Synthesis and characterization of several soluble tetraphenoxy-substituted copper and zinc phthalocyanines

Article abstract of DOI:10.1055/s-2005-861795

Synthesis of copper and zinc phthalocyanines (Pcs) bearing phenoxy-substituents is described. Precursors required for the preparation of PCS 9-16 are prepared by a nucleophilic aromatic substitution reaction between a sterically hindered phenol derivative and 4-nitrophthalonitrile (1) or 3-nitrophthalonitrile (2). Cyclotetramerization of the resulting precursor phthalonitriles in DMAE or in pentan-1-ol catalyzed by DBU gives desired Pcs, which are well soluble in common organic solvents, such as chloroform and dichloromethane. Each of these Pcs are composed of four constitutional isomers and are characterized by ¹H NMR, UV/Vis, IR and mass spectra, as well as elemental analysis, which are consistent with the proposed structures.

Full text of DOI:10.1055/s-2005-861795

PAPER
741
Synthesis and Characterization of Several Soluble Tetraphenoxy-Substituted
Copper and Zinc Phthalocyanines
S
ynthesis of Subs
h
titute
d
Copp
u
e
r
a
nd Zinc
P
hthalocyani
y
nes u Ma,a Dongliang Tian,c Xiaoke Hou,b Yuchun Chang,a,b Fangdi Cong,c Haifeng Yu,c Xiguang Du,*c
Guotong Du*a,b
a
Department of Physics, Dalian University of Technology, Dalian 116023, P. R. China
Fax +86(411)4709304; E-mail: bandaoti@mail.dlut.edu.cn; E-mail: chunyu3ma76@yahoo.com.cn
State Key Laboratory of Integrated Optoelectronics, Jilin University, Changchun 130021, P. R. China
Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China
b
c
Received 18 October 2004; revised 17 November 2004
isomers.10 Thus, a mixture of similar isomers may practi-
Abstract: Synthesis of copper and zinc phthalocyanines (Pcs) bear-
ing phenoxy-substituents is described. Precursors required for the
preparation of Pcs 9–16 are prepared by a nucleophilic aromatic
substitution reaction between a sterically hindered phenol deriva-
tive and 4-nitrophthalonitrile (1) or 3-nitrophthalonitrile (2). Cy-
clotetramerization of the resulting precursor phthalonitriles in
DMAE or in pentan-1-ol catalyzed by DBU gives desired Pcs,
which are well soluble in common organic solvents, such as chloro-
form and dichloromethane. Each of these Pcs are composed of four
constitutional isomers and are characterized by 1H NMR, UV/Vis,
IR and mass spectra, as well as elemental analysis, which are con-
sistent with the proposed structures.
cally be more useful than a single, less soluble isomer.11,12
Tetrasubstituted phthalocyanines are usually obtained as a
mixture of four constitutional isomers, which are formed
in different proportions (D2h:Cs:C2v:C4h = 1:4:2:1). These
constitutional isomers were separated by chromatograph-
ic methods (MPLC, HPLC) using special modified silica
gels.13,14
A commonly used synthetic route to soluble tetrasubsti-
tuted Pcs involves the aromatic nucleophilic substitution
reaction between 4-nitrophthalonitrile or 3-nitrophtha-
lonitrile and a suitable oxygen, nitrogen or sulfur nucleo-
phile followed by cyclotetramerization of the resultant
Key words: phthalocyanines, zinc, copper, synthesis, phenols
phthalonitrile
derivatives,
e.g.
4-(cumylphe-
noxy)phthalonitrile15 and 4-(neopentoxy)phthalonitrile.16
Phthalocyanines (Pcs) and their derivatives have demon-
strated their commercial value as industrial dyes and pig-
ments and photoconductors in xerography. Additionally,
their potential applications in material science, such as
nonlinear optics,1 chemical sensors, liquid crystals, Lang-
muir–Blodgett films,2–4 sensitizers for photodynamic
therapy of cancer,5,6 among others, have been attracting
chemists worldwide for the exploitation of fascinating
properties of Pcs over the past few decades. Due to inter-
molecular interactions between the macrocycles, periph-
We report here synthesis and characterization of new Pcs
9–16 and four Pc precursors 5–8 (Schemes 1– 4) using the
above mentioned synthetic strategy.
