Synthesis and property of novel phthalocyanine having a 3,5-bis-pentafluorosulfanylphenyl group on the ?±-peripheral position

Article abstract of DOI:10.1016/j.jfluchem.2014.09.012

The pentafluorosulfanyl (SF₅) group is bulky, highly lipophilic, highly electronegative, and highly stable. Despite the potential use of SF₅-containing phthalocyanines, no example exists. We herein report the synthesis of 3,5-bis-pentafluorosulfanylphenyl ((SF₅)₂Ph)-substituted phthalocyanine onto the ?±-peripheral position for the first time. Regioselective synthesis was possible by the effect of the SF₅ moiety via macrocyclization. The synthesis of phthalocyanines with CF₃ and H instead of SF₅ was also carried out in order to investigate the effect of SF₅. Phthalocyanines were compared using UV/Vis spectra. Phthalocyanine with SF₅ exists free from aggregation and protonation in dichloromethane solution. The two planes of 3,5-(SF₅)₂Ph and parent Pc ring in space are nearly perpendicular at which they meet is a right angle, while the two planes of CF₃ analogue in space are not.

Full text of DOI:10.1016/j.jfluchem.2014.09.012

Journal of Fluorine Chemistry 168 (2014) 93–98
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Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Short Communication
Synthesis and property of novel phthalocyanine having a 3,5-bis-
pentafluorosulfanylphenyl group on the
a
-peripheral position§
Norihito Iida a, Etsuko Tokunaga b, Norimichi Saito c, Norio Shibata a,b,
*
a Department of Frontier Materials, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan
b Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan
c Pharmaceutical Division, Ube Industries Ltd., Seavans North Bldg., 1-2-1 Shibaura, Minato-ku, Tokyo 105-8449, Japan
A R T I C L E I N F O
A B S T R A C T
Article history:
The pentafluorosulfanyl (SF5) group is bulky, highly lipophilic, highly electronegative, and highly stable.
Despite the potential use of SF5-containing phthalocyanines, no example exists. We herein report the
Received 23 July 2014
Received in revised form 6 September 2014
Accepted 8 September 2014
Available online 17 September 2014
synthesis of 3,5-bis-pentafluorosulfanylphenyl ((SF5)2Ph)-substituted phthalocyanine onto the
a-
peripheral position for the first time. Regioselective synthesis was possible by the effect of the SF5 moiety
via macrocyclization. The synthesis of phthalocyanines with CF3 and H instead of SF5 was also carried out
in order to investigate the effect of SF5. Phthalocyanines were compared using UV/Vis spectra.
Phthalocyanine with SF5 exists free from aggregation and protonation in dichloromethane solution. The
two planes of 3,5-(SF5)2Ph and parent Pc ring in space are nearly perpendicular at which they meet is a
right angle, while the two planes of CF3 analogue in space are not.
Keywords:
Fluorine
Pentafluorosulfanyl
Phthalocyanine
Aggregation
ß 2014 Elsevier B.V. All rights reserved.
