Self-organized one-dimensional columns of benzo[b]thiophene-fused tetraazaporphyrins

Article abstract of DOI:10.1142/S1088424614500114

Ring-expanded metallophthalocyanines fused with thiophene rings 1-4 have been synthesized by ring closing reaction from the o-chloroethynylbenzene substructures with Na₂S 9H₂O. The self-organizing properties of these compounds have been studied by UV-vis spectroscopy in solution, π-A isotherms at air-water interface, X-ray diffraction (XRD) patterns of a solid, and atomic force microscopy (AFM). Whereas all compounds exhibit good solubility in organic solvents, thiophene-fused phthalocyanines form stable aggregates through strong intermolecular π-π interaction. Copper phthalocynaine Cu-2 possessing phenyl spacers produced long nano-fibrous assemblies from solution.

Full text of DOI:10.1142/S1088424614500114

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2014; 18: 259–266
DOI: 10.1142/S1088424614500114
Published at http://www.worldscinet.com/jpp/
Self-organized one-dimensional columns of
benzo[b]thiophene-fused tetraazaporphyrins
Hiroyuki Suzukia, NaoyaYamadab, Ken-ichi Nakayamab and Mutsumi Kimura*a◊
a Division of Chemistry and Materials, Faculty of Textile Science and Technology, Shinshu University,
Ueda 386-8567, Japan
b Graduate School of Science and Engineering, Yamagata University, Yonezawa 992-8510, Japan
Received 11 January 2014
Accepted 24 February 2014
ABSTRACT: Ring-expanded metallophthalocyanines fused with thiophene rings 1–4 have been
synthesized by ring closing reaction from the o-chloroethynylbenzene substructures with Na2S 9H2O.
The self-organizing properties of these compounds have been studied by UV-vis spectroscopy in
solution, p-A isotherms at air-water interface, X-ray diffraction (XRD) patterns of a solid, and atomic
force microscopy (AFM). Whereas all compounds exhibit good solubility in organic solvents, thiophene-
fused phthalocyanines form stable aggregates through strong intermolecular p–p interaction. Copper
phthalocynaine Cu-2 possessing phenyl spacers produced long nano-fibrous assemblies from solution.
KEYWORDS: metallophthalocyanines, ring closing reaction, one-dimensional column, self-organization,
fibrous network.
intermolecular orbital overlap in the solid state as well as
INTRODUCTION
high solubility in solution.
Large-area and flexible electronic devices fabricated
Phthalocyanines (Pcs) and their metal complexes
by simple printing technologies using solution-based
(MPcs) have been used as molecular components in
semiconducting materials have recently been attracting
organic-based devices due to their intense absorbing
much intense attention due to their potential applications
Q-bands(600–700nm), highmolarextinctioncoefficients
suchasflexibledisplays,smartlabels,andlight-weightsolar
cells [1–6]. Various organic and inorganic semiconducting
(e > 100,000 M-1.cm-1), and good thermal, chemical, and
photochemical stabilities [12]. Extended flat hydrophobic
materials have been applied as functional inks for printed
Pc ligands, modified at either four or eight positions on
electronics. Among these semiconducting materials, well-
each Pc with solubilizing side chains, can self-organize
defined thiophene-fused polycyclic aromatic derivatives
to form one-dimensional columns through intermolecular
with solubilizing groups exhibited excellent performance
for organic-based electronic devices [7]. Takimiya et al.
p–p stacking interactions [12]. The p–p overlap of MPcs
within the columnar stacks provides a transport pathway
succeeded at systematic syntheses of solution-processable
for charge or energy parallel to the columnar axis. The
thiophene-fused aromatic derivatives. Solution-processed
long-range transportation of charge and energy in the
organic field-effect transistors (OFETs) fabricated by
columnar stacks can enhance the device performance of
using solution-cast films of these materials have shown
organic-based optical and electronic devices. The length
-1
high field-effect mobility values above 1cm2.V .s-1
[8–11]. The molecular design of solution-processable
organic semiconducting molecules requires long-range
of self-organized columns depends on the strength of
intermolecular p–p stacking interactions among MPcs.