We chose phthalonitriles 1, 2, 4-tert-butylphenol (3), and
2-isopropyl-5-methylphenol (4) as starting materials. In
DMSO, under alkaline conditions, anion of phenol 3 or 4
displaced the nitro group of 1 or 2 to generate a phthaloni-
trile derivative. A modified procedure according to the
previous literature17 was adopted to prepare 5. Treatment
of 3 and 1 in the presence of LiOH and anhydrous DMSO
at room temperature afforded the expected 5 (Scheme 1)
in good yield (79%), which was purified by column chro-
matography on silica gel with petroleum ether–diethyl
ether as the mobile phase. Upon treatment with zinc ace-
tate in refluxing dimethylaminoethanol (DMAE) or cop-
per acetate in the presence of DBU and pentan-1-ol under
nitrogen, phthalonitrile 5 was converted to Pcs 9 and 10,
which could be purified by chromatography on silical gel
as a blue-green powder. Their UV/Vis spectra showed the
characteristic Q-band and B-band.
erally
unsubstituted
metallophthalocyanines
are
practically insoluble in common organic solvents, thereby
minimizing their applications.7 The solubility can be im-
proved by introduction of substituents on the periphery
that, to some extent, increases the distance between the
18p electron conjugated systems of Pcs and facilitates the
solubility. A considerable effort has been applied to gen-
erate novel Pc derivatives possessing enhanced proper-
ties, e.g. higher solubility in common organic solvents.8,9
Generally, tetrasubstituted phthalocyanines possess high-
er solubility than the symmetrically octasubstituted ones,
which bear eight same substituents. The outstanding solu-
bility of some tetrasubstituted phthalocyanines is derived
not only from the steric bulk of the substituents preventing
aggregation, but also from the presence of the very similar
Similar to 5, compound 6 was also prepared in good yield
and excellent purity and converted to Pcs 11 and 12 as
shown in Scheme 2.
As expected, under the same strategy, compound 3 was
reacted with 2 to prepare the analogous 3-substituted
phthalonitrile 7 (Scheme 3) as colorless crystals in pretty
good yield (78%). The good yields of phthalonitriles 5 and
7 seems to suggest that the position of nitro group in 3-
SYNTHESIS 2005, No. 5, pp 0741–0748
Advanced online publication: 09.02.2005
DOI: 10.1055/s-2005-861795; Art ID: F14704SS
© Georg Thieme Verlag Stuttgart · New York
x
x
.
x
x
.2
0
0
5

742
C. Ma et al.
PAPER
OH
CN
CN
(H3C)3C
CN
CN
DMSO, LiOH⋅H2O
+
78%
O2N
O
(H3C)3C
3
1
5
C(CH3)3
O
O
N
M
N
pentan-1-ol, DBU, Cu(OAC)⋅H2O, 39%
or DMAE, Zn(OAC)⋅2H2O, 44%
N
N
N
N
N
C(CH3)3
+other isomers
N
(H3C)3C
O
O
9 M=Cu
10 M=Zn
(H3C)3C
Scheme 1
and 4-nitrophthalonitriles has little influence on the yield converted to Pcs 15 and 16 in reasonable yields and supe-
of the corresponding phenoxy-substituted phthalonitrile rior purity (Scheme 4).