Trifluoromethyl
1. Introduction
homogeneous catalysis. Perfluoro-fluoroalkyl-phthalocyanines,
developed by Gorun et al. [4], are one of the most robust
Phthalocyanines (Pcs) offer many opportunities for creating
novel functional materials including organic solar cells, organic
semiconductors, optical disks and drugs for photo dynamic
therapy [1]. They are also useful as catalysts for organic reactions
such as oxidation [2]. Pcs are highly dependent on their
aggregation states, thus the control of Pc aggregation is of great
importance. Our group, which has been engaged in the design and
synthesis of novel Pcs having trifluoroethoxy (CF3CH2O) sub-
stituents on their peripheral positions, has revealed their unique
non-aggregation properties [3]. Fluorophobic repulsion by the
CF3CH2O substituent is responsible for the behaviour of Pcs, which
exist as monomers totally free from molecular aggregation. Our
next goal is the improved stability of Pcs. Although Pcs are
essentially stable, further robustness and rigid frameworks are
desirable for organic solar cells and catalysts. In particular, Pcs that
are both soluble and resistant to self-oxidation should be ideal for
phthalocyanines for homogeneous catalysis. Their thermal,
photochemical, and chemical stability and high solubility are
amenable to catalyze a variety of reactions even under harsh
conditions including highly reactive singlet oxygen and free
radicals. Inspired by these works, we were interested in Pc 1, a Pc
phenyl introduced onto the
a
-position, [5a] as a template for novel
-position of 1
homogeneous catalysts. If the phenyl moiety on the
a
is suitably functionalized by fluorinated alkyl groups, then the Pcs
are much more attractive because the spaces above/below the Pc
ring can be highly protected by fluorophobic repulsion, which
render these Pcs more robust and durable without losing their non-
aggregation property. In addition,
a
-mono-phenyl-substitution is
suitable to keep Pc planer, while
a
,
a0-bis-phenyl-substitution
completely deform the original Pc structure.[5b,c] In this context,
we designed a novel Pc 2, having a 3,5-bis(pentafluorosulfanyl)-
phenyl ((SF5)2Ph) group on the
a-position of Pc (Fig. 1).
The pentafluorosulfanyl (SF5) group is probably one of the most
obscure, but attractive fluorinated functional groups in future
materials [6]. The SF5 moiety is thermally, hydrolytically and
chemically stable and is considered to be a ‘‘super-trifluoromethyl
(CF3) group’’. Besides, the SF5 group is larger than the CF3 group
with higher lipophilicity and electronegativity. In addition, the
geometry of these two functional groups is completely different:
§
Dedication: To Dr. Teruo Umemoto for his ‘‘ACS Award for Creative Work in
Fluorine Chemistry’’.
*
Corresponding author at: Department of Frontier Materials, Nagoya Institute of
Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan. Tel.: +81 527357543;
fax: +81 527357543.
E-mail addresses: nozshiba@nitech.ac.jp, nozshiba@yahoo.co.jp (N. Shibata).
http://dx.doi.org/10.1016/j.jfluchem.2014.09.012
0022-1139/ß 2014 Elsevier B.V. All rights reserved.

94
N. Iida et al. / Journal of Fluorine Chemistry 168 (2014) 93–98
2. Results and discussion
(SF5)2Ph-substituted Pc
2 was synthesized from highly
functionalized phthalonitrile 6 as a key precursor. Phthalonitrile
6 was obtained by the Suzuki–Miyaura coupling reaction of 2,3-
dicyanophenyl trifluoromethanesulfonate 4 [8] with 3,5-bis(pen-
tafluorosulfanyl)phenylboronic acid 5 under palladium catalysis in
61% yield (Scheme 1).
The macrocyclization of 6 to Pc 2 was initially attempted under
conventional conditions with ZnCl2 in N,N-dimethylaminoethanol
(DMAE) at 140 8C. However, the reaction failed, presumably due to
the steric hindrance of the SF5 moiety. We also attempted the
Fig. 1. Structures of Pc 1 and newly designed Pcs 2 and 3.
reaction using ethylene glycol as
a solvent at 190 8C, but
the decomposition of phthalonitrile 6 was observed instead of
the formation of Pc 2. We then examined the reaction of 6 with
ZnCl2 under rather harsh, solvent-free conditions at 220 8C. The
target Pc 2 was obtained in 35% yield (Scheme 2). It should be noted
that the 1H NMR of 2 is obviously simple which indicates that Pc 2
is produced as a single isomer. The regioselective macrocyclization
of 6 to 2 can be explained by the effect of steric hindrance of the
3,5-(SF5)2Ph group. Pc 2 is highly soluble in a variety of organic
the SF5 group presents a pyramidal electron density while the CF3
displays an inverted cone of density. Although applications of SF5
compounds in material science and medicinal chemistry have been
reported [7], there is no example of the synthesis of Pcs having an
SF5 moiety in their structures. In this paper, we disclose the
synthesis and properties of 3,5-(SF5)2Ph-substituted Pc 2. The CF3
analogue 3 and 1 were also synthesized for comparison.