In this context, many attempts have been made to control
self-organization properties of MPcs by exploring
molecular architecture of Pc ligand [13–18].
◊SPP full member in good standing
In this paper, we report syntheses of thiophene-fused
MPc derivatives 1–4 through a ring closing reaction
from the o-chloroethynylbenzene substructures, and
*Correspondence to: Mutsumi Kimura, email: mkimura@
shinshu-u.ac.jp, tel/fax: +81 268-21-5499
Copyright © 2014 World Scientific Publishing Company

260
H. SUZUKI ET AL.
R
R
R
S
NC
NC
Cl
Cl
NC
NC
1: R = -(CH2)5CH3
2: R =
a
S
+
R
N
(CH2)5CH3
(CH2)5CH3
Cl
N
N
N
N
5-8
R
S
N
3: R =
N
M
b
Cl
R
S
4: R =
N
Cl
N
S
S
H3C(H2C)5
N
N
N
R
R
c
M = Cu or Zn
N
1-4
M
N
N
Fig. 1. Structure of thiophene-fused MPcs 1–4. The structure is
N
one of structural isomers
Cl
R
9-12
Cl
their self-organizing properties of ring-expanded MPcs
in solution and a solid state (Fig. 1). Although several
thiophene-fused tetraazaporphyrins have been synthe-
sized, a benzothiophene-fused teteraazaporphyrin has
not been reported [19–21]. The introduction of peripheral
four alkyl chains with ring-expanded MPcs exhibits high
solubility in organic solvents. Thiophene-fused Cu-2
decorated with n-hexylphenyl substituents formed long
fibrous aggregates through enhanced p–p interaction
among ring-expanded MPcs. We also report preliminary
results of the fabrication of OFETs using spin-coated thin
films of Cu-1 and Cu-2 and the preparation of insoluble
Pc-networked film by the electrochemical polymerization
of Cu-4.
R
5, 9: R = -(CH2)5CH3
6, 10: R =
(CH2)5CH3
(CH2)5CH3
S
7, 11: R =
S
8, 12: R =
H3C(H2C)5
(a) PdCl2(PPh3)2, CuI, triethylamine-THF, (b) M(AcO)2, urea, N,N'-dimethyl-
propyleneurea, (c) Na2S 9H2O, NMP. MPcs 1-4 and 9-12 contain structural
isomers.
Scheme 1. M. Kimura et al.
RESULTS AND DISCUSSION
Scheme 1 illustrates the synthetic route of thiophene-
fused MPcs 1–4. Phthlocyanine precursors 5–8 were
synthesized through palladium-catalyzed Sonogashira
coupling of 4,5-dichlorophthalonitrile with alkynes.
MPcs 9–12 fused with o-chloroethynylbenzene were
prepared in the presence of metal salts, and the final ring
closing reaction with sodium sulfide [22] obtained 1–4
in good yields. The MALDI-TOF-Ms spectra of all final
compounds exhibit an expected parent molecular ion
peak,andtheirpuritieswereconfirmedbyHPLCanalyses.
All MPcs decorated with four flexible substituents at the
a-positions of the fused thiophene rings revealed good
solubility (>10 g.L-1) in organic solvents such as THF,
toluene and CHCl3.
The shape and location of the Q-band of MPcs are
known to be indicators for determining the aggregation
behavior of MPcs. All CuPcs exhibit a broad absorption
Q-band in the range of 550–850 nm in CHCl3 (Fig. 2a
and Table 1). The broadening of the Q-band is caused by
exciton coupling between neighboring phthalocyanine
rings in aggregates [23]. No changes on the absorption
spectral shape in CHCl3 were detected in the concentration
range of 5 mM to 0.1 mM, indicating the formation of
stable aggregates in solution. The absorption maxima
of the Q-bands for thiophene-fused CuPcs 1–4 shift to
longer wavelengths relative to the parent compounds.
The red-shifting of Q-band is ascribed to the enlargement
of the p-conjugated system by fusing thiophenes with
the phthalocyanine ring. The Q-bands of Cu-3 and Cu-4
were red-shifted as compared with the spectra of Cu-1
and Cu-2 due to the attachment of electron-donating
thiophene spacers with thiophene-fused phthalocyanine
ring (Fig. S1). Figure 2b shows the absorption spectra of
Cu-1 and Cu-2 in 1,3,5-trimethylbenzene. The spectrum
of Cu-1 in 1,3,5-trimethylbenzene displayed a peak
at 733 nm, indicating the dissociation of aggregates
into monomeric species caused by solvent changing.