derivatives, which is different from the reported result.18
Compared to Pcs 9–12, Pcs 13–16 have relatively better
Compound 7 was used as the precursor for the preparation solubility in certain organic solvents, such as pentan-1-ol
of Pcs 13 and 14 under the well-established synthetic and DMAE, most possibly due to the result of the position
routes. Compound 8 is a white flocculent solid, which was of substituents in the phthalonitriles 3 and 4 leading to the
correspondingly substituted Pc ring. We also found that
CN
OH
CN
O
CN
DMSO, LiOH⋅H2O
+
83%
O2N
CN
6
1
4
O
O
N
pentan-1-ol, DBU, Cu(OAC)⋅H2O, 52%
or DMAE, Zn(OAC)⋅2H2O, 60%
N
N
N
N
M
N
N
+other isomers
N
O
11 M=Cu
12 M=Zn
O
Scheme 2
Synthesis 2005, No. 5, 741–748 © Thieme Stuttgart · New York

PAPER
Synthesis of Substituted Copper and Zinc Phthalocyanines
743
CN
OH
CN
CN
CN
DMSO, LiOH⋅H2O
+
78%
O
(H3C)3C
NO2
2
3
7
(H3C)3C
C(CH3)3
(H3C)3C
O
pentan-1-ol, DBU, Cu(OAC)⋅H2O, 21%
or DMAE, Zn(OAC)⋅2H2O, 25%
O
N
N
N
M
N
N
N
N
N
O
C(CH3)3
+other isomers
O
13 M=Cu
14 M=Zn
(H3C)3C
Scheme 3
1
Pcs 9–16 display excellent solubility in chloroform or and attempts to obtain H NMR spectra of Pcs 9–16 in
dichloromethane. However, in acetone, while copper Pcs DMSO-d6 were not successful. The difference of steric
9, 11, 13, and 15 are almost insoluble, zinc Pcs hindrance derived from position of bulky substituents in
10, 12, 14, and 16 still have solubility just as good as that Pcs 9–16 can account for the relatively poor yield of Pcs
in chloroform or dichloromethane. Pcs 9–16 are hardly 13–16 as compared to Pcs 9–12.
soluble in certain polar solvents, such as DMF, DMSO
CN
OH
CN
DMSO, LiOH⋅H2O
CN
+
81%
O
CN
NO2
2
4
8
O
N
M
N
pentan-1-ol, DBU, Cu(OAC)⋅H2O, 30%
or DMAE, Zn(OAC)⋅2H2O, 35%
O
N
N
N
N
N
N
O
+other isomers
O
15 M=Cu
16 M=Zn
Scheme 4
Synthesis 2005, No. 5, 741–748 © Thieme Stuttgart · New York

744
C. Ma et al.
PAPER
Table 1 1H NMR Signals (d) of Some Compounds
It is well known that cyclotetramerization of monosubsti-
tuted phthalonitriles leads to the formation of four con-
structional isomers. It could be deduced from the
Compound
Ha
Hb
Hc
1
broadening of absorption peaks of H NMR, and TLC
8.678
8.604
8.084
Hc
analysis that metal Pcs 9–16 are a mixture of four isomers.
The conclusions of this paper do not depend on having a
pure isomer, thus no further purification was attempted.
To the best of our knowledge, there is no literature pres-
ently that reports the successful separation of these four
isomers with ordinary column chromatography. Our at-
tempts to separate these isomers by column chromatogra-
phy were not successful. However, Hanack and co-
workers separated all four isomers of two different tetra-
substituted Pcs by HPLC.19,20
NC
Hb
NC
NO2
Ha
7.464
7.218
7.477
7.295
7.711
7.708
Hc
NC
Hb
O
NC
Ha
All the new Pcs were characterized by elemental analysis
Hc
1
and adequate spectroscopic means including H NMR,
NC
Hb
O
TOF-MS, UV/Vis and IR, all of which were compatible
1
with the proposed structures. The H NMR spectra (500
NC
MHz, CDCl3) of the four precursors 5–8 and Pcs
10, 12, 14, and 16 did not display signals of impurities. 1H
NMR measurements of Pcs 9, 11, 13, and 15 were pre-
cluded owing to paramagnetic nature of the copper(II) ion
in a square planar environment. Table 1 gives the chemi-
cal shifts of the aromatic hydrogen atoms of 1,2 and 5–8.