Scheme 1. Synthesis of phthalonitrile 6.
Scheme 2. Synthesis of 3,5-(SF5)2Ph-substituted Pc 2.
Scheme 3. Synthesis of aryl substituted Pcs 1 and 3.

N. Iida et al. / Journal of Fluorine Chemistry 168 (2014) 93–98
95
solvents such as dichloromethane and diethylether. Unsubstituted
1 and CF3 analogue 3, which were next synthesized for comparison,
were obtained from -phenyl-phthalonitrile 7 [5a] or from -(3,5-
a
a
bis(trifluoromethyl)phenyl)-phthalonitrile 8 under conventional
conditions providing 1 or 3 as mixtures of regioisomers (Scheme 3)
[9]. The lack of regioselectivity for transformation to 1 and 3
strongly indicates that the steric hindrance of the SF5 moiety is
more effective than that of CF3 for the control of regioselective
macrocyclization [5a].
With three Pcs having different aryl groups on the a-position of
the ring in hand, the UV/Vis spectra of 1–3 were investigated in
dichloromethane to ascertain the effect of the SF5 moiety (Fig. 2).
The UV/Vis spectra of 2 shows a clear difference between 1 and
3. The shape of the Q-band of 2 is not changed independent of the
concentration and addition of one drop of pyridine, approximately
100-fold excess relative to Pc (Fig. 2b). Hence, Pc 2 exists as a
monomer without aggregation. On the other hand, those of 1 and 3
are highly dependent of thier concentration (Fig. 2a and c). The
similar sharp and strong Q-bands at 700 nm and 682 nm are
observed respectively, thus both 1 and 3 exist as a monomer at a
concentration of 1.0 ꢀ 10ꢁ4 M. At
a
low concentration
(1 ꢀ 10ꢁ6 M), while 2 maintains the same sharp Q-band peak at
679 nm (Fig. 2b and d), both 1 and 3 are significantly red-shifted
(Fig. 2a, c and d). The red-shift observed in 1 and 3 at a lower
concentration disappears following the addition of pyridine
(Fig. 2a and c). Thus, protonation of the nitrogen on the meso-
position of Pcs 1 and 3 by HCl contamination in dichloromethane is
likely the reason for this observation [10]. These results suggest
that the two planes of 3,5-(SF5)2Ph and parent Pc ring in space are
said to be perpendicular if the dihedral angle at which they meet is
a right angle, and that the
p-electron of the phenyl group is not
conjugated to the parent phthalocyanine ring of 2. On the other
hand, the rotation of dihedral angles of 1 and 3 cannot be
controlled. Therefore, the
p-electron of phenyl groups in 1 and 3
could conjugate with their original phthalocyanine ring. Thus, the
protonated forms of 1 and 3 might be stabilized via conjugation.
Finally,
b
-substituted 3,5-(SF5)2Ph analogue 9 was synthesized
-substituted aryl
for further comparisons (Scheme 4). The
b
analogue of Pcs such as 9 are also attractive due to the potential
of biphenyl-like orientation of a peripheral aryl substituent and its
parent Pc ring [5a,11]. The Pc 9 was obtained as a mixture of
regioisomers in two steps from 5 via Suzuki–Miyaura coupling
reaction with iodide 10 (62% yield) followed by tetramerization in
the presence of ZnCl2 in DMAE (59% yield). The Pc 9 is poorly
soluble in organic solvent which indicates the strong aggregation
property of 9.
Fig. 2. (a) UV/Vis spectra of 1 (blue: 1.0 ꢀ 10ꢁ4 M, pink: 1.0 ꢀ 10ꢁ5 M, green:
1.0 ꢀ 10ꢁ6 M, orange: 1.0 ꢀ 10ꢁ6 M with one drop of pyridine) in dichloromethane.