In contrast, the Q-bands of Cu-2 remained unaltered in
1,3,5-trimethylbenzene. The aggregation properties in
solution were enhanced by the presence of phenyl spacer
in the solubilizing side chains. Whereas Cu-1 exhibits a
broad Q-band in CHCl3, the peak at 734 nm is observed
in the spectrum of Zn-1 (Fig. 1c). The difference in
the aggregation behavior reflected the attracting force
between MPcs that had different central metals. The
attracting force between CuPcs was stronger than that
between ZnPcs.
Copyright © 2014 World Scientific Publishing Company
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SELF-ORGANIZED ONE-DIMENSIONAL COLUMNS OF BENZO[B]THIOPHENE-FUSED TETRAAZAPORPHYRINS
Table 1. Photophysical and electrochemical data for MPcs 1–4
261
Ligand
Metal
l
max, nma
E1/2, V vs. Fc/Fc+b
1
Cu
Zn
Cu
Zn
Cu
Cu
669, 726sh
670sh, 734
665, 740sh
682, 735
672, 750sh
677, 750sh
0.14, 0.83
0.14, 1.03
0.12, 0.90
0.13, 1.14
0.14, 1.02
0.14, 1.02
2
3
4
a
b
In CHCl3. Determined by differential pulse voltammetry in
CH2Cl2 containing0.1MBu4NClO4 at295K,scanrate=50mV/ssh
Shoulder peak.
(HOMO = -5.2 eV). The enlargement of p-system resulted
in the destabilization of the HOMO.
Phthalocyanines substituted with linear or branched
alkyl, alkoxymethyl, or alkoxy chains form a major class
of discotic liquid-crystalline materials that self-organize
in columnar stacks [25–29]. The type of side chain, its
length, the symmetry of Pc molecule influence the self-
organized structure. The self-organizing properties of
Cu-1 and Cu-2 were investigated by differential scanning
calorimetry (DSC), temperature-controlled polarized
optical microscopy (POM), and X-ray diffraction
(XRD). No typical textures in POM and no transitions
in DSC were observed in Cu-1 and Cu-2 on heating
and cooling from -50 to 250°C. The number and length
of alkyl chains in Cu-1 and Cu-2 are not sufficient to
exhibit liquid crystal phases. The XRD patterns of Cu-1
and Cu-2 at room temperature show one reflection peak
corresponding to the d spacing of 2.23 and 2.53 nm,
which is attributed to the average distance between
stacked columns in the solid (Fig. S2). Cu-2 with phenyl
spacer has a longer average distance than Cu-1. Since
the XRD patterns in the small angle region showed only
one peak, two- or three-dimensional lattices could not be
assigned from the XRD patterns. The reflection peak at
0.33 nm characteristic of the p–p stacking is observed,
thus indicating a long-range ordering along the columnar
axis. The broad and diffuse halo around 0.43 nm can be
ascribed to the liquid-like disorder in alkyl chains.
The organized structures of Cu-1 and Cu-2 were
analyzed by a surface pressure vs. area (p-A) isotherm
on pure water as the substrate (Fig. 3) [30]. A continuous
rise in the pressure as area decreased was observed up to
40mN.m-1,whereuponthemonomolecularfilmcollapsed.
The limiting surface areas per molecules of Cu-1 and
Cu-2 were 0.52 and 0.84 nm2/molecule determined by
extrapolating the slope of the p-A isotherms in the liquid-
condensed region to zero pressure. The limiting surface
area of Cu-2 mostly agreed with the area occupied in an
edge-on arrangement of molecules on the water surface.
