Structural modification of unsymmetrically substituted monophthalocyanines by nucleophilic reactions

Article abstract of DOI:10.1007/s11172-006-0083-8

New 2-nitro-substituted phthalocyanine zinc complexes were synthesized. The nucleophilic substitution of the NO₂ group was used for the first time for the structural modification of unsymmetrically substituted monophthalocyanines. The electroni

Full text of DOI:10.1007/s11172-006-0083-8

Russian Chemical Bulletin, International Edition, Vol. 54, No. 9, pp. 2099—2103, September, 2005
2099
Structural modification of unsymmetrically substituted
monophthalocyanines by nucleophilic reactions
b
A. Yu. Tolbin,a L. G. Tomilova,a,b and N. S. Zefirov
ꢀ
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 785 7024. Eꢀmail: tom@org.chem.msu.su
bInstitute of Physiologically Active Compounds, Russian Academy of Sciences,
1 Severnyi proezd, 142432 Chernogolovka, Moscow region, Russian Federation
New 2ꢀnitroꢀsubstituted phthalocyanine zinc complexes were synthesized. The nucleoꢀ
philic substitution of the NO2 group was used for the first time for the structural modification
of unsymmetrically substituted monophthalocyanines. The electronic absorption spectra of
phthalocyanines were studied.
Key words: unsymmetrically substituted monophthalocyanines, synthesis, nucleophilic subꢀ
stitution.
Unsymmetrically substituted monophthalocyanines
have attracted attention because of the unique optical,
spectroscopic, and catalytic properties1 and the ability to
form ordered Langmuir—Blodgett monolayers.2 Unsymꢀ
metrical complexes are used in nonlinear optics3 and phoꢀ
todynamic cancer therapy.4
In recent years, the use of different types of unsymꢀ
metrically substituted monophthalocyanines in the synꢀ
thesis of heteronuclear5 and polynuclear complexes6 has
attracted considerable interest.
fragments by the structural modification of mononitroꢀ
phthalocyanines.
Mononitrophthalocyanines are synthesized primarily
by mixed cyclization starting from phthalonitriles or the
corresponding 1,3ꢀdiiminoisoindolines.7—9 Synthesis of
these compounds by expansion of alkylꢀsubstituted subꢀ
phthalocyanine boron complexes with 5ꢀnitroꢀ1,3ꢀdiꢀ
iminoisoindoline was documented.10,11 However, both
reactions afford the target products of A3B type in rather
low yields.
The aim of the present study was to develop approaches
to the synthesis of unsymmetrical phthalocyanine comꢀ
plexes of the A3B type containing three identical isoindole
The previously unknown phthalocyanines 5a—c were
synthesized by fusion of phthalonitriles 1 and 3a—c in the
presence of zinc acetate in a ratio of 1 : 3 : 4 (Scheme 1, a).
Scheme 1
R = Et (a), Bun (b), OPrn (c)
Reagents and conditions: a. fusion, 160 °C, 3 h; b. DMAE, refluxing, 2.5 h.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2036—2040, September, 2005.
1066ꢀ5285/05/5409ꢀ2099 © 2005 Springer Science+Business Media, Inc.

2100
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Tolbin et al.
A
The reaction afforded a statistical mixture of mixed cyꢀ
clization products, the yields of the target compounds
5a—c being only 1.5—2%. It has been noted4 that it is
necessary to increase the amount of phthalonitrile A by at
least a factor of 10 compared to the amount of phthaloꢀ
nitrile B with the aim of preparing predominantly one
product of the A3B type. Actually, we succeeded in inꢀ
creasing the yields of complexes 5a—c to 5—6% by inꢀ
creasing the amount of phthalonitriles 3a—c to 10 equivaꢀ
lents. Further increase in the amount of 3a—c has virtuꢀ
ally no effect on the yields of 5a—c but is accompanied by
an increase in the amount of byꢀproducts due to their
selfꢀcyclization.
