepared for the
NMR spectroscopic measurements could result in axial co-
ordination of one acetonitrile molecule to ZnII in [1·4Cu+],
which could provide environmental non-equivalence of the
two sides of the globular molecule, which in turn could re-
sult in the appearance of several sets of resonance signals,
leading to complicated NMR spectra. However, in the spec-
trum of [1·4Cu+] each type of protons gave only one reso-
Experimental Section
General: Catechol, 2-(2-chloroethoxy)ethanol, NBS, zinc cyanide,
tris(dibenzalacetone)dipalladium(0) [Pd2(dba)3], dppf, DMAP and
DBU were available from commercial suppliers (Aldrich, Merck)
and used without further purification. Potassium and caesium
carbonates were dried at 120 °C in an oven. The solvents (CHCl3,
EtOAc, hexane) were distilled from CaH2. DMF (Aldrich,
Ն 98.0%) and DMAA (Aldrich, Ն 99%), were used as received
nance signal, suggesting fast exchange of the axial ligands without further purification. 1,2-Bis[2Ј-(2ЈЈ-hydroxyethoxy)ethoxy]-
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A. G. Martynov, J.-P. Sauvage et al.
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benzene (2)[29] and 2,9-bis(p-hydroxyphenyl)-1,10-phenanthroline
(6)[35] were synthesized as reported previously. NMR spectra were
recorded with a Bruker Avance 400 spectrometer (400.14 MHz for
1H and 100.62 MHz for 13C). NMR spectra were referenced against
the residual solvent signal.[39] Melting points were measured with
a Büchi B-540 melting point analyser. Mass spectra (ES-MS) were
recorded with a BrukerMicroTOF spectrometer by the Service de
(m, 8 H, α,β-OCH2), 7.17 (s, 2 H, 3,6-H), 7.32 (d, J = 8.1 Hz, 4 H,
m-H), 7.77 (d, J = 8.1 Hz, 4 H, o-H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.78, 69.25, 69.33, 69.44, 69.45, 109.11, 115.82,
117.02, 128.06, 130.01, 133.04, 145.10, 152.40 ppm. FT-IR (neat):
ν = 2229 (CϵN), 1590, 1521, 1449, 1414, 1368, 1349, 1333, 1293,
˜
1232, 1214, 1188, 1172, 1141, 1095, 1023, 1010, 950, 914, 900, 857,
812, 781, 769 cm–1. HRMS: calcd. for C30H32N2NaO10S2 [M +
Spectrométrie de Masse (Université de Strasbourg). UV/Vis spectra Na]+ 667.139; found 667.138.
were measured with a Varian Cary-100 spectrometer in quartz cu-
Macrocycle 7: A degassed solution of ditosylate 5 (515 mg,
vettes with 1 cm optical path. An FT-IR Nexus (Nicolet) spectro-
photometer with micro-ATR accessory (Pike) was used to record
IR spectra. Elemental analysis was performed with a Carlo–Erba
1106 instrument.
0.8 mmol) and 2,9-bis(p-hydroxyphenyl)-1,10-phenanthroline (6)
(291 mg, 0.8 mmol) in DMF (175 mL) was added dropwise to a
vigorously stirred suspension of Cs2CO3 (2.60 g, 8 mmol) in DMF
(300 mL) at 70 °C over 8 h. After complete addition, the reaction
mixture was stirred for 1 d. The warm reaction mixture was filtered,
the solids were washed with DMF, and the filtrate was concen-
trated. The resulting brown solid was purified by using silica (chlo-
roform) affording target macrocyclic dinitrile 7 as a yellowish solid
(369 mg, 69%); m.p. 256–289 °C (decomp.). 1H NMR (400 MHz,
CDCl3): δ = 3.90 (t, J = 5.2 Hz, 4 H, γ-OCH2), 3.97 (t, J = 5.1 Hz,
1,2-Dibromo-4,5-bis[2Ј-(2ЈЈ-hydroxyethoxy)ethoxy]benzene (3): Diol
2 (3.66 g, 12.8 mmol) was dissolved in DMF (25 mL), and a solu-
tion of NBS (4.98 g, 28.2 mmol) in DMF (25 mL) was added drop-
wise. After stirring for 2 d, the yellow-orange solution was diluted
with water (50 mL), solid Na2SO3 was added to cause bleaching of
the orange colour, and the mixture was extracted with CHCl3 (3ϫ
