Synthesis of a meso-Tetraalkylporphycene Bearing Reactive Sites: Toward Porphycene–Polydimethylsiloxane Hybrids with Enhanced Photophysical Properties

Article abstract of DOI:10.1002/ejoc.201901497

meso-Tetraalkyl porphycenes exhibit unique optical properties with wide potential applications. The very fact that incorporation of porphycenes into polymeric materials is rare, make this approach a particularly attractive one. In this work, meso-tetrakis

Full text of DOI:10.1002/ejoc.201901497

A Journal of
Accepted Article
Title: Synthesis of a meso-tetraalkylporphycene bearing reactive sites:
Toward porphycene–polydimethylsiloxane hybrids with enhanced
photophysical properties
Authors: Toshikazu Ono, Hyuga Shinjo, Daiki Koga, and Yoshio
Hisaeda
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201901497
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10.1002/ejoc.201901497
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Synthesis of a meso-tetraalkylporphycene bearing reactive sites:
Toward porphycene–polydimethylsiloxane hybrids with enhanced
photophysical properties
Toshikazu Ono,*[a,b] Hyuga Shinjo,[a] Daiki Koga,[a] and Yoshio Hisaeda*[a,b]
Abstract: Meso-tetraalkyl porphycenes exhibit unique optical
properties with wide potential applications. The very fact that
incorporation of porphycenes into polymeric materials is rare, make
this approach a particularly attractive one. In this work, meso-
tetrakis(3-butenyl)porphycene bearing four terminal olefin groups is
prepared via two synthetic strategies: 1) the McMurry reaction using
5,5′-diacyl-2,2′-bipyrroles as precursors and 2) the oxidative coupling
of dipyrroethenes. The newly obtained porphycene has been
as precursors (Method A)[1] and the oxidative macrocyclization of
dipyrroethenes (Method B).[3-7]
Because of their unique optical properties, porphycene
derivatives have been investigated as potential photosensitizers
for photodynamic therapy,[8] as artificial heme components, as
[9-12]
catalysts,
as near-infrared absorption dyes,[13-15] as
tautomerization,[16,
and as various functional materials.[18-21]
17]
From the viewpoint of synthetic chemistry, porphycenes can be
modified with substituents at the β- and meso-positions,[22-29]
thereby introducing differences that affect their solubilities,
electronic states, metal coordinating abilities, and intramolecular
hydrogen bonding behaviors. Thus, β-substituted porphycenes
have a square-shaped N4-coordination core, whereas the N4-
coordination core of meso-substituted porphycenes tends to be
more rectangular.[23, 30]
Among porphycenes, the meso-tetraalkyl derivatives exhibit
unusual photoluminescence quenching behavior due to the
formation of strong intramolecular hydrogen bonds in the N4 core
in the framework.[31, 32] In 2010, Waluk and coworkers reported
characterized by single X-ray crystallography.
A porphycene–
polydimethylsiloxane hybrid film is successfully prepared by platinum-
catalyzed hydrosilylation reaction. The hybrid film can be anchored
with tweezers, showing a weak red emission with a quantum yield of
0.4% at room temperature, whose intensity drastically increases
reaching a quantum yield of 6.7% in liquid nitrogen (77 K). This report
represents the first example of porphycene-containing elastomeric
films for potential application in various fields.
Introduction
that
the
photoluminescence
properties
of
meso-
tetraalkylsubstituted porphycenes were influenced by external
environmental stimuli, and their emission properties were
enhanced when embedded in highly viscous fluids or in a polymer
matrix.[31] For example, the fluorescence quantum yields of meso-
tetrapropyl porphycene (TPPc) at 293 K are 0.054% and 0.35%
in n-hexane and DMSO, respectively. The fluorescence lifetimes
at 293 K are 27 ps and 4.4 ns in THF and PMMA as host matrix,
respectively. Moreover, the emission properties were enhanced
at low temperature.[33] These behaviors stem from the
deactivation of the excited state of porphycene induced by
tautomerization, which is suppressed in highly viscous
environments and low temperature.