713
2.1
1.8
1.5
1.2
0.9
0.6
0.3
672
356
648
610
400
500
600
700
800
λ/nm
1,3ꢀDiiminoisoindolines are often used as the starting
compounds to increase the yields of the target mixed cyꢀ
clization products.7,9 Actually, we prepared 5a—c in
14—16% yields by refluxing 1,3ꢀdiiminoisoindolines 2 and
4a—c in N,Nꢀdimethylaminoethanol (DMAE) in the presꢀ
ence of zinc acetate. We failed to prepare the target prodꢀ
ucts by mixed cyclization of 1,3ꢀdiiminoisoindolines with
phthalonitriles in the presence of zinc acetate. In this
case, both components underwent independent selfꢀcyꢀ
clization.
Fig. 1. Electronic absorption spectrum of phthalocyanine 5b
(CHCl3).
Scheme 2
The IR spectra of the previously unknown phthaloꢀ
cyanines 5a—c have absorption bands in the regions of
1336—1340 and 1520—1524 cm–1 belonging to symmetꢀ
ric and antisymmetric vibrations of the NO2 group.
The MALDIꢀTOF mass spectra of compounds 5a—c
contain peaks of molecular ([MH]+) and fragment
([MH – NO2]+) ions. In addition to the molecular
ion peaks, the molecular ions ionized by chlorine,
[M + 35Cl]–, were detected with the use of the ESI method
(CHCl3 + MeCN) in the negative ionization mode. All
peaks observed in the mass spectra are characterized by
isotope splitting corresponding to the natural isotopic
abundance.
The electronic absorption spectra of mononitroꢀ
phthalocyanines 5a—c are characterized by splitting of
their Q bands. Earlier, using related compounds as an
example, this splitting has been demonstrated to be assoꢀ
ciated7,9 with lowering of the symmetry due to the elecꢀ
tronic interaction between the electronꢀwithdrawing and
electronꢀdonating substituents in unsymmetrical molꢀ
ecules. The electronic absorption spectrum of phthaloꢀ
cyanine 5b is shown as an example in Fig. 1. Structurally
related copper and vanadyl complexes are characterized
by analogous electronic spectra.7,9
As a rule, mononitrophthalocyanines are the final tarꢀ
get compounds, and the nucleophilic substitution of the
nitro group in such complexes has not been hitherto inꢀ
vestigated. We demonstrated for the first time that it is
possible, in principle, to perform nucleophilic substituꢀ
tion of the NO2 group in phthalocyanines 5a—c with the
aim of modifying their structures to prepare new unsymꢀ
metrically substituted monophthalocyanines (Scheme 2).
R = R´ = Et (a), Bun (b), OPrn (c); R = But, R´ = H (d)
Reagents and conditions: i. DMSO, K2CO3, 40—80 °C, 50 h or
DMSO, NaH, 20—25 °C, 30—45 min.
The reactions of phthalocyanines 5a—c and the
known1 tertꢀbutyl derivative 5d with benzeneꢀ1,2ꢀdiꢀ
methanol for 50 h in the presence of K2CO3 as a base
afforded 6a—d products, respectively, in trace amounts.
The use of a stronger base, viz., sodium hydride, led to an
increase in the yield of target products 6a—d and a subꢀ
stantial decrease in the reaction time. It was convenient
to monitor the course of the reaction by electronic specꢀ
troscopy. The Q bands of the starting nitrophthalocyanines
5a—d are split. The electronic spectral patterns of the

Modification of unsymmetrical phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
A
2101
A
707
669
672
0.6
0.6
a
b
707
0.5
0.4
0.5
0.4
649
0.3
0.3
646
0.2
0.2
608
612
0.1
0.1
600
650
700
750
λ/nm
600
650
700
750
λ/nm
A
A
675
680
0.6
0.5
0.4
0.3
0.2
0.1
0.6
0.5
0.4
0.3
0.2
0.1
c
d
707
651
613
614
600
650
700
750
λ/nm
600
650
700
750
λ/nm
Fig. 2. Changes in the electronic absorption spectrum of 5d under the action of NaH (DMSO) at 25 °C after 5 (a), 15 (b), 30 (c), and
45 min (d).