50 mL). The organic extracts were washed with water (3ϫ 50 mL), 4 H, β-OCH2), 4.24 (t, J = 5.1 Hz, 4 H, α-OCH2), 4.38 (t, J =
dried with Na2SO4, and the solvent was removed under reduced
pressure. The product was purified by using chromatography on
5.2 Hz, 4 H, δ-OCH2), 7.14 (d, J = 8.6 Hz, 4 H, m-H), 7.20 (s, 2
H, 3Ј,6Ј-H), 7.76 (s, 2 H, 5,6-H), 8.06 (d, J = 8.4 Hz, 2 H, 3,8-H),
8.27 (d, J = 8.4 Hz, 2 H, 4,7-H), 8.36 (d, J = 8.6 Hz, 4 H, o-H)
silica [(acetone/hexane, 7:2–2:8 (v/v)], yielding 3 as a viscous yellow
1
oil (4.42 g, 75%). H NMR (400 MHz, CDCl3): δ = 3.47 (s, 2 H, ppm. 13C NMR (100 MHz, CDCl3): δ = 67.75, 69.24, 69.74, 69.94,
OH), 3.66, 3.73, 3.88, 4.12 (4 m, 4ϫ 4 H, α–δ-OCH2) 7.09 (s, 2 H, 109.08, 115.79, 117.26, 119.37, 125.76, 127.59, 129.29, 133.32,
3,6-HAr) ppm. 13C NMR (100 MHz, CDCl3): δ = 61.75, 69.07,
136.84, 146.18, 152.3, 156.39, 159.86 ppm. FT-IR (neat): ν = 2974,
˜
69.13, 72.93, 115.47, 118.09, 148.49 ppm.
2933, 2883, 2226 (CϵN), 1601, 1587, 1573, 1549, 1513, 1487, 1463,
1426, 1409, 1375, 1349, 1286, 1246, 1225, 1174, 1147, 1127, 1082,
1059, 1046, 1025, 1009, 986, 957, 920, 899, 858, 836, 794 cm–1.
HRMS: calcd. for C40H32N4NaO6 [M + Na]+ 687.221; found
687.220.
1,2-Dicyano-4,5-bis[2Ј-(2ЈЈ-hydroxyethoxy)ethoxy]benzene (4): Di-
bromide 3 (1.74 g, 3.92 mmol), Zn(CN)2 (689 mg, 5.88 mmol) and
dppf (60.8 mg, 0.11 mmol) were placed in a two-necked flask,
DMAA (5 mL) was added, and the mixture was flushed with ar-
gon. A degassed suspension of Pd2(dba)3 (71.8 mg, 78.4 μmol) in
DMAA (5 mL) was added by using a syringe through the septum,
and the mixture was heated to 120 °C for 2.5 h. After cooling to
room temperature, the mixture was diluted with EtOAc (20 mL)
and filtered through a layer of silica. The solids were washed with
EtOAc, and the combined filtrates were concentrated under re-
duced pressure to give a brown oil, which was purified by using
chromatography on silica (CH2Cl2 with 0–3 vol.-% MeOH). The
combined fractions, containing 4, were concentrated. The light-
brown sticky solid obtained was transferred into a 25 mL flask,
CH2Cl2 (10 mL) was added, and the mixture was vigorously stirred
for 2 h. Filtration, washing of the solid with cold CH2Cl2, and dry-
ing afforded dinitrile 4 as a white powder (1.12 g, 85%); m.p. 95–
96 °C. 1H NMR (400 MHz, [D6]acetone): δ = 3.12 (br. s, 2 H, OH),
Zinc(II) Phthalocyaninate 1: Dinitrile 7 (100 mg, 0.15 mmol) and
anhydrous Zn(OAc)2 (13.8 mg, 75.3 μmol) were suspended in
iAmOH (2 mL distilled from Na). Then o-DCB (2 mL distilled
from CaH2) was added, followed by DBU (22 μL, 0.15 mmol). The
mixture was heated to reflux under a slow stream of argon for 1 d.
After cooling to room temperature, the dark-green mixture was
diluted with CHCl3 (10 mL), and EDTA (20 mL aq.) was added.
The two-phase mixture was vigorously stirred overnight and fil-
tered through a vacuum membrane filter. The precipitate was
washed with water and ethanol. Then the membrane with the solid
was moistened with toluene, folded, placed into a Soxhlet glass
thimble with sintered bottom and extracted with toluene for 1 d.
The greenish extract was discarded and the solid phthalocyanine
remaining in the thimble was peeled off the membrane under sonic-
3.64, 3.91, 4.38 (3m, 16 H, α–δ-OCH2) 7.61 (s, 2 H, 3,6-HAr) ppm. ation in toluene, the solvent was evaporated, and a bluish-green
13C NMR (100 MHz, [D6]acetone): δ = 62.06, 69.81, 70.50, 73.79,
powder of compound 1 was dried in vacuo (58 mg, 56%); m.p.