(b) UV/Vis spectra of 2 (blue: 1.0 ꢀ 10ꢁ4 M, pink: 1.0 ꢀ 10ꢁ5 M, green: 1.0 ꢀ 10ꢁ6 M,
orange: 1.0 ꢀ 10ꢁ6 M with one drop of pyridine) in dichloromethane. (c) UV/Vis
spectra of 3 (blue: 1.0 ꢀ 10ꢁ4 M, pink: 1.0 ꢀ 10ꢁ5 M, green: 1.0 ꢀ 10ꢁ6 M, orange:
1.0 ꢀ 10ꢁ6 M with one drop of pyridine) in dichloromethane. (d) UV/Vis spectra of 1
The UV/Vis spectra of 9 in different concentration are shown
here (Fig. 3). Due to the poor solubility of 9, coordinated solvent,
(blue: 1.0 ꢀ 10ꢁ6 M),
2
(pink: 1.0 ꢀ 10ꢁ6 M) and
3
(green: 1.0 ꢀ 10ꢁ6 M) in
dichloromethane. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
Scheme 4. Synthesis of
b-substituted 3,5-(SF5)2Ph analogue 9.

96
N. Iida et al. / Journal of Fluorine Chemistry 168 (2014) 93–98
(3.67 mmol) in dry-THF (4.3 ml) at ꢁ78 8C slowly. The mixture was
allowed to warm up to room temperature slowly and stirred for
overnight. After reaction, 1 M HCl aq. was added, extracted with
AcOEt three times. The organic layer was washed with brine and
dried over Na2SO4. Solvent was removed under reduced pressure
and the crude product was purified by column chromatography on
silica-gel (eluent: Hex/AcOEt = 5/5) to give product 5 (73% yield).
1H NMR (300 MHz, CDCl3):
d
= 5.00 (br s, 2H), 8.22 (s, 1H), 8.31
(s, 2H)
19F NMR (282 MHz, CDCl3):
d
= ꢁ148.5 (quintet, J = 154 Hz, 2F),
ꢁ167.6 (d, J = 154 Hz, 8F)
Fig. 3. UV/Vis spectra of
9
(blue: 0.5 ꢀ 10ꢁ4 M, pink: 0.5 ꢀ 10ꢁ5 M, green:
13C NMR (75.5 MHz, Acetone-d6):
J = 8.89 Hz), 135.3, 134.6, 126.1
d = 154.0 (quintet,
0.5 ꢀ 10ꢁ6 M, orange: 0.5 ꢀ 10ꢁ4 M with one drop of pyridine) in dioxane. (For
interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)
IR (KBr): 3434, 3362, 3106, 1422, 1354, 1138, 1025, 834, 730,
655, 595 cmꢁ1
ESI-MS: 413 [M+K].
3.1.2. General procedure for Suzuki–Miyaura cross coupling reaction
to synthesize 6–8
To a 50-ml flask, the following were added: phthalonitrile
(0.761 mmol),
boronic
acid
(0.761 mmol),
Pd(OAc)2
(0.0380 mmol), PPh3 (0.152 mmol), K3PO4 (2.28 mmol), degassed
H2O (7.0 ml) and toluene (7.0 ml) under N2. The reaction mixture
was stirred at 90 8C for 2.5 h. After cooling at room temperature,
H2O was added, and then extracted with AcOEt three times. The
organic layer was washed with brine and dried over
Na2SO4. Solvent was removed under reduced pressure and the
crude product was purified by column chromatography on silica-
gel (eluent: 6 Hex/AcOEt = 7/3, 7 Benzene/AcOEt = 95/5, 8 Hex/
AcOEt = 7/3) to give the cross-coupling product 6 (61% yield), 7
(67% yield), 8 (91% yield).