This indicates that Cu-2 forms stacks with phthalocyanine
plane perpendicular to the air-water interface. In contrast,
Fig. 2. Absorption spectra of (a) Cu-10 (solid line) and Cu-2
(dashed line) in CHCl3, (b) Cu-1 (solid line) and Cu-2 (dashed
line) in 1,3,5-trimethylbenzene, and (c) Zn-1 (solid line) and
Zn-2 (dashed line) in CHCl3. [MPcs] = 10 mM
Electrochemical studies of thiophene-fused MPcs were
performed through cyclic voltammetry measurement
in CH2Cl2 containing 0.1M Bu4NClO4 as a supporting
electrolyte (Table 1). Cu-1 exhibits two reversible
oxidation waves at +0.14 and +0.83V vs. ferrocene/
ferrocenium redox couple (Fc/Fc+). Since Cu(II) does
not undergo a redox process within the potential window
in CH2Cl2, the observed oxidation processes can be
ascribed to thiophene-fused phthalocyanine-centered ring
oxidations [24]. The highest occupied molecular orbital
(HOMO) energy levels of Cu-1 and Cu-2 were estimated
to be -4.94 and -4.92 eV from the first oxidation potentials
calibrated by the Fc/Fc+ redox potential vs. vacuum
(Table 1). The HOMO energy levels of Cu-1 and Cu-2
were slightly higher than that of copper phthalocyanines
Copyright © 2014 World Scientific Publishing Company
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262
H. SUZUKI ET AL.
Solution-processed OFETs using Cu-1 and Cu-2 were
fabricated using the top-contact device configuration.
Thin films were deposited onto a Si/SiO2 substrate with
hydrophobicsurfacetreatmentusinganinsulatingpolymer
by spin coating using 20 mg/mL solutions of Cu-1 or Cu-2
in CHCl3 containing 1.0 wt% 1,3,5-trichlorobenzene at
1000 rpm for 40 sec. In AFM images, the obtained thin
films appeared to be smooth and have a homogeneous sur-
face with a surface roughness RMS of less than 0.3 nm
in the region of 3 × 3 mm. Gold source and drain
electrodes with 70 nm thickness were vapor-deposited on
top of the thin films. The channel length and the width
of the source and drain electrodes were 50 mm and 5.5
mm, respectively. FET characteristics were measured in
a nitrogen glove box system. Both devices of Cu-1 and
Cu-2 showed typical p-channel FET responses (Fig. 5).
The field-effect mobilities measured in the saturation
Fig. 3. Surface pressure vs. area per molecule isotherms for
Cu-1 (solid line) and Cu-2 (dashed line) on triply distilled water
at 25°C
the limiting area of Cu-1 is smaller than the estimated
edge area (0.74 nm2), suggesting the formation of slipped
stacks on the interface [31].
-1
regime were 1.06 × 10-5 cm2.V .s-1 for Cu-1 and 2.37 ×
-1
10-5 cm2.V .s-1 for Cu-2 with Ion/Ioff of 102–103. The
The organized morphologies of Cu-1 and Cu-2 were
visualized by atomic force scanning microscopy (AFM)
(Fig. 4). A droplet of 5 × 10-5 M solutions of Cu-1 or
Cu-2 in CHCl3 was placed on a mica substrate, and
the solution was evaporated in vacuum. Although the
AFM height image of Cu-1 shows no featured dots,
Cu-2 assembled into network structures of fibers with
a 2.4 nm height. The fibers consist of bundles of finer
strands, and some isolated single strands can be seen.
The length of fibers is in an order of a few micrometers.
The observed height of fibers is in fair agreement with
the average intercolumnar distance as obtained from the
XRD analysis and the diameter of molecular model of
Cu-2. From these results, we may conclude that Cu-2
self-assembles in CHCl3 solution to produce long one-
dimensional stacks. The phenyl spacers in Cu-2 enhance
the attracting force among molecules, and the enhanced
attracting force induces the formation of nanoscopic
fibers in solution. On the other hand, Cu-1 assembles
short stacks in solution relative to Cu-2. The short stacks
result in the slipped stacks in air-water interface and the
dotted structures on mica.
device performance is lower than the reported values
for phthalocyanine-based OFETs [19, 32–38]. The XRD
patterns of spin-coated films on the Si/SiO2 substrate
revealed broad reflection peaks, indicating their low
crystallinity. The low crystallinity of thin films results in
low performance of OFETs.