Porphycenes, which were first prepared by Vogel in 1986, are
constitutional isomers of porphyrins having two direct bonds
between neighboring pyrroles and two ethenyl bridges.[1]
Approaches toward porphycene frameworks are roughly divided
into two strategies (Scheme 1),[2] i.e., the standard method based
on McMurry reductive cyclization of two 5,5′-diacyl-2,2′-bipyrroles
B
NH
R
R
R
R
A
N
H
N
B
A
R
R
R
R
N
N
H
N
H
H
H
N
O
O
N
reactive
site
R= aryl, alkyl
(a)
(b)
Scheme 1. Retrosynthetic analysis of porphycenes.
N
H
N
N
H
N
N
H
N
N
N
H
H
N
H
N
N
N
[a]
Dr. T. Ono, Mr. H. Shinjo, Mr. D. Koga, Prof. Y. Hisaeda
Department of Chemistry and Biochemistry, Graduate School of
Engineering, Kyushu University
744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
E-mail: tono@mail.cstm.kyushu-u.ac.jp
TMPc
1
F1
Figure 1. (a) Chemical structures of tetramethylporphycene (TMPc) and 1
E-mail: yhisatcm@mail.cstm.kyushu-u.ac.jp
Dr. T. Ono, Prof. Y. Hisaeda
Center for Molecular Systems (CMS), Kyushu University
744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
(This work). (b) Schematic illustration of
a
porphycene–
[b]
polydimethylsiloxane hybrid (F1).
However, the abovementioned hybrids consisting of meso-
tetraalkylsubstituted porphycenes embedded in a polymer matrix
are noncovalently bonded dispersions. This prompted us to
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejoc.201901497
European Journal of Organic Chemistry
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Et2NH
EDCl•HCl
DMAP
pyrrole
POCl3
O
Zn
TiCl4
O
O
NH
NH
H
N
N
OH CH2Cl2
THF
CH3CN
3 (97%)
5 (67%)
6 (12%)
2,2’-bipyrrole (2)
CH3CN
CH2Cl2
PIFA
POCl3
H
H
N
H
PIFA
TMSBr
Zn, CuCl
TiCl4
N
N
N
N
H
H
N
CH2Cl2
THF
N
N
N
2 (74%)
H
H
O
O
4 (96 %)
1
(3.7% by 4)
(1.0% by 6)
Figure 2. Synthesis of 1 by Method A (red arrow) and Method B (blue arrow).
investigate whether the interesting photoluminescence properties
of meso-tetraalkylsubstituted porphycenes would be attained by
fixing them to the polymer matrix. To accomplish this, we
designed meso-tetrakis(3-butenyl)porphycene (1), in which the
meso-alkyl moieties were modified with terminal olefins (Figure 1).
We selected the olefin group as reactive site because terminal
olefins are known to react with the Si–H bonds of
polydimethylsiloxanes by hydrosilylation reaction in the presence
of a platinum catalyst. In this study, we demonstrate the synthesis
of 1 by two strategies, i.e., Method A and Method B (Figure 2).
Then, we describe the preparation of porphycene–
polydimethylsiloxane (PDMS) hybrids using the Pt-catalyzed
hydrosilylation reaction, and the photoluminescence properties of
the hybrids are investigated (Figure 4). The novelty of this work
can be summarized as follows: a) so far, there is no study
comparing these two synthetic strategies (Methods A and B) for
the preparation of porphycene derivatives; and b) the
incorporation of porphycene derivatives into polymeric materials
is still rare, with the existing examples being restricted to
porphycene–DNA[34], porphycene–protein[35], and porphycene–
nanoparticle conjugates.[35]
Results and Discussion
As shown in Figure 2, we prepared compound 1 by two synthetic
approaches. Method A is based on the McMurry reaction of
compound 4, and Method
B consists of the oxidative
macrocyclization of compound 6. Method A was performed as
follows. According to previously reported procedures, 2,2′-
bipyrrole (2) was obtained in a yield of 74% by oxidative coupling
of pyrrole using [bis(trifluoroacetoxy)iodo]benzene (PIFA) and
trimethylsilyl bromide (TMSBr) in dry CH2Cl2.[36] Compound 3 was
subsequently obtained in 97% yield by condensation of 4-
pentenoic acid and diethylamine (Et2NH) in the presence of 1-(3-
dimethylaminopropyl)-3-ethylcarbodiimide
hydrochloride
(EDC·HCl) and 4-dimethylaminopyridine (DMAP) in dry CH2Cl2.