The resonances shifts of Ha, Hb and Hc of 5–8 shift to up-
field due to the influence of electron-donating phenoxyl
group. It is noteworthy that the chemical shifts of Ha and
Hb of 6 is unusually smaller than those of Ha and Hb of 5
(Table 1), which can be interpreted.
Ha
8.580
7.093
8.164
7.427
8.083
7.551
Hc
NC
Hb
Ha
NC
NO2
Hb
NC
Hc
Ha
Based on the studies of previous researchers,18,21,22 com-
NC
pound 6 should be a ‘H-inside’ conformation (Figure 1),
which can be judged readily from the H NMR spectra
O
1
analysis. For diphenyl ethers such as the representative
structure in Figure 1, if two large groups ortho to the ox-
ygen linkage exist in one of the phenyl rings, they prefer
to adopt the ‘H-inside’ conformation. Certain electron-
withdrawing groups, e.g. nitrile groups, augment this ten-
dency.23 The H-inside conformation makes the resonan-
ces of the ortho-hydrogens appear in unusually shielded
positions. Although compound 6 only contains one rela-
tively bulky group, namely isopropyl, it still adopts the
‘H-inside’ conformation.
Hb
7.286
7.425
7.543
NC
Hc
Ha
NC
O
Hc
Hb
(Figure 2), all of which are in the range of m/z = 0 to 3000
(exact molecular mass of Pcs 9–16 are 1168.4 or 1167.4).
For certain monosubstituted metal Pcs bearing some rela-
tively small substituents, such as NH2 group,24 its dimer
peak in MS measured in the same mass spectrometer
could be readily found.
NC
O
NC
Ha
Figure 1 Representative ‘H-inside’ conformation of diphenyl
ethers. The balls represent bulky substituents.
The characteristic absorptions B-band and Q-band could
be observed in UV/Vis spectra of Pcs 9–16. UV/Vis spec-
trum of Pc 10 measured in CHCl3 shows the intense Q-
band absorption origining from p→p* transitions at 682
nm. There is also a weak band at slightly higher energy in
this spectrum. B-band of Pcs arising from the deeper p-
In TOF-MS spectra of Pcs 9–16, their peaks of singly
charged molecular ions in the range of m/z = 0 to 3000 are
obvious and peaks of impurities can hardly be found. We
did not find the dimer peaks in the mass spectra measured
in the LDI-1700 TOF mass spectrometer of Pcs 9–16
Synthesis 2005, No. 5, 741–748 © Thieme Stuttgart · New York

PAPER
Synthesis of Substituted Copper and Zinc Phthalocyanines
745
Figure 4 UV/Vis spectra of Pcs.
that the longer wavelength absorption may not be due to a
co-facial dimer which is expected to be dominant in high-
er concentrations as in the cases of zinc(II)26 and alumi-
num(III)27 complexes of tetrasulfonatophthalocyanine in
MeCN–H2O and aqueous alcohol, respectively, which
were also assumed to adopt a dimeric structure with a
face-to-face slipped or tilted conformation. Thus, the ex-
act nature of these bands is not clear and needs to be ex-
plored further, which is compatible with one previous
result.28
Figure 2 Scanned pictures of mass spectra of Pcs 11 and 12.
levels → LUMO transitions is observed in the UV region
at 357 nm (Figure 3).
The UV-Vis spectra of other Pcs obtained at the concen-
tration of 1.2–3.6 × 10–6 M are shown in Figure 4.