Terminal a-positions of Cu-4 are made available
for electrochemical polymerization to produce cross-
linked films. Electrochemical polymerization provides
a convenient way for redox-active monomers to deposit
a polymer film directly onto the surface of electrodes
[39–41]. The electrochemical polymerization of Cu-4
was performed in a three-electrode cell using platinum
as a counter electrode, Ag/AgCl as a reference electrode,
and ITO-coated glass substrate as a working electrode.
Cu-4 was electrodeposited as film using 0.1mM concen-
tration of CH2Cl2 containing 0.1 M Bu4NPF4 as a
supporting electrolyte and scanning between -0.5 and
1.4 V at a scan rate of 50 mV/s. The polymer film of
Cu-4 on an ITO electrode was prepared by five cycles of
potential scans. Two reversible oxidation waves at 0.53
and 1.04 V vs. Ag/AgCl were observed (Fig. 6a). The
Fig. 4. AFM images (area: 5 × 5 mm) of (a) Cu-1 and (b) Cu-2 on mica substrates
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SELF-ORGANIZED ONE-DIMENSIONAL COLUMNS OF BENZO[B]THIOPHENE-FUSED TETRAAZAPORPHYRINS
263
Fig. 5. Drain-source current vs. drain-source voltage characteri-
stics for (a) Cu-1 and (b) Cu-2
peak currents increased upon the repeated scans and a
yellow-green film was deposited onto the surface of an
ITO electrode. The resulting film on ITO is designated
Fig. 6. (a) Repeated CV cycles of Cu-4 in CH2Cl2 containing
0.1 M Bu4NPF4 (scan rate: 100 mV.s-1). (b) Network structure
of electropolymerized Cu-4. (c) Absorption spectrum of
electropolymeized Cu-4 deposited onto an ITO electrode
as polymerized Cu-4. Since four thiophene terminals in
Cu-4 could undergo the oxidative coupling reaction, the
resulting polymers possess a three-dimensional network,
where the thiophene-fused CuPcs are connected with
bithiophene segments in the network polymer. The
polymerized films were rinsed with CH2Cl2 to remove
any residual soluble species (Fig. 6b). The rinsed films
exhibited two oxidation waves at the same positions as
observed in the electrochemical polymerization of Cu-4,
and less than 5% loss of electroactivity after 50 repeated
scans between 0 and 1.4 V in monomer-free electrolyte
solution. The absorption spectrum of polymerized Cu-4
is almost the same as that of Cu-4 in solution, suggesting
the stacking of CuPcs within the three-dimensional
network (Fig. 6c) [42–44].
self-organizing properties of thiophene-fused phthalo-
cyanines were investigated in solution, at air-water
interface, and in the solid state. The attachment of
n-hexylphenyl units at a-positions of the fused thiophene
rings creates the network structure of nanoscopic fibrous
assemblies with excellent long-range stacking through
the intermarocycle interaction with the additional
interaction between peripheral phenyl spacers. Cu-1 and
Cu-2 acted as a soluble p-channel organic semiconductor,
but the field-effect mobility was not high due to the low
crystallinity in the solid state. Cu-4 possessing thiophene
spacers was polymerized into the electrochemically
active films onto an electrode by the connection of four
In summary, we have synthesized thiophene-fused
phthalocyanines 1–4 through the ring closing reaction
from the o-chloroethynylbenzene substructures. The
Copyright © 2014 World Scientific Publishing Company
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264
H. SUZUKI ET AL.
thiophene terminals through the oxidative coupling
reaction. Further structural modifications of thiophene-
fuse phthalocyanines to control molecular ordering in the
solid phase are now underway in our group.