A
final products 6a—d, which have no simultaneously elecꢀ
tronꢀdonating and electronꢀwithdrawing substituents,
should be typical of mononuclear metal complexes, which
is actually observed. The changes in the electronic abꢀ
sorption spectrum of the reaction mixture in the course of
the synthesis of compound 6d is shown as an example
in Fig. 2.
680
1.0
0.8
0.6
0.4
0.2
0
355
During the nucleophilic substitution, splitting of the
Q band gradually disappeared.
613
A prolonged contact of phthalocyanines with a strong
base is undesirable and leads to their gradual decomposiꢀ
tion, which was confirmed by control experiments.
The IR spectra of new complexes 6a—d contain charꢀ
acteristic broad absorption bands of the OH group in the
3100—3400 cm–1 region. The mass spectra obtained by
the MALDIꢀTOF and ESI (CHCl3) methods have the
molecular ion peaks [MH+] and [M + Cl]– (for ESI) and
the characteristic fragment ions [M – C8H9O•]+. The
peaks of all ions observed in the mass spectra are characꢀ
terized by isotope splitting corresponding to the natural
isotopic abundance.
400
500
600
700
λ/nm
Fig. 3. Electronic absorption spectrum of phthalocyanine 6c
(CHCl3).
containing the phthalonitrile fragment. The reactions of
complexes 6a—d with 4ꢀnitrophthalonitrile in DMSO in
the presence of NaH afforded phthalocyanines 7a—d in
virtually quantitative yields (Scheme 3).
Compounds 6a—d were characterized also by elecꢀ
tronic absorption spectra. The spectrum of phthalocyaꢀ
nine 6c is shown as an example in Fig. 3.
The introduction of the OH group allowed us to perꢀ
form further modification giving rise to phthalocyanines
The aboveꢀdescribed approach to the synthesis of
unsymmetrically substituted phthalocyanines containing
active CN groups is an alternative to mixed cyclization of
phthalonitriles with different structures, which we have
developed earlier.12 We used these compounds in the

2102
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Tolbin et al.
Scheme 3
4.89 mmol) in MeOH was saturated with gaseous NH3 for 30 min
and kept in a closed vessel for 80 h. Then the reaction mixture
was concentrated and the product was reprecipitated with hexꢀ
ane from a solution in MeOH. Compound 4a was obtained in a
yield of 0.98 g (97%). IR (Nujol mulls), ν/cm–1: 3290 (N—H),
1
1577 (C=NH). H NMR (CD3OD), δ: 1.03 (t, 6 H, CH3CH2,
J = 6.2 Hz); 1.82 (q, 4 H, CH3CH2, J = 7.5 Hz); 3.28 (s, 1 H,
NH); 4.89 (s, 2 H, NH); 7.40 (s, 2 H, Ar). 5,6ꢀDibutylꢀ1,3ꢀ
diiminoisoindoline (4b) was synthesized analogously in 95% yield.
IR (Nujol mulls), ν/cm–1: 3210 (N—H), 1550 (C=NH).
1H NMR (CD3OD), δ: 1.06 (t, 6 H, CH3CH2CH2CH2, J =
6.5 Hz); 1.86—1.98 (m, 4 H, CH3CH2CH2CH2); 2.02—2.16
(m, 4 H, CH3CH2CH2CH2); 3.09 (t, 4 H, CH3CH2CH2CH2,
J = 8.0 Hz); 3.34 (s, 1 H, NH); 4.82 (s, 2 H, NH); 7.54 (s, 2 H,
Ar). 5,6ꢀDipropyloxyꢀ1,3ꢀdiiminoisoindoline (4c) was synthesized
analogously in 96% yield. IR (Nujol mulls), ν/cm–1: 3240
(N—H), 1561 (C=NH). 1H NMR (CD3OD), δ: 1.09 (t,
6 H, CH3CH2CH2O, J = 6.3 Hz); 1.82—1.97 (m, 4 H,
CH3CH2CH2O); 3.12 (t, 4 H, CH3CH2CH2O, J = 7.8 Hz);
3.41 (s, 1 H, NH); 4.78 (s, 2 H, NH); 7.48 (s, 2 H, Ar).