109.25, 116.77, 118.12, 153.44 ppm. FT-IR (neat): ν = 3285, 3122, Ͼ 400 °C. FT-IR (neat): ν = 2919, 2852, 1603, 1586, 1574, 1485,
˜
˜
3057, 2942, 2881, 2227 (CϵN), 1590, 1568, 1517, 1448, 1410, 1353, 1398, 1277, 1251, 1173, 1114, 1095, 1053, 924, 892, 833, 791 cm–1.
1291, 1229, 1120, 1089, 1057, 1025, 926, 881, 826 cm–1. HRMS:
calcd. for C16H20N2NaO6 [M + Na]+ 359.121; found 359.123.
C160H128N16O24Zn (2724.20): calcd. C 70.54, H 4.74, N 8.23; found
C 70.64, H 5.00, N 8.24.
1,2-Dicyano-4,5-bis[2Ј-(2ЈЈ-tosyloxyethoxy)ethoxy]benzene (5): Di-
nitrile 4 (672 mg, 2 mmol) was dissolved in dry acetonitrile
(15 mL), dry K2CO3 (1.656 g, 12 mmol) was added, and the sus-
pension was cooled to 0 °C. A solution of TsCl (1.146 g, 6 mmol)
in CH3CN (15 mL) was added dropwise. The mixture was warmed
to room temperature and vigorously stirred for 40 h. Then, it was
filtered, the solids were washed with CH3CN, the combined filtrates
were concentrated resulting in a brown oil that was purified with
silica [pentane/CHCl3, 7:3–3:7 (v/v)], yielding target ditosylate 5 as
Preparation of the NMR Sample of [1·4Cu+]: Solid compound 1
(5.4 mg, 2.0 μmol) and [Cu(CH3CN)4](PF6) (3.0 mg, 8.0 μmol)
were dissolved in a mixture of CDCl3 (0.3 mL) and CD3CN
(0.3 mL) under sonication in the presence of several crystals of
ascorbic acid. The dark-green solution was filtered through a small
1
piece of cotton into an NMR tube. H NMR [400 MHz, CDCl3/
CD3CN (1:1), 55 °C]: δ = 4.18 (br. s, 16 H, γ-OCH2), 4.29 (br. s,
16 H, β-OCH2), 4.66 (br. s, 16 H, δ-OCH2), 4.74 (br. s, 16 H, α-
OCH2), 6.76 (br. s, 8 H, 5,6-H Phen), 7.39 (br. d, 16 H, m-H), 7.68
(m, 16 H, 3,8- + 4,7-H Phen), 7.90 (br. d, 16 H, o-H), 8.87 (br. s,
8 H, HPc) ppm. ESI MS: calcd. for C160H128CuN16O24Zn [1 + Cu]+
1
a viscous clear oil (793 mg, 63%). H NMR (400 MHz, CDCl3): δ
= 2.44 (s, 6 H, CH3), 3.77, 3.86 (2 m, 2ϫ 4 H, γ,δ-OCH2), 4.17
6892
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Eur. J. Org. Chem. 2012, 6888–6894

Disaggregation of a Zinc-Complexed Phthalocyanine Derivative
2787.75, found 2786.80; calcd. for C160H128N16O24Zn [1]+ 2724.20,
found 2723.89; calcd. for C160H128Cu2N16O24Zn/2 [1 + 2Cu]2+
1426.29, found 1425.65.
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Acknowledgments
This work was performed in the framework of ARCUS Alsace –
Russia/Ukraine project and European Research Association “Sup-
rachem”. It was sponsored by the Russian Foundation for Basic
Research (grant number 09-03-93117), by the Foundation of the
Russian President for support of young scientists and leading scien-
tific school (grant number MK-3595.2011.3) and by the Centre
National de la Recherche Scientifique (CNRS). The authors are
grateful to Lionel Allouche (Service Commun de RMN, Université
de Strasbourg), Jean-Louis Schmitt (Institut de Science et d’Ingéni-
erie Supramoléculaires, Strasbourg) and Kirill P. Birin (A. N.
Frumkin Institute of Physical Chemistry and Electrochemistry
RAS, Moscow) for their assistance in NMR spectroscopic studies.
The authors are also grateful to Prof. I. P. Stolyarov (N. S. Kur-
nakov Institute of General and Inorganic Chemistry RAS, Mos-
cow) for elemental analysis.
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A. G. Martynov, J.-P. Sauvage et al.
FULL PAPER
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Received: July 17, 2012
Published Online: October 29, 2012
6894
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2012, 6888–6894