MHz): d, ppm 141.6, 137.7, 134.3, 130.4, 114.8, 114.7,
114.6, 114.4, 105.6, 75.9, 31.6, 28.9, 28.4, 22.9, 20.2,
14.4. IR (ATR): n, cm-1 2230 (–CN).
6. Compound 6 was synthesized from 4,5-dichloro-
phthalonitrile and 1-ethynyl-4-hexylbenzene by the same
1
procedure of 1. Yield 52%. H NMR (CDCl3, 400.13
EXPERIMENTAL
MHz): d, ppm 7.91 (1H, s, ArH), 7.83 (1H, s, ArH),
7.49 (2H, d, J = 8.4 Hz, ArH), 7.22 (2H, d, J = 8.4 Hz,
ArH), 2.65 (2H, t, J = 7.6 Hz, –CH2–), 1.58–1.66 (2H,
m, –CH2–), 1.28–1.35 (6H, m, –CH2–), 0.89 (3H, t,
J = 6.8 Hz, –CH3). 13C NMR (CDCl3, 100.61 MHz):
d, ppm 146.4, 141.3, 137.4, 134.4, 132.5, 130.0, 129.3,
118.5, 115.0, 114.7, 114.6, 114.5, 103.1, 83.5, 36.5, 32.1,
31.5, 29.3, 23.0, 14.5. IR (ATR): n, cm-1 2230 (–CN).
7. Compound 7 was synthesized from 4,5-dichloro-
phthalonitrile and 2-ethynyl-5-hexylthiophene by the
General procedures
NMR spectra were recorded on a Bruker AVANCE
400 FT NMR spectrometer at 399.65 MHz and 100.62
1
MHz for H and 13C in CDCl3 solution. Chemical shifts
are reported relative to internal TMS. IR spectra were
obtainedonaSHIMAZUIRPrestige-21withDuraSample
IR II. UV-vis spectra were measured on a JASCO V-650.
MALDI-TOF mass spectra were obtained on a Bruker
autoflex spectrometer with dithranol as matrix.
All chemicals were purchased from commercial
suppliers and used without purification. Column chroma-
tography was performed with activated alumina (Wako,
200 mesh) or silica gel (Wakogel C-200). Recycling
preparative gel permeation chromatography was carried
out by a JAI recycling preparative HPLC using CHCl3
as an eluent. Analytical thin layer chromatography was
performed with commercial Merck plates coated with
1
same procedure of 1. Yield 42%. H NMR (CDCl3,
400.13 MHz): d, ppm 7.88 (1H, s, ArH), 7.83 (1H, s,
ArH), 7.27 (1H, d, J = 3.6 Hz, ArH), 6.76 (1H, d, J =
3.6 Hz, ArH), 2.84 (2H, t, J = 7.6 Hz, –CH2–), 1.65–1.73
(2H, m, –CH2–), 1.29–1.40 (6H, m, –CH2–), 0.89 (3H,
t, J = 6.8 Hz, –CH3). 13C NMR (CDCl3, 100.61 MHz):
d, ppm 152.7, 140.6, 136.8, 135.4, 134.3, 129.8, 125.5,
118.3, 114.7, 114.6, 114.5, 96.9, 87.4, 31.9, 31.3, 30.8,
29.1, 22.9, 14.5. IR (ATR): n, cm-1 2232 (–CN).
8. Compound 8 was synthesized from 4,5-dichloro-
phthalonitrile and 2-ethynyl-3-hexylthiophene by the
silica gel 60 F254 or aluminum oxide 60 F254
.
The transition temperatures were measured by
differential scanning calorimetry with a SII DSC 6200
operated at a scanning rate of 10°C.min-1 on heating
and cooling. The apparatus was calibrated with indium
as standard. The XRD patterns were obtained with a
Rigaku XRD-DSC with Cu Ka radiation. Spacings were
obtained from Bragg’s law. Atomic force microscopy
images were acquired in non-contact mode by a JEOL
JSPM-5400 system.
1
same procedure of 1. Yield 25%. H NMR (CDCl3,
400.13 MHz): d, ppm 7.89 (1H, s, ArH), 7.85 (1H, s,
ArH), 7.37 (1H, d, J = 5.2 Hz, ArH), 6.96 (1H, d, J =
5.2 Hz, ArH), 2.81 (2H, t, J = 7.6 Hz, –CH2–), 1.63–1.70
(2H, m, –CH2–), 1.28–1.37 (6H, m, –CH2–), 0.88 (3H,
t, J = 6.8 Hz, –CH3). 13C NMR (CDCl3, 100.61 MHz):
d, ppm 152.1, 140.4, 136.7, 134.4, 130.0, 129.8, 129.2,
116.4, 114.7, 114.6, 96.4, 90.3, 32.0, 30.7, 30.3, 29.4,
23.0, 14.5. IR (ATR): n, cm-1 2232 (–CN).