Fig. 4. Estimated 3D-structures of 2 generated by computation. Left: top view; right:
side view.
dioxane was used for investigation. It is known that the Q-band of
electron-donating substituted phthalocyanine on
shifted to longer wavelength side than that of
a
-position is
b
-substituted
3.1.3. 30,50-Bis-pentafluorosulfanyl-biphenyl-2,3-dicarbonitrile (6)
analogue [12]. However, the Q-band of 9 appears at 681 nm and
this value is almost the same as that of Pc 2 679 nm (Figs. 2b vs 3).
These facts strongly indicate that the p-electron of phenyl group of
2 is not conjugated to the parent phthalocyanine ring due to the
perpendicular relationship.
1H NMR (300 MHz, CDCl3):
d = 7.82 (d, J = 6.5 Hz, 1H), 7.92 (q,
J = 7.7 Hz, 1H), 7.96 (d, J = 6.5 Hz, 1H), 8.11(s, 2H), 8.30 (s, 1H)
19F NMR (282 MHz, CDCl3):
d
= -150.0 (quintet, J = 150.8 Hz, 2F),
= 115.7, 116.3, 119.5, 117.7,
-167.3 (d, J = 150.8 Hz, 8F)
13C NMR (75.5 MHz, Acetone-d6):
d
An estimated 3D-molecular structure of
2 generated by
125.3 (quintet, J = 4.98 Hz), 134.8, 134.90, 135.8, 140.6, 141.5,
143.7, 154.2 (quintet, J = 70.5 Hz)
IR (KBr): 3109, 3090, 2231, 1585, 1443, 1141, 854, 731, 659,
599 cmꢁ1
computation (DFT/B3LYP/6-31G*) shows the two planes in space
to be nearly perpendicular and they are not conjugated each other,
which supports the expected structure from the UV/Vis spectra of 2
(Fig. 4).
ESI-MS: 479 [M+Na].
3.1.4. Biphenyl-2,3-dicarbonitrile (7) [5a]
3. Conclusion
1H NMR (300 MHz, CDCl3):
d = 7.54 (br 5H), 7.77–7.81 (m, 3H)
We report the design and synthesis of 3.5-bis(pentafluorosul-
fanyl)phenyl-substituted phthalocyanine 2 by Suzuki–Miyaura
coupling and regioselective macrocyclization. Pc 2 has an SF5 group
obtained as a single regioisomer, while Pc 3 with a CF3 group was
produced as a mixture of regioisomers. The SF5 substituent is bulky
enough, even at the meta-potion (3,5-position) of phenyl ring, to
control the regioselective cyclization and dihedral angle, while an
ortho-substituted phenyl is generally required [5a]. The SF5 moiety
also inhibits protonation on nitrogen on the meso-position of the
phthalocyanine ring. The application and utility of this novel Pc 2
are under investigation.
3.1.5. 30,50-Bis-trifluoromethyl-biphenyl-2,3-dicarbonitrile (8)
1H NMR (300 MHz, CDCl3):
= 7.84 (dd, J = 2.1, 7.5 Hz, 1H), 7.92
d
(q, J = 7.5 Hz, 1H), 7.95 (dd, J = 2.1, 7.5 Hz, 1H), 8.02 (s, 2H), 8.05 (s,
1H)
19F NMR (282 MHz, CDCl3):
13C NMR (75.5 MHz, CDCl3):
d
= -63.4 (s, 6F)
= 114.3, 114.8, 115.1, 117.7,
d
122.8 (q, J = 273 Hz), 123.5 (quintet, J = 3.59 Hz), 129.0, 132.6 (q,
J = 34.1 Hz), 133.4, 133.6, 134.0, 138.3, 143.9
IR (KBr): 3068, 3040, 2238, 1622, 1457, 1388, 1284, 1189, 1137,
902, 810, 746, 711, 683 cmꢁ1
ESI-MS: 363 [M+Na].
