Trifluoroethoxy-coating improves the axial ligand substitution of subphthalocyanine

Article abstract of DOI:10.1002/chem.201000373

A novel trifluoroethoxy (TFEO)-coated SubPc (1) and various axially functionalised derivatives thereof (2) have been efficiently synthesised. The advantage of the TFEO-coating on SubPcs compared to conventional fluorine-coated or uncoated molecules has be

Full text of DOI:10.1002/chem.201000373

DOI: 10.1002/chem.201000373
Trifluoroethoxy-Coating Improves the Axial Ligand Substitution of
Subphthalocyanine
Norio Shibata,*[a] Banibrata Das,[a] Etsuko Tokunaga,[a] Motoo Shiro,[c] and
Nagao Kobayashi*[b]
Abstract:
A
novel trifluoroethoxy
further used as a building block for the
synthesis of donor–acceptor SubPc–C60
hybrid 8, while iodo-SubPc 2e has
been used for the synthesis of trifluor-
oethoxy-coated SubPc–Pc dyads 9 and
10. All of these compounds are highly
soluble in all common organic solvents,
which greatly facilitates their purifica-
tion and characterisation. The SubPcs
2a–c incorporating oligoethylene glycol
moieties are attractive from a biologi-
cal point of view, while SubPcs 8–10
may prove useful for studies of intra-
molecular electron- and energy-transfer
processes.
(TFEO)-coated SubPc (1) and various
axially functionalised derivatives there-
of (2) have been efficiently synthesised.
The advantage of the TFEO-coating on
SubPcs compared to conventional fluo-
rine-coated or uncoated molecules has
been clearly demonstrated, as axial de-
rivatisation has been realised in very
good yields. Among various SubPcs
synthesised, formyl-SubPc 2 f has been
Keywords: fluorine
· phthalocya-
nines · porphyrinoids · substitution
reaction · synthesis
Introduction
promising chromophores with potential applications in opti-
cal data storage,[3] nonlinear optics,[4] photosynthetic models
for studying energy- and electron-transfer processes,[5] supra-
molecular chemistry,[6] and photodynamic therapy (PDT).[7]
The optoelectronic properties of SubPcs can be fine-tuned
by 1) varying their axial ligands and/or 2) peripheral func-
tionalisation.[1,8] However, the peripheral functionalisation
approach is not suitable for the synthesis of diverse SubPc
derivatives, since the harsh reaction conditions for SubPc
formation preclude the incorporation of a number of impor-
tant functional groups at the peripheral positions. Moreover,
this approach is somewhat tedious because an independent
phthalonitrile is required for each target SubPc. Therefore,
the substitution of axial ligands of SubPcs is the main route
for the synthesis of diverse SubPcs, although the chemical
yields are not always high. Indeed, Ng et al. have recently
reported the synthesis of biologically very effective SubPcs
axially substituted with oligoethylene glycol moieties, but
the key axial substitution reaction of SubPcs by oligoethy-
lene glycols could only be achieved in low to moderate
yields.[7] Recently, we discovered the unique non-aggrega-
tion property of trifluoroethoxy (TFEO)-coated phthalocya-
nines conjugated with deoxyribonucleosides, which are suita-
ble as PDT agents.[9a] We also synthesised TFEO-coated bi-
nuclear Pc, in which the two Pcs are covalently linked with
a conjugated rigid diyne spacer, and noted its prominent
avoidance of intermolecular aggregation.[9b] Fluorophobic
Subphthalocyanines (SubPcs), which can be regarded as
phthalocyanine (Pc) analogues with lower symmetry, are
nonplanar cone-shaped aromatic macrocycles composed of
three diimino-isoindoline units N-fused around a boron
centre.[1] Owing to their curved geometry, as confirmed by
X-ray crystallography,[2] these compounds show a reduced
tendency for aggregation and have a higher solubility index
than phthalocyanines. Their 14 p-electron core also facili-
tates strong absorption and leads to high emission quantum
yields in the visible region. These features make SubPcs
[a] Prof. N. Shibata, B. Das, E. Tokunaga
Department of Frontier Materials, Graduate School of Engineering
Nagoya Institute of Technology, Gokiso
Showa-ku, Nagoya, 466-8555 (Japan)
Fax : (+81)52-735-7543
E-mail: nozshiba@nitech.ac.jp
[b] Prof. N. Kobayashi
Department of Chemistry, Graduate School of Science
Tohoku University, Aobayama, Sendai 980-8578 (Japan)
Fax : (+81)22-795-7719
E-mail: nagaok@mail.tains.tohoku.ac.jp
[c] Dr. M. Shiro
Rigaku Corporation, 3-9-12 Matsubara-cho, Akishima
Tokyo 196-8666 (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201000373.
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FULL PAPER
repulsion is responsible for the observed lack of aggrega-
tion, which is seen even in the case of the 18 p-conjugated
system. As part of our ongoing research programs directed
towards the development of novel functionalised Pcs[9] and
the synthesis of fluorine-containing biologically active com-
pounds,[10] we disclose herein the synthesis of novel TFEO-
substituted subphthalocyanine (SubPc) 1, which has proved
to be an effective precursor for the synthesis of diverse
SubPcs bearing a variety of substituents at their axial posi-
tion. The electron-withdrawing effect and non-aggregation
property of the twelve trifluoroethoxy moieties on 1 have
been found to dramatically facilitate nucleophilic axial
ligand substitution reactions on the SubPcs. Indeed, the
TFEO-coating is revealed to be far more effective than the
conventional fluorine-coating or no coating in facilitating
this axial ligand substitution reaction.
Figure 1. X-ray crystallographic structure of 1 with hydrogen atoms omit-
ted for clarity (CCDC-758071 can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
Results and Discussion
tion using perfluoro-substituted SubPc 6 as the substrate, an-
ticipating that the replacement of all peripheral hydrogen
atoms of 4 with fluorine would render the nucleophilic sub-
stitution reaction chemically high-yielding. Contrary to our
expectations, 6 proved to be unreactive toward 3a in the
presence of triethylamine under reflux conditions (entry 2).