Then, compound 4 was obtained in a yield of 96% using the
Vilsmeier–Haack reaction of 2 and 3 in the presence of POCl3 in
dry CH3CN. Finally, compound 1 was successfully obtained in
3.7% yield by the conventional McMurry reaction of 4. Meanwhile,
the synthesis of 1 by Method B was carried out as described as
follows: Compound 5 was obtained in 67% yield via the Vilsmeier–
Haack reaction of 3 and pyrrole in the presence of POCl3 in dry
CH3CN.[23] Then, compound 6 was obtained in 12% yield by
subjecting 5 to the McMurry reaction. Finally, compound 1 was
obtained in a yield of 1.0% by oxidative coupling of 6 using PIFA
in CH2Cl2.
The total yields of 1 were 2.5% with Method A and 0.08%
using Method B, in both cases starting from commercially
available reagents. The relatively new synthetic Method B
requires the crucial isolation of Z-dialkyldipyrroethene (6) from the
E/Z-mixture after the McMurry coupling of compound 5, which
results in low yields. We recently found that it is possible to
synthesize meso-tetraarylporphycenes using a E/Z-mixture of
diaryldipyrroethene with p-TSA as an acid catalyst;[6] however,
Figure 3. Crystal structure of 1 at 123 K. Hydrogen atoms are
omitted for clarity. The thermal ellipsoid is drawn at 30% probability.
Color code: N, light blue; C, gray; disordered C, red. Selected bond
distances (Å): N1–N2, 2.899(4); N2–N3, 2.542(4); N3–N4, 2.909(4);
N1–N4, 2.550(4); C9–C21, 1.526(5); C21–C22, 1.528(5); C22–C23,
1.481(6); C23–C24, 1.222(6); C19–C29, 1.537(5); C29–C30,
1.552(5); C30–C31, 1.503(6); C31–C32, 1.293(7).
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Si-H
(a)
Si-H
Si-H
H-Si
H-Si
H-Si
N
H
N
N
P1
N
H
N
N
N
N
H
H
Pt catalyst
Toluene
N
H
N
N
N
1-P1
1
H
Si-H
Si-H
Pt catalyst
Toluene
Si-H
P2
Si-H
Pt catalyst
Toluene
F1
7
7-P1
(b)
O
CH3 CH3
CH3
CH3
H
CH3
CH3
H
Si O Si O Si
H
H3C Si O Si
CH3 CH3
O
Si
O
Si CH3
CH3
n
≡
O
O
CH3 CH3
CH3
CH3
l
m
7
P1
P2
Figure 4. (a) Schematic representation of the preparation of F1 film. The inset shows a photograph of F1. (b) Chemical structures of P1, P2, and 7.