9,10,16,17,23,24ꢀHexaethylꢀ2ꢀnitrophthalocyanine zinc
complex (5a). A mixture of compounds 2 (50 mg, 0.26 mmol)
and 4a (158 mg, 0.78 mmol) and Zn(OAc)2•2H2O (113 mg,
0.52 mmol) in DMAE was refluxed for 2.5 h. After cooling, the
reaction mixture was treated with water. The products that preꢀ
cipitated were filtered off, successively washed with water and
hot MeOH, and chromatographed on SiO2 (CHCl3—Py, 100 : 1,
as the eluent). Phthalocyanine 5a was obtained in a yield of 29
mg (14%). IR (KBr), ν/cm–1: 1338 (ν (NO2)), 1520 (ν (NO2)).
s
as
MS (ESI), m/z (Irel (%)): 790 [M + H]+ (100), 744 [M +
1
H – NO2]+ (16). H NMR (CDCl3 + Pyꢀd5), δ: 1.18 (t, 18 H,
CH3CH2, J = 8.0 Hz); 1.56—1.69 (m, 12 H, CH3CH2); 8.74
and 9.08 (both d, 1 H each, Ar, J = 9.0 Hz); 8.79, 8.89, 8.98,
9.00, 9.14, 9.17, and 9.92 (all s, 1 H each, Ar). Absorption
spectrum (CHCl3), λmax/nm (logε): 360 (4.31), 610 (3.83), 650
(4.15), 670 (4.43), 713 (4.49).
R = R´ = Et (a), Bun (b), OPrn (c); R = But, R´ = H (d)
Reagents and conditions: i. DMSO, NaH, 35—40 °C, 5—10 min.
9,10,16,17,23,24ꢀHexabutylꢀ2ꢀnitrophthalocyanine zinc
complex (5b) was prepared analogously. Phthalocyanine 5b was
isolated by chromatography on SiO2 (CHCl3—Py, 1000 : 1, as
the eluent) in a yield of 40 mg (16%). IR (KBr), ν/cm–1: 1340
(ν (NO2)), 1522 (ν (NO2)). MS (ESI), m/z (Irel (%)): 959 [M +
synthesis of heterometallic and heteroligand dinuclear
phthalocyanines.12
Experimental
s
as
H]+ (100), 913 [M + H – NO2]+ (6). 1H NMR (CDCl3
+
The 1H NMR spectra were recorded on a Bruker AMꢀ300
instrument operating at 300.13 MHz. The electronic absorption
spectra were measured on a Heliosꢀα spectrophotometer in
0.5 cm quartz cells in CHCl3 and DMSO. The mass spectra
were obtained on Autoflex II (MALDIꢀTOF, 2,5ꢀdihydroxyꢀ
benzoic acid as the matrix) and Finnigan LCQ (electrospray
ionization (ESI)) instruments. The IR spectra were recorded on
a Nicolet Nexus IRꢀFourier spectrometer in KBr pellets or as
Nujol mulls. Column chromatography was performed on silica
gel 60 (40—63 µm; Merck) and BioBeads SXꢀ1 and SXꢀ8
(BioRad). All solvents were purified according to standard proꢀ
cedures immediately before use. Prior to syntheses, Zn(OAc)2•
•2H2O was kept in vacuo at 100 °C for 4 h. Phthalonitriles 1,13
3a,14 3b,15 and 3c 16 were prepared according to known proceꢀ
dures. 5ꢀNitroꢀ1,3ꢀdiiminoisoindoline (2) and 2ꢀnitroꢀ9,16,23ꢀ
triꢀtertꢀbutylphthalocyanine zinc complex (5d) were synthesized
according to a procedure described earlier.1
Pyꢀd5), δ: 1.18 (t, 18 H, CH3CH2CH2CH2, J = 8.0 Hz);
1.60—1.70 (m, 12 H, CH3CH2CH2CH2); 1.75—2.05 (m, 12 H,
CH3CH2CH2CH2); 3.47 (t, 12 H, CH3CH2CH2CH2, J =
8.0 Hz); 8.75 and 9.08 (both d, 1 H each, Ar, J = 9.0 Hz); 8.70,
8.88, 8.94, 8.96, 9.14, 9.16, and 9.95 (all s, 1 H each, Ar).