We next examined the ligand substitution reaction of our
novel SubPc 1 with 3a. Gratifyingly, the desired compound
2a was isolated in 68% yield (entry 3), which represents a
vast improvement compared with the aforementioned two
results (entries 1 and 2). Encouraged by this result, ligand
substitution reactions of SubPcs 1, 4, and 6 with phenol de-
rivatives 3b or 3c bearing a di- or triethylene glycol methyl
moiety were evaluated and compared, since SubPcs bearing
the units of 3b or 3c have been shown to be promising can-
didates for photodynamic therapy of cancers.[7] While the
yields of the ligand substitutions of 4 and 6 to give 5b,c and
7b,c were low (30–41%, entries 4, 5, 7, and 8), TFEO-SubPc
1 gave 2b,c in high yields (83–85%, entries 6 and 9). It
should be mentioned that compounds 2a–c could be easily
purified by column chromatography on silica gel using
common organic solvents, in marked contrast to the tedious
size-exclusion chromatography required for compounds 5a–
c.[7] These results clearly demonstrate that a trifluoroethoxy
coating at the periphery of SubPc plays a crucial role in en-
hancing chemical efficiency and facilitating product isola-
tion.
Motivated by this favourable outcome, we next embarked
on the synthesis of a number of TFEO-SubPcs 2d–h axially
substituted with a variety of phenol and alcohol derivatives
bearing synthetically useful functional groups such as iodo,
formyl, and ethynyl (Table 1, entries 10–14). Substitutions of
the chlorine atom by phenol (3d) and 4-iodophenol (3e) af-
forded the corresponding products 2d and 2e in yields of 81
and 80%, respectively (entries 10 and 11). Formyl and eth-
ynyl substituents as well as aliphatic 3-butyn-1-ol 3h were
also well tolerated under the same conditions, the reactions
with 1 affording SubPcs 2 f–h in good yields of 63–73%. All
compounds bearing the TFEO groups were purified and
SubPc 1 was synthesised in 32% yield by cyclotrimerisation
of 3,4,5,6-tetrakis(2,2,2-trifluoroethoxy)phthalonitrile in the
presence of boron trichloride in p-xylene under reflux condi-
tions (Scheme 1).[11] The SubPc 1 was purified by column
Scheme 1. Synthesis of 1.
1
chromatography on silica gel and characterised by H and
19F NMR spectroscopies, UV/Vis spectrophotometry,
MALDI-TOF mass spectrometry, and FTIR spectroscopy
(see the Supporting Information). The molecular structure
of 1 was also determined by X-ray diffraction analysis.
Single crystals suitable for X-ray analysis were grown by
slow evaporation of the solvent from a solution in toluene.
As shown in Figure 1, the boron centre is tetracoordinated,
thus forming a cone-shaped structure.
Axial substitution reactions of 1 to afford 2 were carried
out by classical substitutions of the chlorine atom with vari-
ous alcohol derivatives 3 in toluene (Table 1). Ethylene
glycol 3a was first selected as a nucleophile due to the diffi-
culty of the axial ligand substitution reaction as well as the
biological importance of the corresponding substituted
SubPcs.[7] Ng and co-workers reported that the axial ligand
substitution of conventional SubPc 4 by 3a gave the SubPc
5a bearing an ethylene glycol moiety in just 5% yield[7]
(Table 1, entry 1). We attempted a similar substitution reac-
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7555

N. Shibata, N. Kobayashi et al.
in chloroform at 1ꢁ10À5 m. Sim-
ilar non-aggregation behaviour
was also found in a variety of
other solvents at different con-
centrations (Figure 2 and the
Supporting Information). It is
interesting to note that the
shape and size of these spectra
did not change even after the
addition of pyridine as a metal-
coordinating molecule that is
known to disrupt aggregation
(see also Figure S53 in the Sup-
porting Information for colour
graphics). Compared with liter-
ature data,[1b,7] the Q-band ab-
sorption maxima of 1 and 2a–c
are red-shifted by 30–35 nm
due to the strong electron-with-
drawing effect of the twelve ap-
pended trifluoroethoxy groups.
Almost superimposable singlet
ground-state transitions of the
compounds demonstrate that
the macrocyclic p-system is not
perturbed by the various axial
ligands. As compounds 2a–c
may have potential application
as PDT agents,[7] the observed
non-aggregation property is ex-
tremely important because in-
termolecular aggregation facili-
Table 1. Axial ligand substitution reactions of subphthalocyanines.
Entry
1[a]
SubPc-Cl
R
H
R1OH 3
SubPc-OR1
Yield [%]
5
4
5a
2[b]
6
1
F
3a
3a
7a
2a
NR
68
3[c]
OCH2CF3
4[a]
4
H
5b
30
5[b]
6[c]
6
1
F
3b
3b
7b
2b
41
83
OCH2CF3
7[a]
4
H
5c
37
8[b]
9[c]
6
1
F
3c
3c
7c
2c
39
85
OCH2CF3
10[c]
1
1
OCH2CF3
OCH2CF3
2d
2e
81
80
11[c]
12[c]
1
OCH2CF3
2 f
73
13[c]
14[c]
1
1
OCH2CF3
OCH2CF3
2g
2h
73
63
[a] Data taken from ref. [7]. [b] Et3N (1.65 equiv was used). [c] Et3N (3.5 equiv was used).
1
then characterised by H and 19F NMR spectroscopies, UV/
Vis and fluorescence spectroscopies, MALDI-TOF mass
spectrometry, and FTIR spectroscopy (see the Supporting
Information). They were found to be appreciably soluble in
both polar and less-polar organic solvents, presumably due
to the character of the trifluoroethoxy substituents on the
1
SubPc macrocycle. It should be noted that both the H and
19F NMR spectra of the compounds showed extremely re-
solved, easily assignable signals that were in accordance
with the proposed structures and independent of the func-
tional groups present (see the Supporting Information). The
high resolution of these spectra is indicative of non-aggrega-
tion in the solution state, demonstrating the strong repulsion
effect of the trifluoroethoxy groups and SubPc geometry.