3.1. Experimental
3.1.6. 30,50-Bis-pentafluorosulfanyl-biphenyl-3,4-dicarbonitrile (11)
3.1.1. 3,5-Bis(pentafluorosulfonyl)-phenylboronic acid (5)
To a 30-ml flask, the following were added: phthalonitrile
To a solution of 1-bromo-3,5-bis(pentafluorosulfanyl)benzene
(2.44 mmol) and dry-THF (3.0 ml) at ꢁ78 8C under N2 was added
solution of isopropyl magnesium bromide in THF (4.1 ml, 0.71 M,
2.93 mmol) slowly. The resulting solution was stirred at room
temperature for 30 min, was added to solution of trimethylborate
(0.394 mmol),
boronic
acid
(0.394 mmol),
Pd(OAc)2
(0.00394 mmol), PPh3 (0.00787 mmol), K3PO4 (0.787 mmol),
degassed H2O (2.0 ml) and toluene (2.0 ml) under N2. The reaction
mixture was stirred at 80 8C for overnight. After cooling at room
temperature, H2O was added, and then extracted with AcOEt three

N. Iida et al. / Journal of Fluorine Chemistry 168 (2014) 93–98
97
times. The organic layer was washed with brine and dried over
Na2SO4. Solvent was removed under reduced pressure and the
crude product was purified by column chromatography on silica-
gel (eluent: Hex/AcOEt = 8/2) to give the cross-coupling product 11
(62% yield).
MALDI-TOFMASS:m/z = 1422.6–1431.6([M]+, isotopicpattern).
3.1.12. Synthesis of Pcs 9
To a 20-ml flask, the following were added: phthalonitrile
(0.197 mmol), ZnCl2 (0.0493 mmol) and DMAE (1.0 ml) under
N2. The reaction mixture was stirred at 140 8C for 5 h. After cooling
at room temperature, H2O was added. The green precipitate was
filtrated, washed with H2O, dried under reduced pressure with
P2O5. The precipitate was recrystallized with AcOEt/hexane to
obtained phthalocyanine 9 in 59% yield.
1H NMR (300 MHz, CDCl3):
d = 7.93–8.043 (m, 3H), 8.09 (d, 2H,
J = 1.8 Hz), 8.27 (t, 1H, J = 2.4 Hz, 1.8 Hz)
19F NMR (282 MHz, CDCl3):
d
= ꢁ149.9 (quintet, 2F, J = 151 Hz)
ꢁ167.3 (d, 8F, J = 149 Hz)
13C NMR (75.5 MHz, Acetone-d6):
d
= 116.19, 116.22, 116.5,
117.2, 125.06 (quintet, J = 4.72 Hz), 129.7 (t, J = 4.42 Hz), 133.9,
134.3, 135.4, 141.3, 143.1, 154.7 (quintet, J = 19.4 Hz)
3.1.13. Zinc 2(3),9(10),16(17),23(24)-tetra(30,50-bis-
pentafluorosulfanyl-phenyl) phthalocyaninate (9)
IR (KBr): 3114, 3086, 3040, 2238, 1603, 1454, 1383, 1283, 1188,
1143, 858, 729, 662, 598 cmꢁ1
.
1H NMR (300 MHz, Pyridine-d5):
d = 8.00 (br, 2H), 8.21 (br, 2H),
8.63 (br, 3H), 8.81 (br, 7H), 9.03–9.18 (m, 6H), 9.81 (br, 4H)
3.1.7. Synthesis of Pc 2
19F NMR (282 MHz, Pyridine-d5):
ꢁ165.4 to ꢁ166.0 (m, 32F)
d
= ꢁ146.2 to ꢁ146.7 (m, 8F),
To
a test tube, phthalonitrile (0.110 mmol) and ZnCl2
(0.0365 mmol) were added. The reaction mixture was heated at
220 8C for 90 min. After the reaction, the test tube was cooled to
room temperature and the crude product was purified by column
chromatography on silica-gel (Hex/AcOEt = 80/20) to give Pc 2 in
35% yield.