this approach was not applicable in the case of meso-
tetraalkylporphycene derivatives.[5] Therefore, Method A is more
appropriate for the synthesis of the target compound 1. New
compounds 1 and 3–6 were characterized using 1H NMR, 13C
NMR, and HI-MS (Figures S2–S11). The stretching vibration of
the terminal olefin groups of 1 was observed at 1638 cm−1 in the
IR spectrum (Figure S12). Compound 1 was also subjected to X-
ray analysis, and the corresponding single-crystal structure is
depicted in Figure 3. As can be seen, the four nitrogen atoms are
distributed in a near rectangular fashion with N1•••N2 and
N3•••N4 distances of 2.899(4) and 2.909(4) Å and N1•••N4 and
N2•••N3 distances of 2.550(4) and 2.542(4) Å, respectively. The
packing modes of the butenyl chain of 1 are disordered at 10- and
20-position and ordered at 9- and 19-position in the crystal
structure. The C31•••C32 and C23•••C24 distances are 1.293(7)
and 1.222(6) Å, respectively. Figure S13 displays the UV–vis
absorption spectrum of 1, which exhibits similar properties to
those of tetramethylporphycene (TMPc).[5] Thus, 1 showed
extremely weak photoluminescence behavior with a quantum
yield of 0.18%, 0.08%, 0.13%, and 0.33% in THF, CH3CN, hexane,
and DMSO, respectively (Table S2). These values are similar to
those of TMPc and TPPc in the corresponding solutions.[31]
Next, a hybrid material of compound 1 and PDMS was
prepared according to a published method.[37] We chose PDMS
as polymeric matrix because its transparency facilitates the
evaluation of the optical properties of incorporated 1. Compound
1 was readily introduced into the PDMS networks through
hydrosilylation of its four terminal olefin moieties. As can be seen
in Figure 4, P1 is a hydride-terminated polydimethylsiloxane (Mn,
6000; d, 0.97; viscosity, 100 cSt; n, 1.403), and P2 is a copolymer
Figure 5. (a) Diffuse reflectance spectra of F1–F3. (b) Emission spectra of
F1 at r.t. and 77 K. Excitation at 380 nm. (c) Emission decay curves of F1
at r.t. and 77 K.
of dimethylsiloxane and methylhydrosiloxane (Mn, 1900–2000;
methylhydrosiloxane, 15–18 mol%; d, 0.97; viscosity, 25–35 cSt;
n, 1.400). First, an excess amount of P1 (350 mg, 140 µmol of
SiH units) was reacted with 1 (66 nmol) in the presence of
Karstedt's catalyst (6.5 µL) in toluene (750 µL) under N2
atmosphere, and the solution was stirred for 1 h at room
temperature. Then, a mixture of P2 (21 mg, 40 µmol of SiH units),
a 0.16 M toluene solution of 6 (500 µL), and Karstedt's catalyst
(5.0 µL) was added to the reaction mixture. The resultant mixture
was stirred several seconds and transferred onto a Teflon
substrate (20 mm ×40 mm), and an elastomeric film (F1) was
obtained by a crosslinking hydrosilylation reaction under gradual
evaporation of toluene at room temperature overnight. For
comparative purposes, a film without reactive sites (F2) prepared
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Materials and chemicals. A hydride-terminated polydimethylsiloxane P1
and a copolymer of dimethylsiloxane P2 were purchased from GELEST,
Inc. Platinum (0)-(1,1,3,3-tetramethyl-1,3-divinyldisiloxane) complex in
xylene (Karstedt’s catalyst) was purchased from Sigma-Aldrich. All other
reagents and solvents were purchased from TCI, Sigma-Aldrich, Kanto
Chemical or FUJIFILM Wako Chemicals and used as received. TMPc was
prepared according to the established method.[5]
under the same conditions using TMPc in place of 1 and a film
(F3) obtained in the absence of porphycene were also examined.
The obtained films (F1–F3) were ca. 20 mm long, 10 mm wide,
and 1 mm thick and were anchored with tweezers. Figure S14
shows the photographs of the prepolymer toluene solution and
the obtained films (F1–F3). Under the synthetic condition of F1,
the blue–green color derived from porphycene was maintained
before and after the film formation. On the other hand, under the
synthetic condition of F2, the blue–green prepolymer solution
became brown after the film formation. The films F1 and F2 were
immersed in toluene overnight to confirm that the porphycene was
covalently immobilized in the polymer matrix (Figure S15). No
dissolution of porphycene was observed in F1, whereas
dissolution of porphycene occurred in F2. It can be concluded that
1 was covalently immobilized in the PDMS polymer matrix in F1.
On the other hand, TMPc was not hybridized with PDMS and
aggregated in the PDMS polymer matrix due to their low
compatibility.