The UV/Vis spectra of SubPcs 1 and 2a–c were recorded
in a variety of solvents (chloroform, benzotrifluoride, diox-
ane, and DMF) at concentrations ranging from 1ꢁ10À4 m to
1ꢁ10À6 m. All of these compounds were found to be essen-
tially non-aggregated, irrespective of the solvent and con-
centration, and were characterised by sharp absorption
bands in the B-band region at around 330 nm and in the Q-
band region at around 600 nm. Figure 2 shows representa-
tive examples of the absorption spectra of SubPc 1 and 2a–c
Figure 2. UV/Vis absorption spectra of 1 (a), 2a (b), 2b (c), and 2c (d) in
CHCl3 (1ꢁ10À5 m).
tates an efficient nonradiative energy relaxation pathway,
greatly shortening the excited-state lifetimes.[12]
Steady-state fluorescence spectra of the SubPcs 1 and 2a–
c were also measured in different organic solvents. The com-
pounds showed very high fluorescence, a further important
consequence of the low aggregation tendency (see Figure 3
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Trifluoroethoxy Groups on Subphthalocyanine
FULL PAPER
and the Supporting Information). As shown in Figure 3,
SubPc 1 exhibits a strong emission band at 620 nm with a
fluorescence quantum yield (fF) of 0.83, while SubPc 2a
emits at 613 nm with a fF value of 0.56 in chloroform upon
excitation at 530 nm. SubPcs 2b and 2c show fluorescence
at 612–614 nm with quantum yields in the range 0.05–0.11
(Table 2; see also Figure S71 in the Supporting Information
for colour graphics). The fluorescence quenching of the
latter two compounds can be attributed to the presence of
the phenyl moiety, which is likely to facilitate an intramolec-
ular photo-induced electron-transfer process.[7]
synthesised by palladium-catalysed Sonogashira cross-cou-
plings of SubPc iodide 2e and terminal alkynes as the key
reaction. For example, homo dyad 9 was synthesised in 70%
yield by the cross-coupling of iodo-SubPc 2e with monoal-
kynyl TFEO-ZnPc 11 in the presence of catalytic amounts
of [PdCl2ACHTNUGTRNEUNG(PPh3)2] and CuI in anhydrous THF. Similarly,
hetero SubPc–Pc hybrid 10 was obtained in a good yield of
56% by the reaction of 2e with ethynyl-tert-butyl zinc Pc 12.
All of these hybrid compounds were purified by column
1
chromatography on silica gel and were characterised by H
and 19F NMR spectroscopies, UV/Vis spectrophotometry,
MALDI-TOF mass spectrometry, and FTIR spectroscopy
(see the Supporting Information).
Table 2. Fluorescence quantum yields[a] (fF) and emission maxima (lem
Absorption spectra were recorded for the hybrid com-
pounds 8–10 and their constituent monomers 1, 11, and 12
(Figure 4) (see also the Supporting Information). Figure 4
(top) shows the absorption and magnetic circular dichroism
(MCD) spectra of a SubPc with twelve CF3CH2O- substitu-
ents (1), and of low-symmetry ZnPc compounds with twelve
peripheral CF3CH2O- groups and one ethynyl group (11)
and three peripheral tert-butyl groups and one ethynyl
group (12). These compounds represent the constituent
chromophores of the dyads 9 and 10 (middle) and 8
(bottom) giving rise to the spectra in these figures. A com-
parison of the spectral data reveals many intriguing proper-
ties. The major p-p* bands shift to longer wavelength in the
order 1, 12, and 11. The absorption coefficients of 1 are
smaller than those of 11 or 12. Of the two Pc compounds,
the Q band of 11 is more intense and is red-shifted relative
to that of 12. This red-shift can be ascribed primarily to
ligand nonplanarity due to the presence of the bulky
CF3CH2O- groups at the a-positions.[15,16] The MCD spectra
are broadly similar to those of the parent SubPc[17,18] and
MPc complexes.[19–21] Derivative-shaped Faraday A-terms
are observed for each major absorption peak, so three- or
fourfold axes of symmetry are clearly retained and the main
p-p* excited states remain orbitally degenerate. The MCD
intensity of the Q band is enhanced relative to that observed
in the B1/B2 (or Soret) band region due to the larger orbital
angular momentum change associated with the forbidden Q
transition. It should be noted that the MCD intensity of the
Q band of SubPc 1 is significantly weaker than those of Pcs
11 and 12 due to the doming of the p-system.
[nm]) of TFEO-coated SubPcs.
SubPc CHCl3
PhCF3
Dioxane
DMF
1
0.83 (620)
0.95 (618)
0.63 (610)
0.05 (612)
0.05 (612)
0.55 (613)
–
0.85 (621)
–
–
–
0.51 (616)
0.49 (618)
0.007 (796, 616)
–
2a
2b
2c
2d
2 f
8
0.56 (613)
0.06 (614)
0.07 (614)
0.55 (615)
0.47 (618)
0.55 (612)
0.11 (614)
0.11 (614)
–
–
–
–
–
0.005 (795, 614) 0.005 (612)
9
10
0.07 (767, 616)
0.005 (796, 615)
0.13 (714, 614) 0.24 (718, 617)
– 0.02 (686, 619)
[a] Fluorescence quantum yields were calculated using tetraphenylpor-
phyrin (TPP) in benzene as a reference (fF =0.11).[17]
Figure 3. Steady-state emission spectra of 1 (a), 2a (b), 2b (c), and 2c (d)
in CHCl3 with excitation at 530 nm.
Figure 4 (middle) shows the spectra of dyads comprised of
1 and either 11 (compound 9) or 12 (compound 10). Before
recording these spectra, we confirmed that the species were
well dispersed by carrying out Beerꢂs experiments; that is, it
was ensured that the Q band intensified in a linear manner
as the concentration was increased. Taking the band shape,
position, and intensity of the constituent chromophores into
account, Figure 4 (top), the spectra can be approximately
expressed as a summation of the spectra of the constituent
moieties. The broad B1/B2 band region of 9 can be attribut-
ed to an overlap of the n-p* bands of the ether oxygen and
p-p* transitions of the ligand p-system.[16] The Q-band in-
tensity of the SubPc moiety (at ca. 600 nm) is much lower
than that of the Pc moiety, as would be anticipated based on
Photo-induced energy- and electron-transfers are impor-
tant processes that lead to useful applications in photosyn-
thetic model systems for the conversion of solar energy into
profitable chemical energy.[13] In this context, donor–accept-
or hybrids with well-defined spacers can mimic the natural
photosynthetic process. With this objective, we synthesised
trifluoroethoxy-SubPc–C60 hybrid 8 along with subphthalo-
cyanine–phthalocyanine dyads 9 and 10 to demonstrate the
utility of SubPcs 2 (Scheme 2). SubPc–C60 hybrid 8 was pre-
pared by a 1,3-dipolar cycloaddition reaction according to
the Prato procedure.[14] Thus, heating a mixture of SubPc 2 f
and sarcosine with C60 gave compound 8 in 57% yield. On
the other hand, SubPc–Pc dyads 9 and 10 were conveniently
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N. Shibata, N. Kobayashi et al.