Absorption spectrum (CHCl3), λmax/nm (logε): 356 (4.32), 610
(3.90), 648 (4.19), 672 (4.47), 713 (4.51).
2ꢀNitroꢀ9,10,16,17,23,24ꢀhexapropyloxyphthalocyanine zinc
complex (5c) was prepared analogously. Phthalocyanine 5c was
isolated in a yield of 35 mg (14%) by chromatography succesꢀ
sively on BioBeads SXꢀ1 and SXꢀ8 (THF as the eluent).
IR (KBr), ν/cm–1: 1339 (ν (NO2)), 1524 (ν (NO2)). MS (ESI),
s
as
m/z (Irel (%)): 971 [M + H]+ (100), 925 [M + H – NO2]+ (11).
1H NMR (CDCl3 + Pyꢀd5), δ: 1.16 (t, 18 H, CH3CH2CH2O,
J = 7.0); 1.55—1.68 (m, 12 H, CH3CH2CH2O); 3.66 (t, 12 H,
CH3CH2CH2O, J = 8.0 Hz); 8.76 and 9.10 (both d, 1 H each,
Ar, J = 8.0 Hz); 8.72, 8.84, 8.95, 8.97, 9.13, 9.15, and 9.96 (all s,
1 H each, Ar). Absorption spectrum (CHCl3), λmax/nm (logε):
361 (4.32), 610 (3.86), 651 (4.14), 669 (4.45), 708 (4.50).
5,6ꢀDialkylꢀ1,3ꢀdiiminoisoindolines 4a—c (general proceꢀ
dure). A solution of 4,5ꢀdiethylphthalonitrile (3a) (0.90 g,

Modification of unsymmetrical phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2103
2ꢀ(2ꢀHydroxymethylbenzyloxy)ꢀ9,10,16,17,23,24ꢀhexaethylꢀ
phthalocyanine zinc complex (6a). A mixture of NaH (3 mg,
0.130 mmol), benzeneꢀ1,2ꢀdimethanol (8 mg, 0.065 mmol), and
5a (10 mg, 0.013 mmol) in DMSO (2 mL) was kept at 20—25 °C
for 30 min. After completion of the reaction, the mixture was
treated with water. The phthalocyanine products that precipiꢀ
tated were filtered off, successively washed with water and hot
MeOH, and chromatographed on SiO2 (CHCl3—THF, 50 : 1,
as the eluent). Phthalocyanine 6a was obtained in a yield
was filtered off and successively washed with water and hot
MeOH to obtain complex 7a in a yield of 5.5 mg (97%).
2 ꢀ [ 2 ꢀ ( 3 , 4 ꢀ D i c y a n o p h e n o x y m e t h y l ) b e n z y l o x y ] ꢀ
9,10,16,17,23,24ꢀhexabutylphthalocyanine zinc complex (7b)
(98% yield), 2ꢀ[2ꢀ(3,4ꢀdicyanophenoxymethyl)benzyloxy]ꢀ
9,10,16,17,23,24ꢀpropyloxyphthalocyanine zinc complex (7c)
(98% yield), and 2ꢀ[2ꢀ(3,4ꢀdicyanophenoxymethyl)benzyloxy]ꢀ
9,16,23ꢀtriꢀtertꢀbutylphthalocyanine zinc complex (7d) (97%
yield) were prepared analogously.
of
8
mg (75%). IR (KBr), ν/cm–1
:
3100—3600 (OH).
Proof of the structures of compounds 7a—d and their elecꢀ
tronic absorption spectra have been published earlier.12
MS (MALDIꢀTOF), m/z (Irel (%)): 882 [M + H]+ (100), 761
[M – C8H9O•]+ (22). H NMR (THFꢀd8 + Pyꢀd5), δ: 1.75 (t,
1
We thank E. V. Shulishov for recording NMR spectra
and help in their interpretation.
This study was financially supported by the Interꢀ
national Science and Technology Center (ISTC,
Grant 1526).