Characterization. 1H NMR and 13C NMR spectra were recorded by using
Bruker Avance 500 NMR spectrometer. Chemical Shifts were referenced
against tetramethylsilane or the residual solvent peak as an internal
standard. UV-vis diffuse reflectance measurements were recorded using
a JASCO V-670 spectrometer (JASCO) with an integration sphere
attachment. The HRMS (FAB-MS) were performed with a JEOL JMS-700
instrument. IR spectra were recorded from dry powder spread over KBr
pellets and by using a JASCO FT/IT-460 plus instrument. UV/Vis
absorption spectra were recorded by using
spectrophotometer. Fluorescence excitation and emission spectra were
collected at room temperature on Hitachi F-7000 fluorescence
spectrometer. The absolute photoluminescence quantum yields (ΦPL
a
Hitachi U-3310
a
)
were determined using absolute PL quantum yields measurement system
C9920-02 or C13534-23 (Hamamatsu photonics). Time-resolved
photoluminescence lifetimes were carried out by using time-correlated
single photon counting lifetime spectroscopy system, Quantaurus-Tau
C11367-02 (Hamamatsu photonics). The decay constants and fitting
parameters for transient decays were determined using the embedded
software of Quantaurus-Tau.
Figure 5 shows the optical properties of the F1–F3 films.
The UV–vis diffuse reflectance spectra of the films were obtained
using an integrating sphere. The typical Soret band and Q band
of porphycene were observed in the spectrum of F1, which was
similar to that of 1 in solution. This indicates that 1 was
homogeneously dispersed in the elastomeric PDMS film matrix.
The emission spectrum of F1 excited at 380 nm showed a red
emission at a lmax of 670 nm. The quantum yield and the average
lifetime at room temperature were 0.4% and 1.2 ns, respectively
(Table 5(c) and Table S3). Interestingly, the emission spectrum of
F1 in liquid nitrogen (77 K) showed a drastic increase of emission
intensity. In this condition, the quantum yield and the average
lifetime were 6.7% and 9.4 ns, respectively. These results
suggest that the hybridization of meso-tetraalkylporphycene 1
with the PDMS matrix suppressed the tautomerization-induced
excited state quenching of porphycene. Meanwhile, the diffuse
reflectance spectrum of F2 was similar to that of F3, showing the
lack of a visible absorption derived from porphycene.
X-ray crystal structural analysis. The crystal (1) was mounted on a loop.
Data from X-ray diffraction were collected under 123 by a Rigaku XtaLAB
mini CCD diffractometer equipped with graphite monochromated Mo-
Ka radiation (l = 0.71073 Å). Collected data were integrated, corrected,
and scaled using the program CrysAlisPro.[38] The structures were refined
using SHELXT (Sheldrick, 2015)[39] Intrinsic Phasing and SHELXL
(Sheldrick, 2015).[40] All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were located at calculated positions and included in the
structure factor calculation but were not refined. The program Olex2 was
used as a graphical interface.[41] The crystallographic data of 1 is listed in
Tables S1, and their CCDC number is 1944912, respectively. The data
have been deposited with the Cambridge Crystallographic Data Centre.
The data can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB21EZ, UK (fax: (+44) 1223-336-033; email:
deposit@ccdc.cam.ac.uk).
Conclusions
Synthesis of N,N-diethyl-4-pentenamide (3). 4-Pentenoic acid (3.0 mL,
30 mmol) and diethylamine (3.6 mL, 36 mmol) were added to a two-necked
flask containing EDCI•HCl (6.9 g, 36 mmol), DMAP (4.5 g, 36 mmol) and
dry dichloromethane (150 mL) under N2. The solution was stirred for 22 h
at room temperature. The reaction was quenched with 10% aqueous citric
acid. The mixture was extracted three times with dichloromethane. The
organic layer was dried over Na2SO4. The solvents were removed under
reduced pressure, the crude product was purified using silica-gel column
chromatography (hexane/AcOEt = 2/1) to yield 3 as colorless oil (4.5 g,
97%).1H NMR (500 MHz, CDCl3): δ = 5.96-5.83 (m, 1H), 5.08 (d, J = 17.0
Hz, 1H), 5.00 (d, J = 10.1 Hz, 1H), 3.39 (q, J = 7.2 Hz, 2H), 3.32 (q, J = 7.0
Hz, 2H), 2.46-2.36 (m, 4H), 1.17 (t, J = 7.1 Hz, 3H), 1.11 (t, J = 7.0 Hz, 3H).