Steady-state emission spectra
of the SubPc dyads were mea-
sured in a variety of solvents
(see the Supporting Informa-
tion). Figure 5 shows a repre-
sentative comparative fluores-
cence spectrum of SubPc–C60
dyad 8 along with that of the
precursor formyl-SubPc 2 f, the
excited-state interactions be-
tween the photo- and redox-
active constituents in which are
quite revealing (see also Fig-
ure S73 in the Supporting Infor-
mation for colour graphics). A
strong quenching of the SubPc
fluorescence compared to the
reference precursor 2 f is ob-
served, irrespective of the sol-
vent, which can be attributed to
a substantial amount of elec-
tron-transfer from the SubPc
moiety to the fullerene accept-
or. It is interesting to note that
the TFEO-coated SubPc moiety
still acts as a donor in this dyad
8, since the TFEO-Pc can no
longer act as a donor in the
TFEO-Pc–C60 dyad.[9e] This
phenomenon is also supported
by fluorescence quantum yield
data (Table 2). While SubPc 2 f
shows fF values of 0.47 and
0.49 in CHCl3 and dioxane, re-
spectively, the corresponding
values for the SubPc–C60 dyad 8
are significantly decreased to
0.005 and 0.007 in the respec-
tive solvents.
Scheme 2. Structures of SubPc–C60 dyad 8 and SubPc–Pc dyads 9 and 10.
Conclusion
In conclusion, we have synthes-
ised a novel trifluoroethoxy-coated SubPc (1) and various
axially functionalised derivatives thereof (2). The advantage
of the TFEO-coating of the SubPc compared to convention-
al fluorine-coated or uncoated molecules is clearly apparent
as axial derivatisation has been realised in very good yields.
Some of the resulting products have been further used as
building blocks for synthesising a donor–acceptor SubPc–C60
hybrid and trifluoroethoxy-coated SubPc–Pc dyads. All of
the prepared compounds are highly soluble in all common
organic solvents (see the Supporting Information),[23] which
facilitates their easy purification and characterisation and
may also prove to be of considerable interest in fields such
as catalysts for organic reactions or dyes for solar cells. The
Figure 4 (top). The trough and peak observed in the MCD
spectrum of 10 at 684 and 669 nm correspond directly to an
absorption peak and a shoulder in the intensity. Since these
bands are clearly Faraday B-terms, there must be a ground-
state interaction between the SubPc and Pc moieties.
Figure 4 (bottom) shows the spectra of the SubPc–C60
dyad 8. As is the case with 9 and 10, the spectra can be
viewed as a summation of the spectra of the component
SubPc and C60 moieties. Most of the absorption band inten-
sity in the 250–300 nm region can be ascribed to the C60
moiety.[22] In the MCD spectrum, the intensity associated
with the C60 moiety is relatively low since 1 has similar in-
tensity in this region; Figure 4 (top).
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Trifluoroethoxy Groups on Subphthalocyanine
FULL PAPER
SubPcs 2a–c are attractive from a biological point of view,
while SubPcs 8–10 could be useful for studies of intramolec-
ular electron- and energy-transfer processes, although fur-
ther investigation is required.
Experimental Section
General methods: All solvents were dried and distilled according to stan-
dard procedures. All of the reactions were monitored by thin-layer chro-
matography (TLC) on 0.25 mm Merck silica gel plates (60F-254).
Column chromatography was carried out on a column packed with silica
1
gel 60N (spherical, neutral, size 63–210 mm). H and 19F NMR (200 MHz)
spectra were recorded on
a Varian Gemini-200 spectrometer, while
13C NMR (600 MHz) spectra were recorded on a Bruker-600 spectrome-
ter. Chemical shifts (d) are expressed in ppm downfield from tetrame-
thylsilane and internal acetone. Infrared (IR), UV/Vis, and steady-state
fluorescence spectra were recorded on a JASCO FTIR-200 spectrometer,
V-530 spectrometer, and FP-6200 spectrofluorimeter, respectively. Fluo-
rescence quantum yields were calculated according to a procedure de-
scribed elsewhere.[17] MALDI-TOF mass spectra were taken on a SHI-
MADZU Axima CFR Plus and ESI mass spectra were recorded on a
SHIMADZU LCMS-2010 EV.
Subphthalocyanine 1: BCl3 (3.46 mL, 1m solution in p-xylene) was added
to dry 3,4,5,6-tetrakis(2,2,2-trifluoroethoxy)phthalonitrile (500 mg,
0.961 mmol) under an argon atmosphere. The reaction mixture was
stirred under reflux (ꢀ1408C) for 3 h. The purple solution was then
flushed with argon and the solvent was evaporated. The resulting solid
was purified by column chromatography on silica gel, eluting with 10–
12% ethyl acetate in hexane, to afford SubPc 1 as a purple solid (163 mg,
32%). 1H NMR (200 MHz, CDCl3): d=5.28 (q, J=8.2 Hz, 12H; OCH2 ꢁ
6), 4.67 ppm (q, J=8.2 Hz, 12H; OCH2 ꢁ6); 19F NMR (188 MHz,
CDCl3): d=À74.13 (t, J=7.0 Hz, 18F; CF3 ꢁ6), À74.74 ppm (t, J=
˜
7.0 Hz, 18F; CF3 ꢁ6); IR (KBr): n=3417, 2973, 1607, 1542, 1492, 1432,
1281, 1238, 1166, 1131, 1092, 1068, 968, 834, 661 cmÀ1; UV/Vis (CHCl3):
lmax (loge)=602 (4.95), 558 (4.49), 331 (4.50), 281 nm (4.62); PhCF3: lmax
(loge)=599 (4.94), 552 (4.48), 330 nm (4.49); dioxane: lmax (loge)=603
(4.94), 558 (4.49), 333 (4.48), 281 nm (4.59); MALDI-TOF MS: m/z:
calcd for C48H24BClF36N6O12: 1606.07; found: 1604.45 (most abundant
peak in the isotopic envelope).
Standard procedure (SP) for axial substitution reactions of SubPc 1: A
mixture of SubPc 1, triethylamine, and the requisite alcohol in toluene
was heated at reflux (ꢀ1208C) for 15–24 h under an inert atmosphere.
After cooling to room temperature, the solvents were removed under re-
duced pressure and the residue was purified by column chromatography
on silica gel using mixtures of ethyl acetate and hexane in different pro-
portions as eluents. In some cases, the product was further purified by re-
crystallisation.
Figure 4. Absorption and MCD spectra of monomeric 1, 11, 12 (top),
SubPc–Pc dyads 9, 10 (middle), and SubPc–C60 dyad 8 (bottom) in diox-
ane.