IR (KBr): 3450, 2962, 1725, 1604, 1445, 1388, 1092, 870, 730,
661, 597, 574, 469 cmꢁ1
MALDI-TOF MASS: m/z = 1888.5–1893.5 ([M]+, isotopic pattern).
Acknowledgements
3.1.8. Zinc 1,8,15,22-tetra(30,50-bis-pentafluorosulfanyl-phenyl)
phthalocyaninate (2)
This research was financially supported in part by the Platform
for Drug Discovery, Informatics, and Structural Life Science from
MEXT Japan, JSPS Grand-in-Aid Scientific Research (B) (25288045)
and JSPS Grand-in-Aid for Exploratory Research (25670055).
1H NMR (300 MHz, CDCl3):
d
= 8.18 (d, J = 6.9 Hz, 4H), 8.22 (s,
4H) 8.53 (d, J = 6.9 Hz, 4H) 8.92 (s, 4H), 9.02 (s, 8H)
19F NMR (282 MHz, CDCl3):
= ꢁ146.9 (quintet, J = 149.4 Hz,
8F), ꢁ165.5 (d, J = 149.5 Hz, 32F)
d
References
IR (KBr): 3418, 3111, 2923, 2849, 1601, 1482, 1444, 1387, 1325,
1238, 1141, 1089, 862, 722, 659, 595 cmꢁ1.
MALDI-TOF MASS: m/z = 1887.4–1894.4 ([M]+, isotopic pat-
tern).
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3.1.9. Synthesis of Pcs 1 and 3
To a 20-ml flask, the following were added: phthalonitrile
(0.490 mmol), ZnCl2 (0.163 mmol) and DMAE (2.0 ml) under
N2. The reaction mixture was stirred at 140 8C for overnight. After
cooling at room temperature, H2O was added, and then extracted
with AcOEt three times. The organic layer was washed with brine
and dried over Na2SO4. Solvent was removed under reduced
pressure and the crude product was purified by column
chromatography on silica-gel (eluent: 1 Hex/AcOEt = 7/3, 3 Hex/
AcOEt = Hex/AcOEt = 8/2) to give the phthalocyanine 1 (41% yield),
3 (28% yield).
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3.1.10. Zinc 1,8(11),15(18),22(25)-tetra(phenyl) phthalocyaninate
(1) in 41% yield
1H NMR (300 MHz, CDCl3):
d = 7.22–7.26 (m, 8H), 7.38 (br, 2H),
7.56–7.59 (m, 9H), 7.68 (br, 6H), 7.76–7.89 (m, 5H), 8.24–8.49 (m,
2H)
IR (KBr): 3434, 3053, 2924, 2849, 1699, 1570, 1480, 1389, 1322,
1225, 1097, 1051, 898, 814, 740, 699, 557 cmꢁ1
MALDI-TOF MASS: m/z = 879.67–885.44 ([M]+, isotopic pat-
tern).
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3.1.11. Zinc 1,8(11),15(18),22(25)-tetrakis(30,50-bis-trifluoromethyl-
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1H NMR (300 MHz, CDCl3):
d = 7.03–7.06 (m, 1H), 7.18–7.20 (m,
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2H), 7.31–7.37 (m, 3H), 7.57 (br, 1H), 7.71–7.77 (m, 3H), 8.06–8.09
(m, 2H), 8.19 (br, 2H), 8.28–8.48 (m, 3H), 8.55–8.63 (m, 2H), 8.76
(br, 2H), 8.89–8.95 (m, 2H), 9.67–9.70 (m, 1H)
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19F NMR (282 MHz, CDCl3):
d
= ꢁ61.44 to ꢁ61.49 (m, 12F),
ꢁ62.00 to ꢁ62.11 (m, 12F)
IR (KBr): 3735, 3649, 2927, 1559, 1457, 1379, 1336, 1276, 1176,
1137, 1106, 932, 897, 814, 744, 712, 685 cmꢁ1

98
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