Phthalocyanines
Syntheses
Cu-9. A mixture of 5 (150 mg, 0.55 mmol), urea
(67 mg, 1.1 mmol), and Cu(OAc)2 H2O (28 mg, 0.14
mmol) in N,N′-dimethylpropyleneurea (3.0 mL) was
heated at 160°C for 12 h under N2 atmosphere. After
cooling to 60°C, methanol was added to the reaction
mixture and stirred for 15 min. The resulting suspension
was filtered off and washed with methanol. The solid
residue was purified by column chromatography on
activated alumina by eluting with CHCl3 and recycling
preparative HPLC to give Cu-9 (53 mg, 33%). UV-vis
(10 mM in CHCl3): l, nm 628 and 695. MALDI-TOF
MS (dithranol): m/z 1146.5 ([M + H], 100%), calcd. for
C64H60Cl4N8Cu: m/z 1146.6.
Phthalonitriles
5. To a solution of 4,5-dichlorophthalonitrile (0.60 g,
3.05 mmol) and 1-octyne (0.50 g, 4.56 mmol) in
triethylamine (4.0 mL) and THF (2.0 mL) was added
PdCl2(PPh3)2 (64 mg, 0.91 mmol) and Cu(I) (17 mg, 0.90
mmol). The reaction mixture was heated at 80°C for 12 h
under N2 atmosphere. After cooling to room temperature,
the reaction mixture was poured into water and extracted
with CH2Cl2. The organic layer was dried over MgSO4
and the solvent was evaporated. The residues was purified
by column chromatography on silica gel by eluting with
CH2Cl2 and n-hexane (1:1 v/v) and recycling preparative
HPLC to give 5 (0.39 g, 47%). 1H NMR (CDCl3, 400.13
MHz): d, ppm 7.82 (1H, s, ArH), 7.80 (1H, s, ArH), 2.53
(2H, t, J = 7.2 Hz, –CH2–), 1.62–1.69 (2H, m, –CH2–),
1.46–1.52 (2H, m, –CH2–), 1.31–1.35 (4H, m, –CH2–),
0.90 (3H, t, J = 7.2 Hz, –CH3). 13C NMR (CDCl3, 100.61
Zn-9. Zn-9 was synthesized from 5 and Zn(OAc)2 by
the same procedure of Cu-9. Yield 55%. UV-vis (10 mM
in CHCl3): l, nm 696. 1H NMR (CDCl3, 400.13 MHz): d,
ppm 8.5–9.0 (4H, br, ArH), 6.4–6.7 (4H, br, ArH), 2.7–
2.9 (8H, m, –CH2–), 1.7–2.0 (16H, m, –CH2–), 1.0–1.2
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265
(16H, m, –CH2–), 0.8 (12H, br, –CH3). MALDI-TOF
MS (dithranol): m/z 1148.4 ([M + H], 100%), calcd. for
C64H60Cl4N8Zn: m/z 1148.4.
Cu-10. Cu-10 was synthesized from 6 and Cu(OAc)2
H2O by the same procedure of CuCu-9. Yield 49%.
UV-vis (10 mM in CHCl3): l, nm 634 and 710sh. MALDI-
TOF MS (dithranol): m/z 1449.2 ([M + H], 100%), calcd.
for C88H76Cl4N8Cu: m/z 1450.9.
H 5.59, N 7.77; found C 73.4, H 5.6, N 7.8. Purity
(HPLC) > 99%.
Zn-2.Yield 25%. UV-vis (10 mM in CHCl3): l, nm 682
and 735. 1H NMR (CDCl3, 400.13 MHz): d, ppm 6.6–8.5
(28H, br, ArH), 3.6–3.8 (8H, m, –CH2–), 2.4–2.6 (8H,
m, –CH2–), 1.9 (8H, br, –CH2–), 1.3 (16H, br, –CH2–),
0.9 (12H, br, –CH3). MALDI-TOF MS (dithranol): m/z
1443.4 ([M + H], 100%), calcd. for C88H80N8S4Zn: m/z
1443.3. Elemental analysis calcd. (%) for C88H80N8S4Zn:
C 73.23, H 5.59, N 7.76; found C 73.3, H 5.6, N 7.7.