Subphthalocyanine 2a: According to the SP, SubPc
1 (150 mg,
0.093 mmol) was reacted with triethylene glycol 3a (0.075 mL,
0.56 mmol) by refluxing in toluene (10 mL) containing triethylamine
(0.046 mL, 0.327 mmol) for 20 h. The resulting crude purple product was
subjected to column chromatography on silica gel, eluting with 30–40%
ethyl acetate in hexane. SubPc 2a was isolated as a purple solid (109 mg,
68%). 1H NMR (200 MHz, CDCl3): d=5.36–5.22 (m, 12H; OCH2 ꢁ6),
4.66 (q, J=8.2 Hz, 12H; OCH2 ꢁ6), 3.48–3.44 (m, 2H; CH2OH), 3.39–
3.31 (m, 4H; CH2CH2OH, CH2), 3.15–3.10 (m, 2H; CH2), 2.68 (t, J=
4.6 Hz, 2H; BOCH2CH2), 1.68 ppm (t, J=4.6 Hz, 2H; BOCH2);
19F NMR (188 MHz, CDCl3): d=À74.13 (t, J=7.0 Hz, 18F; CF3 ꢁ6),
˜
À74.78 ppm (t, J=7.0 Hz, 18F; CF3 ꢁ6); IR (KBr): n=3446, 2972, 1733,
1670, 1542, 1492, 1458, 1433, 1282, 1238, 1165, 1127, 1067, 1017, 969, 853,
663 cmÀ1; UV/Vis (CHCl3): lmax (loge)=595 (4.92), 548 (4.46), 330 (4.50),
278 nm (4.62); PhCF3: lmax (loge)=592 (4.89), 547 (4.44), 327 nm (4.45);
DMF: lmax (loge)=594 (4.88), 549 (4.43), 321 nm (4.49); MALDI-TOF
MS: m/z: calcd for C54H37BF36N6O16: 1720.18; found: 1718.59 (most abun-
dant peak in the isotopic envelope).
Figure 5. Steady-state emission spectra of SubPc–C60 dyad 8 in CHCl3 (a),
dioxane (b); SubPc-2 f in CHCl3 (c) and dioxane (d) with excitation at
530 nm. Inset: Corresponding emission spectra of dyad 8.
Chem. Eur. J. 2010, 16, 7554 – 7562
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
7559

N. Shibata, N. Kobayashi et al.
Subphthalocyanine 2b: According to the SP, SubPc
1
(150 mg,
then dry toluene (2 mL) and Et3N (0.026 mL, 0.185 mmol) were added
under N2 atmosphere. The reaction mixture was stirred under reflux
(ꢀ1208C) for 24 h, and then the solvent was evaporated. The residual
purple solid was subjected to column chromatography on silica gel elut-
ing with 10–12% ethyl acetate in hexane. SubPc 2d was isolated as a
purple solid (71 mg, 81%). 1H NMR (200 MHz, CDCl3): d=6.86–6.74
(m, 3H; Ar-H), 5.41 (d, J=7.2 Hz, 2H; Ar-H), 5.22 (q, J=8.0 Hz, 12H;
OCH2 ꢁ6), 4.66 ppm (q, J=8.0 Hz, 12H; OCH2 ꢁ6); 19F NMR (188 MHz,
CDCl3): d=À74.10 (t, J=8.0 Hz, 18F; CF3 ꢁ6), À74.77 ppm (t, J=
0.093 mmol) was reacted with 4-(3,6-dioxaheptoxy)phenol 3b[7] (119 mg,
0.56 mmol) by refluxing in toluene (10 mL) containing triethylamine
(0.046 mL, 0.327 mmol) for 15 h. The resulting crude purple product was
subjected to column chromatography on silica gel, eluting with 30%
ethyl acetate in hexane. The product was further purified by recrystallisa-
tion from chloroform/hexane to furnish SubPc 2b as a purple solid
(138 mg, 83%). 1H NMR (200 MHz, CDCl3): d=6.36 (d, J=9.0 Hz, 2H;
Ar-H), 5.34 (d, J=9.0 Hz, 2H; Ar-H), 5.22 (q, J=8.2 Hz, 12H; OCH2 ꢁ
6), 4.66 (q, J=8.0 Hz, 12H; OCH2 ꢁ6), 3.90–3.85 (m, 2H; CH2), 3.75–
3.70 (m, 2H; CH2), 3.67–3.62 (m, 2H; CH2), 3.55–3.50 (m, 2H; CH2),
3.35 ppm (s, 3H; CH3); 19F NMR (188 MHz, CDCl3): d=À74.08 (t, J=
7.9 Hz, 18F; CF3 ꢁ6), À74.77 ppm (t, J=7.9 Hz, 18F; CF3 ꢁ6); IR (KBr):
n˜ =2973, 1541, 1492, 1459, 1432, 1282, 1238, 1216, 1165, 1130, 1068, 1016,
970, 854, 753, 662 cmÀ1; UV/Vis (CHCl3): lmax (loge)=597 (5.00), 553
(4.55), 329 (4.54), 276 nm (4.70); PhCF3: lmax (loge)=594 (4.98), 550
(4.52), 328 nm (4.51); DMF: lmax (loge)=597 (4.96), 552 (4.52), 326 nm
˜
8.0 Hz, 18F; CF3 ꢁ6); IR (KBr): n=3421, 2979, 1493, 1459, 1431, 1281,
1237, 1166, 1129, 1068, 1018, 970, 854, 755, 662 cmÀ1; UV/Vis (CHCl3):
lmax (loge)=597 (4.97), 550 (4.51), 331 (4.51), 276 nm (4.64); PhCF3: lmax
(loge)=594 (4.98), 547 (4.52), 328 nm (4.52); dioxane: lmax (loge)=597
(4.97), 550 (4.52), 330 (4.52), 275 nm (4.64); MALDI-TOF MS: m/z:
calcd for C54H29BF36N6O13: 1664.13; found: 1663.38 (most abundant peak
in the isotopic envelope).
Subphthalocyanine 2e: SubPc 1 (285 mg, 0.177 mmol) was reacted with
4-iodophenol 3e (195 mg, 0.887 mmol) by refluxing in toluene (5 mL)
containing triethylamine (0.087 mL, 0.621 mmol) for 24 h. The resulting
crude purple product was purified by column chromatography on silica
gel eluting with toluene/hexane (70:30) to give SubPc 2e as a purple
solid (253 mg, 80%). 1H NMR (200 MHz, CDCl3): d=7.12–7.08 (m, 2H;
Ar-H), 5.29–5.24 (m, 2H; Ar-H), 5.24–5.15 (m, 12H; OCH2 ꢁ6), 4.73–
4.60 ppm (m, 12H; OCH2 ꢁ6); 19F NMR (188 MHz, CDCl3): d=À74.05
(t, J=8.0 Hz, 18F; CF3 ꢁ6), À74.77 ppm (t, J=8.0 Hz, 18F; CF3 ꢁ6); IR
(4.51); MALDI-TOF MS: m/z: calcd for C59H39BF36N6O16
found: 1781.64 (most abundant peak in the isotopic envelope).