13C NMR (125 MHz, CDCl3): δ = 171.0, 137.5, 114.7, 41.7, 39.8, 32.2, 29.2,
14.1, 12.8. HRMS (FAB, positive): m/z calcd (%) for C9H18NO [M+H]+
156.1388; found for 156.1370.
In conclusion, we have demonstrated the synthesis of a meso-
tetraalkylporphycene
1 bearing terminal olefin moieties as
reactive sites following two synthetic strategies, and we found that
the desired product could be successfully synthesized by both
methods. A PDMS hybrid material was successfully prepared via
the platinum-catalyzed hydrosilylation reaction between the olefin
groups of the porphycene and the Si–H bonds of
polydimethylsiloxane. An increase in photoluminescence intensity
and lifetime of the meso-tetraalkylporphycene was observed in
the film owing to the suppression of excited state deactivation.
These results pave the way for the development of hybrid
materials with potential applications as optical materials and solid-
state catalysts via the post-modification of porphycene derivatives.
Synthesis of 5,5’-bis(4-pentenoyl)-2,2’-bipyrrole (4). POCl3 (1.96 mL,
21.0 mmol) was added dropwise to a two-necked flask containing 3 (1.09
g, 7.00 mmol) at 0 ᴼC under N2. The solution was stirred for 10 min at 0
ᴼC. Dry acetonitrile (4.67 mL) and 2 (308 mg, 2.33 mmol) were added into
Experimental Section
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10.1002/ejoc.201901497
European Journal of Organic Chemistry
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the reaction solution and then the mixture was refluxed for 8 h. The
reaction was quenched with saturated aqueous NaHCO3. The mixture was
stirred at 90 ᴼC for 1 h. The precipitate was washed with water and dried
under vacuum to yield 4 as a yellow solid (663 mg, 96%); m.p.: 258-260
ᴼC. 1H NMR (500 MHz, DMSO-d6): δ = 12.02 (brs, 2H), 7.07 (m, 2H), 6.75
(m, 2H), 5.91-5.82 (m, 2H), 5.08 (d, J = 17.0 Hz, 2H), 4.98 (d, J = 10.1 Hz,
2H), 2.85 (t, J = 7.4 Hz, 4H), 2.36 (m, 4H). 13C NMR (125 MHz, DMSO-d6):
δ = 188.4, 137.6, 132.0, 130.2, 117.7, 115.1, 108.9, 36.2, 28.5. HRMS
(FAB, positive): m/z calcd (%) for C18H20N2O2 [M]+ 296.1525; found for
296.1528.
Synthesis of 9,10,19-20-tetrabutenyl porphycene (1) (Method B). PIFA
(159 mg, 0.37 mmol) in dry dichloromethane (15 mL) was quickly added
to a stirred solution of 6 (98 mg, 0.37 mmol) in dry dichloromethane (37
mL) in an ice bath. The solution was stirred for 1.5 h and the reaction was
quenched with silica gel 60N (37 mL) and methanol (37 mL). The mixture
was dried carefully under reduced pressure. The resultant silica-gel
mixture was charged on fresh silica gel 60N and eluted with
dichloromethane to give a purple solid. Silica-gel column chromatography
(dichloromethane 100%), and then washed with methanol in solid state to
yield 1 as a purple solid (1.0 mg, 1.0%).