Purity (HPLC) > 99%.
Zn-10. Yield 51%. UV-vis (10 mM in CHCl3): l, nm
1
655 and 705. H NMR (CDCl3, 400.13 MHz): d, ppm
6.4–9.0 (24H, br, ArH), 3.5–3.9 (8H, m, –CH2–), 2.3–
2.6 (8H, m, –CH2–), 1.6–1.9 (8H, m, –CH2–), 1.2–1.4
(16H, m, –CH2–), 0.8 (12H, br, –CH3). MALDI-TOF
MS (dithranol): m/z 1452.2 ([M + H], 100%), calcd. for
C88H76Cl4N8Zn: m/z 1452.8.
3. Yield 50%. UV-vis (10 mM in CHCl3): l, nm 670sh
and 734. MALDI-TOF MS (dithranol): m/z 1463.3
([M + H], 100%), calcd. for C80H72N8S8Cu: m/z 1463.3.
Elemental analysis calcd. (%) for C80H72N8S8Cu: C
65.57, H 4.95, N 7.65; found C 65.5, H 5.0, N 7.6. Purity
(HPLC) > 99%.
4.Yield 43%. UV-vis (10 mM in CHCl3): l, nm 682 and
735. MALDI-TOF MS (dithranol): m/z 1464.7 ([M + H],
100%), calcd. for C80H72N8S8Cu: m/z 1463.3. Elemental
analysis calcd. (%) for C80H72N8S8Cu: C 65.57, H 4.95, N
7.65; found C 65.6, H 4.9, N 7.7. Purity (HPLC) > 99%.
Cu-11. Cu-11 was synthesized from 7 and Cu(OAc)2
H2O by the same procedure of CuCu-9. Yield 49%.
UV-vis (10 mM in CHCl3): l, nm 644 and 712sh. MALDI-
TOF MS (dithranol): m/z 1472.7 ([M + H], 100%), calcd.
for C80H68Cl4N8S4Cu: m/z 1471.2.
Cu-12. Cu-12 was synthesized from 8 and Cu(OAc)2
H2O by the same procedure of CuCu-9. Yield 66%.
UV-vis (10 mM in CHCl3): l, nm 648 and 711. MALDI-
TOF MS (dithranol): m/z 1473.7 ([M + H], 100%), calcd.
for C80H68Cl4N8S4Cu: m/z 1471.2.
Acknowledgements
This work has been partially supported by Grants-in-
Aid for Scientific Research (B) (No. 22350086) from
Japan Society for the Promotion of Science (JSPS).
Thiophene-fused phthalocyanines
Cu-1. A mixture of Cu-9 (27 mg, 0.23 mmol), NaS
9H2O(45mg,18.8mmol)inN-methylpyrrolidone(5.0mL)
was stirred at 190°C with stirring for 12 h under N2
atomosphere. After cooling to room temperature, the
reaction mixture was poured into 50 mL saturated
NH4Cl aqueous solution and stirred for 30 min. The
resulting suspension was filtered off and washed with
methanol. The solid residue was purified by column
chromatography on activated alumina by eluting with
CHCl3 and recycling preparative HPLC to give Cu-1 (11
mg, 41%). UV-vis (10 mM in CHCl3): l, nm 669 and
726. MALDI-TOF MS (dithranol): m/z 1135.1 ([M + H],
100%), calcd. for C64H64N8S4Cu: m/z 1135.4. Elemental
analysis calcd. (%) for C64H64N8S4Cu: C 67.60, H 5.67, N
9.85; found C 67.7, H 5.7, N 9.7. Purity (HPLC) > 99%.
Zn-1, Cu-2, Zn-2, Cu-3, and Cu-4 were synthesized by
the same procedure of Cu-1.
Supporting information
Figures S1 and S2 are given in the supplementary
material. This material is available free of charge via the
Internet at http://www.worldscinet.com/jpp/jpp.shtml.
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J. Porphyrins Phthalocyanines 2014; 18: 266–266