:
1782.19;
Subphthalocyanine 2c: According to the SP, SubPc
1
(150 mg,
0.093 mmol) was reacted with 4-(3,6,9-trioxadecoxy)phenol 3c[7] (144 mg,
0.56 mmol) by refluxing in toluene (10 mL) containing triethylamine
(0.046 mL, 0.327 mmol) for 16 h. The resultant crude product was sub-
jected to column chromatography on silica gel, eluting with 30–35%
ethyl acetate in hexane. The product was further purified by recrystallisa-
˜
tion from chloroform/hexane to afford SubPc 2c as
a
purple solid
(KBr): n=3442, 2971, 1492, 1460, 1431, 1282, 1238, 1215, 1166, 1129,
(144 mg, 85%). 1H NMR (200 MHz, CDCl3): d=6.36 (d, J=9.0 Hz, 2H;
Ar-H), 5.34 (d, J=9.0 Hz, 2H; Ar-H), 5.22 (q, J=8.2 Hz, 12H; OCH2 ꢁ
6), 4.66 (q, J=8.2 Hz, 12H; OCH2 ꢁ6), 3.89–3.84 (m, 2H; CH2), 3.75–
3.70 (m, 2H; CH2), 3.67–3.59 (m, 6H; CH2 ꢁ3), 3.53–3.48 (m, 2H; CH2),
3.35 ppm (s, 3H; CH3); 19F NMR (188 MHz, CDCl3): d=À74.08 (t, J=
7.9 Hz, 18F; CF3 ꢁ6), À74.77 ppm (t, J=7.9 Hz, 18F; CF3 ꢁ6); IR (KBr):
1068, 1018, 970, 834, 753, 662 cmÀ1; MALDI-TOF MS: m/z: calcd for
C54H28BF36IN6O13: 1790.03; found: 1789.32 (most abundant peak in the
isotopic envelope).
Subphthalocyanine 2 f: According to the SP, SubPc 1 (80 mg, 0.05 mmol)
was reacted with 3-hydroxybenzaldehyde 3 f (30 mg, 0.25 mmol) by re-
fluxing in toluene (2 mL) containing triethylamine (0.024 mL,
0.174 mmol) for 16 h. The resulting crude purple product was purified by
column chromatography on silica gel eluting with 20% ethyl acetate in
hexane. The product was further purified by recrystallisation from tolu-
ene/hexane to afford formyl-SubPc 2 f as a purple solid (61 mg, 73%).
1H NMR (200 MHz, CDCl3): d=9.68 (s, 1H; CHO), 7.22–7.18 (m, 1H;
Ar-H), 7.03–6.96 (m, 1H; Ar-H), 5.82–5.78 (m, 2H; Ar-H), 5.26 (q, J=
8.2 Hz, 12H; OCH2 ꢁ6), 4.66 ppm (q, J=8.0 Hz, 12H; OCH2 ꢁ6);
19F NMR (188 MHz, CDCl3): d=À74.08 (t, J=8.1 Hz, 18F; CF3 ꢁ6),
˜
n=2971, 1541, 1492, 1459, 1432, 1283, 1238, 1165, 1129, 1067, 1017, 970,
854, 753, 662 cmÀ1; UV/Vis (CHCl3): lmax (loge)=597 (4.99), 553 (4.53),
330 (4.53), 276 nm (4.68); PhCF3: lmax (loge)=594 (4.96), 550 (4.50),
328 nm (4.49); DMF: lmax (loge)=597 (4.96), 552 (4.52), 327 nm (4.51);
MALDI-TOF MS: m/z: calcd for C61H43BF36N6O17: 1826.22; found:
1824.27 (most abundant peak in the isotopic envelope).
Subphthalocyanine 7b: Dodecafluorosubphthalocyanato boronACTHNUGTRNEUNG(III) chlo-
ride 6[11] (50 mg, 0.077 mmol) was reacted with 4-(3,6-dioxaheptoxy)phe-
nol 3b[7] (98.5 mg, 0.464 mmol) by refluxing in toluene (4.5 mL) contain-
ing triethylamine (0.018 mL, 0.128 mmol) for 24 h. The resulting crude
purple product was subjected to column chromatography on silica gel
eluting with 30% ethyl acetate in hexane to furnish SubPc 7b as a purple
solid (26 mg, 41%). 1H NMR (200 MHz, CDCl3): d=6.30 (dd, J=6.8,
2.2 Hz, 2H; Ar-H), 5.24 (dd, J=6.6, 2.2 Hz, 2H; Ar-H), 3.90–3.85 (m,
2H; CH2), 3.74–3.70 (m, 2H; CH2), 3.66–3.62 (m, 2H; CH2), 3.55–3.50
(m, 2H; CH2), 3.36 ppm (s, 3H; CH3); 19F NMR (188 MHz, CDCl3): d=
À136.20 (dd, J=18.9, 4.5 Hz, 6F), À146.87 ppm (dd, J=19.6, 4.5 Hz,
˜
À74.77 ppm (t, J=8.1 Hz, 18F; CF3 ꢁ6); IR (KBr): n=3442, 2977, 1698,
1492, 1432, 1281, 1239, 1166, 1130, 1104, 1067, 1017, 970, 854, 753,
662 cmÀ1; UV/Vis (CHCl3): lmax (loge)=599 (4.97), 551 (4.52), 331 (4.57),
275 nm (4.69); dioxane: lmax (loge)=600 (4.95), 552 (4.51), 332 (4.55),
274 nm (4.68); MALDI-TOF MS: m/z: calcd for C55H29BF36N6O14
1692.13; found: 1690.70 (most abundant peak in the isotopic envelope).