UV-Vis spectra of 14 and 16 are peculiar and worth men-
tioning. Besides the Q-bands at about 700 nm, additional
absorption bands emerged at 744 and 748 nm, respective-
ly (Figure 5). The similar phenomena were also observed
previously for Mg(II) and Zn(II) complexes of 1,8,15,22-
tetrakis(3-pentyloxy)phthalocyanine and the longest
wavelength band was tentatively attributed to a slipped
face to-face dimer.25 To reveal the origin of this band, the
concentration dependency of the absorption spectra of 14
and 16 was studied. For both compounds in CHCl3, the in-
tensity of the ‘monomer’ bands at about 700 nm increased
dramatically while the so-called ‘dimer’ bands at around
740 nm could hardly be observed at concentration as high
as 1.2 × 10–5 M or 1.5 × 10–5 M (Figure 6). This suggests
Figure 5 UV/Vis spectra of 14 (1.5 × 10–6 mol/L, dashed line) and
16 (1.3 × 10–6 mol/L, solid line) in CHCl3.
Aggregation in phthalocyanine systems is readily detect-
ed from optical absorption studies resulting in a decrease
of the maximum extinction coefficient and a blue shift of
the Q-band.29 When the UV/Vis spectrum of compound
16 was measured in CHCl3 at concentrations as high as
1.2 × 10–4 M, the peak corresponding to the monomer at
703 nm is still evident.30 Pcs 9–15 also show the analo-
gous phenomena as 16. These non-aggregation behavior
could have important advantages not only for studying in-
termolecular processes in compounds but also for the ap-
plication of these compounds in photodynamic
therapy.31,32
Figure 3 UV/Vis spectra of Pc 10 and 13 in CHCl3 (10–5 M).
Synthesis 2005, No. 5, 741–748 © Thieme Stuttgart · New York

746
C. Ma et al.
PAPER
vacuum filtration. The crude product was purified by column chro-
matography with petroleum ether–anhyd Et2O (9:1) as the mobile
phase to afford colorless crystals of 6; yield: 229 mg (83%).
IR (KBr): 2229 m (C≡N), 1246 vs cm–1 (C–O–C).
1H NMR (500 MHz,CDCl3): d = 7.708 (d, 1 H, J = 8.5 Hz, ArH),
7.295 (d, 1 H, J = 8.5 Hz, ArH), 7.219 (s, 1 H, ArH), 7.189 (d, 1 H,
J = 8 Hz), 7.109 (d, 1 H, J = 8 Hz, ArH), 6.745 (s, 1 H, ArH), 2.958
(m, 1 H, CH), 2.331 (s, 3 H, ArCH3), 1.154 [d, 6 H, J = 6.5 Hz, 2
CH(CH3)2].
MS (QUSTAR-TOF): m/z calcd for [M + Na+]: 299.1160;
found: 298.9497 (an isotopic cluster peak) [M + Na+] .
UV/Vis (CHCl3): lmax = 261, 297, 306 nm.
4-(4-tert-Butylphenoxy)phthalonitrile (5)
Yield: 217 mg (79%).
IR (KBr): 2230 m (C≡N), 1244 vs cm–1 (C–O–C).
1H NMR (500 MHz,CDCl3): d = 1.358 (s, 9 H, t-C4H9), 6.994 (q, 2
H, J = 2 Hz, Ar H), 7.248 (q, 2 H, J = 2 Hz, ArH), 7.464 (s, 1 H,
ArH), 7.477 (d, 1 H, J = 2 Hz, ArH), 7.711 (d, 1 H, J = 2 Hz, ArH).
Figure 6 UV/Vis spectra of Pc 14 (1.5 × 10–5 M) and 16 (1.2 × 10–5 M)
in CHCl3.
MS (QUSTAR-TOF): m/z calcd for [M + Na+]: 299.1160;
From IR spectra we could find the stretching vibration
peaks of C≡N (usually at ca. 2230 cm–1) and C–O–C
stretching vibration peaks (usually in the rang from 1050
to 1250 cm–1) of 5–8.
found: 298.9504 (an isotopic cluster peak) [M + Na+].
UV/Vis (CHCl3): lmax = 264, 306 nm.