Synthesis of 9,10,19-20-tetrabutenyl porphycene (1) (Method A). TiCl4
(9.5 g, 50 mmol) was added dropwise to dry THF (200 mL) suspension of
activated Zn powder (6.54 g, 100 mmol) and CuCl (396 mg, 4.00 mmol) at
0 ºC under N2. The reaction mixture was refluxed for 3 h and then 4 (593
mg, 2.00 mmol) in THF (200 mL) was added dropwise over 2.5 h at room
temperature. The solution was refluxed for 16 h. The reaction was
quenched with 10% aqueous K2CO3 (200 mL). The mixture was extracted
three times with dichloromethane; the organic layer was washed twice with
water and dried over anhydrous Na2SO4. The solvents were removed
under reduced pressure and the crude product was purified using silica-
gel column chromatography (dichloromethane/hexane = 1/4), and then
washed with methanol in solid state to yield 1 as a purple solid (19.2 mg,
3.7%); m.p.: 240-242 ᴼC. 1H NMR (500 MHz, CDCl3): δ = 9.47 (d, J = 4.4
Hz, 4H), 9.22 (d, J = 4.7 Hz, 4H), 6.82 (brs, 2H), 6.42-6.23 (m, 4H), 5.44
(d, J = 17.1 Hz, 4H), 5.26 (d, J = 10.1 Hz, 4H), 4.65–4.46 (m, 8H), 3.20–
3.07 (m, 8H). 13C NMR (125 MHz, CDCl3): δ = 146.4, 138.2, 134.5, 128.8,
127.8, 125.8, 115.2, 40.7, 35.7. HRMS (FAB, positive): m/z calcd for
C36H38N4 [M]+ 526.3096; found for 526.3097. UV/Vis (CH2Cl2): λmax (log ε,
L mol–1 cm–1) = 378 (5.17), 595 (3.19), 662 (4.60) nm.
Synthesis of 1,3,5-tris(5-hexenyloxyl)benzene (7). A mixture of
phloroglucinol (472 mg, 3.74 mmol) and potassium carbonate (6.20 g, 44.9
mmol) in dry N,N-dimethylformamide (15 mL) was stirred at 70 ºC for 2 h,
then, 6-bromo-1-hexene (2.00 mL, 15.0 mmol) was added. The reaction
mixture was stirred at 70 ºC for further 6 h. After cooling to room
temperature, the reaction mixture was diluted in ether, washed with water,
and the organic layer was dried over anhydrous Na2SO4. The solvents
were removed under reduced pressure and the crude product was purified
using silica-gel column chromatography (hexane/chloroform = 7/3) to yield
7 as a colorless oil (628 mg, 45%). The spectral data were identical with
the reported data.[37]
Synthesis of Film 1. Karstedt’s catalyst (6.5 µL) and toluene (750 µL)
were added to a two-necked flask containing 1 (65.8 nmol) and P1 (350
mg, 140 µmol of SiH units) under N2. The solution was stirred for 1 h at
room temperature. A mixture of P2 (21 mg, 40 µmol of SiH units), a toluene
solution containing 6 of 0.16 M (500 µL) and Karstedt’s catalyst (5.0 µL)
was added to the reaction mixture. The mixture was stirred by pipetting
and the resultant solution was transferred onto a Teflon substrate (20 mm
× 40 mm) and the solvent was evaporated overnight under ambient
conditions to give Film 1.
Synthesis of 2-(4-penten-1-one)pyrrole (5). POCl3 (932 µL, 10 mmol)
was added dropwise to a two-necked flask containing 3 (1.55 g, 10.0
mmol), at 0 ºC under N2. The solution was stirred for 15 min at 0 ºC. Dry
acetonitrile (3.6 mL) and pyrrole (694 mL, 10.0 mmol) were added and
then the mixture was refluxed for 40 min. The solution was diluted with
sodium acetate (4.18 g) in water (8.8 mL) and was refluxed for 30 min. The
mixture was extracted three times with ethyl acetate; the organic layer was
washed three times with water, and dried over anhydrous Na2SO4. The
solvents were removed under reduced pressure and the crude product
was purified using silica-gel column chromatography (dichloromethane
100%) to yield 5 as a white solid (1.10 g, 74%); m.p.: 32-34 ᴼC. 1H NMR
(500 MHz, CDCl3): δ = 9.35 (brs, 1H), 7.02 (m, 1H), 6.92 (m, 1H), 6.28 (m,
1H), 5.96-5.83 (m, 1H), 5.10 (d, J = 17.0 Hz, 1H), 5.01 (d, J = 10.1 Hz, 1H),
2.87 (t, J = 7.6 Hz, 2H), 2.55-2.45 (m, 2H). 13C NMR (125 MHz, CDCl3): δ
= 190.2, 137.3, 131.8, 125.0, 116.5, 115.1, 110.4, 37.0, 28.9. HRMS (FAB,
positive): m/z calcd (%) for C9H12NO [M+H]+ 150.0919; found for 150.0879.