Subphthalocyanine 2g: According to the SP, SubPc (50 mg,
:
1
0.031 mmol) was reacted with 3-hydroxyphenylacetylene 3g (0.017 mL,
0.156 mmol) by refluxing in toluene (1 mL) containing triethylamine
(0.015 mL, 0.109 mmol) for 21 h. The resulting crude purple product was
subjected to column chromatography on silica gel eluting with 12% ethyl
acetate in hexane. SubPc 2g was isolated as a purple solid (38.4 mg,
73%). 1H NMR (200 MHz, CDCl3): d=6.88–6.72 (m, 2H; Ar-H), 5.49–
5.42 (m, 2H; Ar-H), 5.30–5.19 (m, 12H; OCH2 ꢁ6), 4.66 (q, J=8.2 Hz,
12H; OCH2 ꢁ6), 2.94 ppm (s, 1H; CH); 19F NMR (188 MHz, CDCl3): d=
À74.10 (t, J=7.9 Hz, 18F; CF3 ꢁ6), À74.77 ppm (t, J=7.9 Hz, 18F; CF3 ꢁ
6); IR (KBr): n˜ =3438, 3304, 2974, 1492, 1458, 1431, 1281, 1238, 1166,
1130, 1067, 1016, 970, 853, 662 cmÀ1; MALDI-TOF MS: m/z: calcd for
C56H29BF36N6O13: 1688.13; found: 1686.54 (most abundant peak in the
isotopic envelope).
˜
6F); IR (KBr): n=3446, 2882, 1650, 1533, 1485, 1428, 1394, 1264, 1223,
1164, 1113, 991, 966, 835, 773, 742, 715, 640 cmÀ1; ESI MS: m/z: calcd for
C35H15BF12N6O4: 822.11; found: 845.10 [M+Na]+.
Subphthalocyanine 7c: Dodecafluorosubphthalocyanato boronACTHNUGTRNEUNG(III) chlo-
ride 6[11] (50 mg, 0.077 mmol) was reacted with 4-(3,6,9-trioxadecoxy)phe-
nol 3c[7] (119 mg, 0.464 mmol) by refluxing in toluene (4.5 mL) contain-
ing triethylamine (0.018 mL, 0.128 mmol) for 24 h. The resulting crude
product was subjected to column chromatography on silica gel eluting
with 40% ethyl acetate in hexane to afford SubPc 7c as a purple solid
(26 mg, 39%). 1H NMR (200 MHz, CDCl3): d=6.31 (dd, J=6.5, 2.1 Hz,
2H; Ar-H), 5.26 (dd, J=6.8, 2.2 Hz, 2H; Ar-H), 3.89–3.85 (m, 2H; CH2),
3.74–3.69 (m, 2H; CH2), 3.68–3.60 (m, 6H; CH2 ꢁ3), 3.54–3.50 (m, 2H;
CH2), 3.36 ppm (s, 3H; CH3); 19F NMR (188 MHz, CDCl3): d=À136.23
(dd, J=19.5, 5.7 Hz, 6F), À146.87 ppm (dd, J=19.0, 5.6 Hz, 6F); IR
Subphthalocyanine 2h: According to the SP, SubPc
1 (50 mg,
0.031 mmol) was reacted with 3-butyn-1-ol 3h (0.012 mL, 0.156 mmol) by
refluxing in toluene (1 mL) containing triethylamine (0.015 mL,
0.109 mmol) for 17 h. The resulting crude purple product was purified by
column chromatography on silica gel eluting with 20% ethyl acetate in
˜
(KBr): n=3481, 2878, 1650, 1533, 1485, 1429, 1395, 1264, 1222, 1162,
1112, 994, 965, 836, 773, 742, 714, 675, 640 cmÀ1; ESI MS: m/z: calcd for
C37H19BF12N6O5: 866.13; found: 889.10 [M+Na]+.
1
hexane. SubPc 2h was obtained as a purple solid (32 mg, 63%). H NMR
Subphthalocyanine 2d: SubPc 1 (85 mg, 0.053 mmol) and phenol 3d
(200 MHz, CDCl3): d=5.35–5.17 (m, 12H; OCH2 ꢁ6), 4.72–4.59 (m,
(25 mg, 0.265 mmol) were placed in a 20 mL round-bottomed flask and
12H; OCH2 ꢁ6), 2.35 (s, 1H; CH), 1.69–1.57 (m, 2H; CH2), 1.49–
7560
www.chemeurj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 7554 – 7562

Trifluoroethoxy Groups on Subphthalocyanine
FULL PAPER
1.43 ppm (m, 2H; CH2); 19F NMR (188 MHz, CDCl3): d=À74.11 (t, J=
8.1 Hz, 18F; CF3 ꢁ6), À74.77 ppm (t, J=8.1 Hz, 18F; CF3 ꢁ6); IR (KBr):
the solvent, the blue solid was purified by column chromatography on
silica gel, eluting first with CH2Cl2/MeOH (98:2) and then with hexane/
dioxane (3:1) to give TFEO-SubPc–tBuPc hybrid 10 as a blue solid
(34 mg, 56%). 19F NMR (188 MHz, [D6]acetone): d=À72.89 (br, 18F;
˜
n=3421, 3309, 2973, 1492, 1459, 1433, 1281, 1237, 1215, 1165, 1127, 1068,
1018, 969, 854, 834, 754, 732, 662 cmÀ1; MALDI-TOF MS: m/z: calcd for
C52H29BF36N6O13: 1640.13; found: 1638.57 (most abundant peak in the
isotopic envelope).
˜
CF3 ꢁ6), À73.61 ppm (t, J=8.0 Hz, 18F; CF3 ꢁ6); IR (KBr): n=3437,
2964, 1612, 1490, 1458, 1429, 1281, 1239, 1167, 1129, 1068, 1017, 969, 923,
833, 749, 661 cmÀ1; UV/Vis (CHCl3): lmax (loge)=686 (4.91), 598 (4.96),
550 (4.55), 382 (4.80), 334 (4.95), 300 (4.93), 277 nm (4.93); dioxane: lmax
(loge)=683 (5.30), 603 (4.99), 546 (4.45), 349 (5.06), 278 nm (4.88);
MALDI-TOF MS: m/z: calcd for C100H67BF36N14O13Zn: 2430.38; found:
2432.77 (most abundant peak in the isotopic envelope).
TFEO-subphthalocyanine–C60 dyad 8: A solution of SubPc 2 f (38 mg,
0.022 mmol), C60 fullerene (18 mg, 0.025 mmol), and sarcosine (N-meth-
ylglycine) (6 mg, 0.067 mmol) in dry toluene (15 mL) was heated under
reflux conditions for 7 h. The solution was then cooled to room tempera-
ture and concentrated under vacuum. The resulting crude mixture was
subjected to column chromatography on silica gel eluting with toluene/
hexane (4:1) to give SubPc–C60 dyad 8 as a blue solid (31 mg, 57%).