18 H, CH3CH2, J = 8.0 Hz); 3.09—3.33 (m, 12 H, CH3CH2);
5.00 and 5.54 (both s, 2 H each, CH2); 7.33—7.90 (m, 4 H,
Ar); 8.76—9.18 (m, 9 H, Ar). Absorption spectrum (CHCl3),
λ
max/nm (logε): 352 (4.55), 617 (4.15), 686 (4.90).
2ꢀ(2ꢀHydroxymethylbenzyloxy)ꢀ9,10,16,17,23,24ꢀhexabutylꢀ
phthalocyanine zinc complex (6b) was prepared analogously.
Phthalocyanine 6b was isolated by chromatography on SiO2
(CHCl3—THF, 100 : 1, as the eluent) in a yield of 7 mg (79%).
IR (KBr), ν/cm–1: 3150—3550 (OH). MS (MALDIꢀTOF),
m/z (Irel (%)): 1050 [M + H]+ (100), 929 [M – C8H9O•]+ (26).
1H NMR (THFꢀd8 + Pyꢀd5), δ: 1.16 (t, 18 H, CH3CH2CH2CH2,
J = 8.0 Hz); 1.60—1.75 (m, 12 H, CH3CH2CH2CH2); 1.80—2.05
(m, 12 H, CH3CH2CH2CH2); 3.22 (t, 12 H, CH3CH2CH2CH2,
J = 7.0 Hz); 4.95 and 5.70 (both s, 2 H each, CH2); 7.30—7.89
(m, 4 H, Ar); 8.82—9.24 (m, 9 H, Ar). Absorption spectrum
(CHCl3), λmax/nm (logε): 352 (4.61), 617 (4.21), 686 (4.94).
2ꢀ(2ꢀHydroxymethylbenzyloxy)ꢀ9,10,16,17,23,24ꢀhexaꢀ
propyloxyphthalocyanin zinc complex (6c) was prepared analoꢀ
gously. Phthalocyanine 6c was isolated by chromatography on
SiO2 (CHCl3—THF, 25 : 1, as the eluent) in a yield of
7 mg (72%). IR (KBr), ν/cm–1: 3100—3590 (OH). MS
(MALDIꢀTOF), m/z (Irel (%)): 1060 [M + H]+ (100), 939
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1
[M – C8H9O•]+ (12). H NMR (THFꢀd8 + Pyꢀd5), δ: 1.33 (t,
18 H, CH3CH2CH2O, J = 7.0 Hz); 2.10—2.18 (m, 12 H,
CH3CH2CH2O); 4.49 (t, 12 H, CH3CH2CH2O, J = 8.0 Hz);
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2ꢀ(2ꢀHydroxymethylbenzyloxy)ꢀ9,16,23ꢀtriꢀtertꢀbutylꢀ
phthalocyanine zinc complex (6d) was prepared analogously.
Phthalocyanine 6d was isolated by chromatography on SiO2
(CHCl3—THF, 50 : 1, as the eluent) in a yield of 13 mg (80%).
IR (KBr), ν/cm–1: 3100—3610 (OH). MS (MALDIꢀTOF),
m/z (Irel (%)): 882 [MH]+ (100), 761 [M – C8H9O•]+ (13).
1H NMR (THFꢀd8 + Pyꢀd5), δ: 1.79 (s, 27 H, Me); 4.92 and
5.73 (both s, 2 H each, CH2); 7.36—8.34 (m, 4 H, Ar); 9.18—9.63
(m, 12 H, Ar). Absorption spectrum (CHCl3), λmax/nm (logε):
350 (4.56), 613 (4.18), 680 (4.96).
2 ꢀ [ 2 ꢀ ( 3 , 4 ꢀ D i c y a n o p h e n o x y m e t h y l ) b e n z y l o x y ] ꢀ
9,10,16,17,23,24ꢀhexaethylphthalocyanine zinc complex (7a).
A mixture of NaH (1.4 mg, 0.057 mmol), 4ꢀnitrophthalonitrile
(1) (5 mg, 0.028 mmol), and 6a (5 mg, 0.006 mmol) in DMSO
(2 mL) was kept at 35—40 °C for 6 min. Then the reaction
mixture was treated with water. The flaky precipitate that formed
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Received March 1, 2005;
in revised form May 20, 2005