Synthesis of Film 2. Karstedt’s catalyst (6.5 µL) and toluene (750 µL)
were added to a two-necked flask containing TMPc (65.8 nmol) and P1
(350 mg, 140 µmol of SiH units) under N2. The solution was stirred for 1 h
at room temperature. A mixture of P2 (21 mg, 40 µmol of SiH units), a
toluene solution containing 6 of 0.16 M (500 µL) and Karstedt’s catalyst
(5.0 µL) was added to the reaction mixture. The mixture was stirred by
pipetting and the resultant solution was transferred onto a Teflon substrate
(20 mm × 40 mm) and the solvent was evaporated overnight under
ambient conditions to give Film 2.
Synthesis of Film 3. Karstedt’s catalyst (6.5 µL) and toluene (750 µL)
were added to a two-necked flask containing P1 (350 mg, 140 µmol of SiH
units) under N2. The solution was stirred for 1 h at room temperature. A
mixture of P2 (21 mg, 40 µmol of SiH units), a toluene solution containing
6 of 0.16 M (500 µL) and Karstedt’s catalyst (5.0 µL) was added to the
reaction mixture. The mixture was stirred by pipetting and the resultant
solution was transferred onto a Teflon substrate (20 mm × 40 mm) and the
solvent was evaporated overnight under ambient conditions to give Film
3.
Synthesis of (Z)-bis(3butenyl)dipyrroethene (6). TiCl4 (2.79 g,
20.0mmol) was added dropwise to dry THF (40 mL) suspension of
activated Zn powder (2.62 g, 40.0 mmol), at 0 ºC under N2. The reaction
mixture was refluxed for 3 h and then 5 (746 mg, 5.00 mmol) in THF (10
mL) was added dropwise. The solution was refluxed for 5 h. The reaction
was quenched with 1 M aqueous NaHCO3 solution. The mixture was
extracted with diethyl ether; the organic layer was washed with brine and
dried over anhydrous Na2SO4. The solvents were removed under reduced
pressure and the crude product was purified using silica-gel column
chromatography (dichloromethane/hexane = 1/2) to yield 6 as a flesh-
colored oil (79 mg, 12%). 1H NMR (500 MHz, CDCl3): δ = 7.67 (brs, 2H),
6.58 (m, 2H), 6.17 (m, 4H), 5.91-5.80 (m, 2H), 5.04 (d, J = 17.0 Hz, 2H),
Acknowledgments
This work was supported JSPS KAKENHI Grant Numbers
JP17H04875, JP16H06514, and JP18H04265. This work was
also supported by Mazda Foundation, Izumi Science and
Technology Foundation, and Nissan Chemical Corporation.
4.98 (d, J = 10.1 Hz, 2H), 2.55 (t, J = 7.9 Hz, 4H), 2.24-2.15 (m, 4H). 13
C
NMR (125 MHz, CDCl3): δ = 138.3, 131.9, 127.5, 118.1, 114.7, 108.5,
107.9, 33.4, 33.0. HRMS (FAB, positive): m/z calcd for C18H22N2 [M]+
266.1783; found for 266.1782.
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10.1002/ejoc.201901497
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10.1002/ejoc.201901497
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Entry for the Table of Contents (Please choose one layout)
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Meso-tetrakis(3-butenyl)porphycene is
synthesized following two synthetic
Toshikazu Ono*, Hyuga Shinjo, Daiki
Koga, Yoshio Hisaeda*
strategies
hybridized with polydimethylsiloxane
by Pt-catalyzed hydrosilylation
and
is
successfully
Page No. – Page No.
Synthesis of a meso-
reaction. The hybrid film shows a weak
red emission with a quantum yield of
0.4% at room temperature, and the
emission intensity drastically increases
at 77 K, reaching a quantum yield of
6.7%.
tetraalkylporphycene bearing reactive
sites: Toward porphycene–
polydimethylsiloxane hybrids with
enhanced photophysical properties
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