3-Substituted Phthalonitriles; 3-(4-tert-Butylphenoxy)phtha-
lonitrile (7); Typical Procedure
In summary, we have synthesized copper Pcs 9, 11, 13,
and 15 and zinc Pcs 10, 12, 14, and 16 from phthaloni-
triles 1, 2, 3 and 4 as the starting materials. All of them
A mixture of 3 (1.50 g, 10 mmol), 2 (1.73 g, 10 mmol), and LiOH
(10 g, 25 mmol) in anhyd DMSO (30 mL) was stirred at r. t. for 48
h. The progress of the reaction was monitored by TLC analysis. The
mixture was poured into H2O (400 mL) and stirred till a slightly yel-
low solid appeared. The crude product was collected and purified by
chromatography with Et2O–petroleum ether (1:9) to afford color-
less crystals of 7.
1
were sufficiently characterized by H NMR, TOF-MS,
UV/Vis, IR spectra, and elemental analyses, which are
consistent with the proposed structures. The bulky phe-
noxy substituents in the peripheral moieties will not only
decrease the molecular aggregation in solution but also
expand the Pc π-electron conjugated system to generate
Yield: 215 mg (78%).
new photoelectric properties for Pcs 9–16. Excellent sol- IR (KBr): 2230 m (C≡N), 1236 w cm–1 (C–O–C).
1H NMR (500 MHz, CDCl3): d = 1.342 (s, 9 H, t-C4H9), 7.022 (d, 2
H, J = 9 Hz, Ar H), 7.093 (d, 1 H, J = 8 Hz, ArH), 7.451 (d, 2 H,
J = 9 Hz, ArH), 7.427 (d, 1 H, J = 8 Hz, ArH), 7.551 (dd, 1 H, J = 8
Hz, ArH).
ubility for Pcs 9–16 in common organic solvents, such as
chloroform or dichloromethane, is advantageous in the es-
tablishment of molecular order systems and helpful in the
investigation of physical and chemical properties of mo-
lecular order systems.
MS (QUSTAR-TOF): m/z calcd for [M + Na+]: 299.1160; found:
299.0608 (an isotopic cluster peak) [M + Na+]
UV/Vis (CHCl3): lmax = 321 nm.
Pentan-1-ol was distilled from Na prior to use. DMSO was predried
over BaO and distilled under reduced pressure. Column chromatog-
raphy purifications were preformed on silica gel unless otherwise
stated. All other reagents and solvents are commercial available and
used without further purification. Petroleum ether used had bp 60–
90 °C.
High-resolution 1H NMR spectra were recorded on a Varian Unity
500 spectrometer unless otherwise stated. IR spectra were measured
on a Magna 560 FT-IR spectrometer. UV/Vis spectra were taken on
a Cary 500 UV-VIS-NIR spectrophotometer. MS spectra were ob-
tained on a QUSTAR-TOF mass spectrometer or a LDI-1700-TOF
mass spectrometer. Elemental analyses were performed on a Flash
EA1112 Elemental Analyzer.
3-(2-Isopropyl-5-methylphenoxy)phthalonitrile (8)
Yield: 223 mg (81%).
IR (KBr): 2229 m (C≡N), 1242 w cm–1 (C–O–C).
1H NMR (500 MHz, CDCl3): d = 7.543 (dd, 1 H, J = 8 Hz, ArH),
7.425 (d, 1 H, J = 8 Hz, ArH), 7.286 (d, 1 H, J = 8 Hz, ArH), 7.091
(d, 1 H, J = 9 Hz, ArH), 6.971 (d, 1 H, J = 9 Hz, ArH), 6.769 (s, 1
H, ArH), 3.023 (m, 1 H, CH), 2.320 (s, 3 H, ArCH3), 1.182 [d, 6 H,
J = 6.5 Hz, CH(CH3)2].
MS (QUSTAR-TOF): m/z calcd for [M + Na+]: 299.1160; found:
299.0597 (an isotopic cluster peak) [M + Na+].
UV/Vis (CHCl3): lmax = 321 nm.