1H NMR (200 MHz, CDCl3): d=7.1–6.9 (m, 1H; Ar-H), 6.80 (t, J=
7.7 Hz, 1H; Ar-H), 5.94–5.66 (m, 1H; Ar-H), 5.34–5.08 (m, 13H; Ar-H,
OCH2 ꢁ6), 4.73 (brd, J=9.6 Hz, 1H; CH2-pyrr), 4.59 (q, J=8.0 Hz, 12H;
OCH2 ꢁ6), 4.42 (brs, 1H; CH-pyrr), 3.99 (brd, J=9.4 Hz, 1H; CH2-
pyrr), 2.54 ppm (s, 3H; CH3); 19F NMR (188 MHz, CDCl3): d=À74.03 (t,
J=7.9 Hz, 18F; CF3 ꢁ6), À74.68 ppm (t, J=8.1 Hz, 18F; CF3 ꢁ6);
13C NMR (150.9 MHz, CDCl3): d=156.2, 153.9, 153.2, 148.7, 146.5, 146.4,
146.2, 146.15, 146.1, 145.9, 145.7, 145.3, 145.2, 145.1, 145.0, 144.8, 144.6,
144.4, 144.3, 144.2, 144.1, 143.8, 143.7, 143.6, 143.3, 142.2, 142.0, 141.65,
141.6, 141.5, 141.4, 141.3, 141.1, 141.0, 140.9, 140.5, 139.2, 139.0, 138.8,
138.5, 136.2, 136.1, 135.4, 135.3, 126.5, 125.9, 124.7, 124.1, 122.8, 122.2,
121.0, 120.4, 120.2, 71.9, 71.7, 71.6, 71.4, 71.3, 71.2, 71.1, 70.9, 69.6, 68.9,
39.4 ppm; IR (KBr): n˜ =3435, 2961, 1604, 1491, 1428, 1281, 1238, 1215,
1166, 1127, 1067, 1020, 970, 855, 662 cmÀ1; UV/Vis (CHCl3): lmax (loge)=
598 (4.95), 549 (4.51), 429 (3.62), 326 (4.87), 257 nm (5.35); PhCF3: lmax
(loge)=597 (4.93), 549 (4.50), 429 (3.61), 326 nm (4.86); dioxane: lmax
(loge)=599 (4.94), 546 (4.50), 430 (3.61), 327 (4.86), 255 nm (5.28);
MALDI-TOF MS: m/z: calcd for C117H34BF36N7O13: 2439.17; found:
2437.20 (most abundant peak in the isotopic envelope).
Acknowledgements
This study was financially supported in part by Grants-in-Aid for Scien-
tific Research (B) no. 21390030 (JSPS) and by the Research Foundation
for Electrotechnology of Chubu (REFEC).
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TFEO-subphthalocyanine–phthalocyanine hybrid 9: A 30 mL round-bot-
tomed flask was charged with SubPc 2e (35 mg, 0.0195 mmol), 23-ethyn-
yl-1,2,3,4,8,9,10,11,15,16,17,18-dodecakis(2,2,2-trifluoroethoxy)phthalo-
cyaninate zinc(II) 11[9b] (43.5 mg, 0.024 mmol), [PdCl
2ACHTNUTRGNE(UGN PPh3)2] (2 mg,
0.0028 mmol), and CuI (0.5 mg, 0.0026 mmol). Dry tetrahydrofuran
(2.5 mL) and dry triethylamine (0.5 mL) were then added under an argon
atmosphere, and the mixture was stirred for 9 h at room temperature and
then concentrated under vacuum. Water was added to the residual crude
mixture, and the resulting mixture was extracted with CH2Cl2. The com-
bined organic layers were washed with brine and dried over Na2SO4.
After removal of the solvent, the crude solid was purified by column
chromatography on silica gel, eluting first with CH2Cl2/MeOH (50:1) and
then with hexane/dioxane (7:3) to afford SubPc–Pc hybrid 9 as a green-
ish-blue solid (47 mg, 70%). 1H NMR (200 MHz, [D6]acetone): d=9.02
(br, 2H; Ar-H), 8.12 (br, 1H; Ar-H), 7.30 (d, J=8.4 Hz, 2H; Ar-H), 5.76
(d, J=8.4 Hz, 2H; Ar-H), 5.65 (q, J=8.4 Hz, 16H; OCH2 ꢁ8), 5.28–5.11
(m, 16H; OCH2 ꢁ8), 5.03–4.85 ppm (m, 16H; OCH2 ꢁ8); 19F NMR
(188 MHz, [D6]acetone) d=À72.57 to À73.20 (m, 36F; CF3 ꢁ12),
À73.65 ppm (m, 36F; CF3 ꢁ12); IR (KBr): n˜ =3436, 2972, 1602, 1488,
1456, 1431, 1278, 1240, 1162, 1068, 1014, 969, 853, 833, 753, 662 cmÀ1
;
UV/Vis (CHCl3): lmax (loge)=761 (5.22), 720 (4.96), 598 (4.80), 322
(4.91), 275 nm (4.88); PhCF3: lmax (loge)=702 (5.38), 631 (4.68), 596
(4.78), 351 nm (4.93); dioxane: lmax (loge)=704 (5.40), 633 (4.70), 599
(4.79), 355 (4.95), 275 nm (4.83); MALDI-TOF MS: m/z: calcd for
C
112H55BF72N14O25Zn: 3438.17; found: 3441.01 (most abundant peak in
the isotopic envelope).
TFEO-subphthalocyanine–tBu-phthalocyanine hybrid 10:
A
30 mL
round-bottomed flask was charged with SubPc 2e (45 mg, 0.025 mmol),
23-ethynyl-2(3),9(10),16(17)-tri-tert-butylphthalocyaninate zinc(II) 12[24]
(24 mg, 0.031 mmol), [PdCl2ACHTNUTRGNE(UNG PPh3)2] (2 mg, 0.0028 mmol), and CuI
(0.5 mg, 0.0026 mmol). Dry tetrahydrofuran (2.5 mL) and dry triethyl-
amine (0.5 mL) were then added under an argon atmosphere, and the
mixture was stirred for 9 h at room temperature and then concentrated
under vacuum. Water was added to the residual crude mixture, and the
resulting mixture was extracted with CH2Cl2. The combined organic
layers were washed with brine and dried over Na2SO4. After removal of
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Received: February 11, 2010
Published online: May 18, 2010
7562
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Chem. Eur. J. 2010, 16, 7554 – 7562