4-Substituted Phthalonitriles; 4-(2-Isopropyl-5-methylphen-
oxy)phthalonitrile (6); Typical Procedure
Phthalocyaninatocopper; Copper 2,9(10),16(17),23(24)-Tet-
ra(4-tert-butylphenoxy)phthalocyanine (9); Typical Procedure
Phthalonitrile 5 (1.104 g, 4 mmol) and Cu(OAc)2 (0.20 g, 1 mmol)
were added under stirring to pentan-1-ol (10 mL) in a 25 mL one-
neck round-bottomed flask equipped with an air condenser. Then, a
catalytic amount of DBU was added, and the mixture was stirred
and heated at 135 °C under N2 over 12 h. After cooling under N2,
To anhyd DMSO (30 mL) were added 1 (1.73 g, 10 mmol) and 4
(1.5 g, 10 mmol) at r.t. The reaction mixture was stirred and LiOH
(0.60 g, 25mmol) was added over a 2 h period and the mixture was
then stirred for 2 days. The progress of the reaction was monitored
by TLC analysis. The mixture was then poured into H2O (400 mL)
and stirred till a grey solid appeared. The product was collected by
Synthesis 2005, No. 5, 741–748 © Thieme Stuttgart · New York

PAPER
Synthesis of Substituted Copper and Zinc Phthalocyanines
747
pentan-1-ol was removed under reduced pressure. The collected
solid was purified by column chromatography with CHCl3 and sub-
sequently with a mixture of CHCl3–MeOH (90:1) as eluents to af-
ford 9; yield: 455 mg (39%).
Zinc 2,9(10),16(17),23,(24)-Tetra(2-isopropyl-5-methylphen-
oxy)phthalocyanine (12)
Yield: 701 mg (60%).
1H NMR (500 MHz, CDCl3): d = 7.340 (br s, 12 H, ArH), 7.044 (br
s, 12 H, ArH), 3.452 (br s, 4 H, 4 CH), 2.300 (br s, 12 H, 4 ArCH3),
1.394 [br s, 24 H, 4 CH(CH3)2].
IR (KBr): 1238 vs cm–1 (C–O–C).
MS (LDI-1700-TOF): m/z calcd for [M + H+]: 1168.4; found:
1168.6 [M + H+].
MS (LDI-1700-TOF): m/z calcd for [M +
H+]: 1169.4;
found: 1169.5 [M + H+].
UV/Vis (CHCl3): lmax (log e) = 341 (4.68), 614 (4.56), 683 nm
(5.21).
UV/Vis (CHCl3): lmax (log e) = 348 (4.28), 352 (4.28), 615 (3.82),
683 nm (4.52).
Anal. Calcd for C72H64CuN8O4 (1168.4): C, 73.87; H, 5.51; N, 9.57.
Found: C, 73.85; H, 5.86; N, 9.43.
Anal. Calcd for C72H64N8O4Zn (1168.4): C, 73.98; H, 5.52; N, 9.59.
Found: C, 73.62; H, 5.26; N, 9.30.
Copper 2,9(10),16(17),23,(24)-Tetra(2-isopropyl-5-methylphen-
oxy)phthalocyanine (11)
Yield: 607 mg (52%).
Zinc 1,8(11),15(18),22(25)-Tetra(4-tert-butylphenoxy)phthalo-
cyanine (14)
Yield: 292 mg (25%).
1H NMR (500 MHz, CDCl3): d = 7.305–7.389 (m, 12 H, ArH),
6.857–7.031 (m, 16 H, ArH), 1.290–1.347 (m, 36 H, 4 t-C4H9).
MS (LDI-1700-TOF): m/z calcd for 1168.4 [M
+
H+];
found: 1168.4 [M + H+].
UV/Vis (CHCl3): lmax (log e) = 344 (3.57), 385 (3.49), 615 (3.85),
684 nm (4.53).
MS (LDI-1700-TOF): m/z calcd for [M + H+]: 1169.4; found:
1169.3 [M + H+].
Anal. Calcd for C72H64CuN8O4 (1168.4): C, 73.87; H, 5.51; N, 9.57.
Found: C, 73.54; H, 5.70; N, 9.23.
UV/Vis (CHCl3): lmax (log e) = 368 (4.38), 630 (4.40), 700 (5.18),
744 nm (4.43).
Copper 1,8(11),15(18),22(25)-Tetra(4-tert-butylphenoxy)phtha-
locyanine (13)
Yield: 245 mg (21%).
Anal. Calcd for C72H64N8O4Zn (1168.4): C, 73.98; H, 5.52; N, 9.59.
Found: C, 73.74; H, 5.40; N, 9.46.
MS (LDI-1700-TOF): m/z calcd for [M + H+]: 1168.4; found:
Zinc 1,8(11),15(18),22(25)-Tetra-(2-isopropyl-5-methylphen-
oxy)phthalocyanine (16)
1168.5 [M + H+].
Yield: 409 mg (35%).
UV/Vis (CHCl3): lmax (log e) = 340 (5.09), 630 (5.03), 703 nm
(5.75).
1H NMR (500 MHz, CDCl3): d = 7.309–7.622 (m, 12 H, ArH),
6.912–7.065 (m, 12 H, ArH), 3.538 (br s, 4 H, 4 CH), 2.145–2.227
(m, 12 H, 4 ArCH3), 1.187–1.340 [m, 24 H, 4 CH(CH3)2].
Anal. Calcd for C72H64CuN8O4 (1168.4): C, 73.87; H, 5.51; N, 9.57.
Found: C, 73.47; H, 5.38; N, 9.37.
MS (LDI-1700-TOF): m/z calcd for [M + H+]: 1169.4 found:
Copper 1,8(11),15(18),22(25)-Tetra(2-isopropyl-5-methylphen-
oxy)phthalocyanine (15)
Yield: 350 mg (30%).
1169.5 [M + H+] .
UV/Vis (CHCl3): lmax (log e) = 348 (4.51), 632 (4.27), 703 (5.04),
748 nm (4.30).
MS (LDI-1700-TOF): m/z calcd for [M
+
H+]: 1168.4;
Anal. Calcd for C72H64N8O4Zn (1168.4): C, 73.98; H, 5.52; N, 9.59.
Found: C, 73.82; H, 5.33; N, 9.80.
found: 1168.4 [M + H+].
UV/Vis (CHCl3): lmax (log e) = 348 (4.21), 634 (4.45), 707 nm
(5.16).
Acknowledgment
Anal. Calcd for C72H64CuN8O4 (1168.4): C, 73.87; H, 5.51; N, 9.57.
Found: C, 73.70; H, 5.90; N, 9.32
Financial support of this project was provided by NSFC
(60307002). We also wish to thank Shukun Yu for the purification
of Pcs 9–16.
Phthalocyaninatozinc; Zinc 2,9(10),16(17),23,(24)-Tetra(4-tert-
butylphenoxy)phthalocyanine (10); Typical Procedure
Phthalonitrile 5 (1.104 g, 4 mmol) and Zn(OAc)2 (0.220 g, 1 mmol)
were added under stirring to DMAE (10 mL) in a 25 mL one-neck
round-bottomed flask equipped with an air condenser and heated at
135 °C under N2 for 12 h. After cooling under N2, DMAE was re-
moved under reduced pressure. The collected solid was purified
twice by column chromatography with Et2O–petroleum ether (1:3)
as the mobile phase to give pure 10; yield: 514 mg (44%).
IR (KBr): 1235 vs cm–1 (C–O–C).
1H NMR (500 MHz, CDCl3): d = 7.359–7.469 (m, 12 H, ArH),
7.139–7.243 (m, 16 H, ArH), 1.361–1.555 (m, 36 H, 4 t-C4H9).
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Synthesis 2005, No. 5, 741–748 © Thieme Stuttgart · New York

748
C. Ma et al.
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Synthesis 2005, No. 5, 741–748 © Thieme Stuttgart · New York