Eosin Y dye-based porous organic polymers for highly efficient heterogeneous photocatalytic dehydrogenative coupling reaction

Article abstract of DOI:10.1039/c6ra25123d

Construction of porous organic polymers (POPs) as metal-free heterogeneous organic photocatalysts for highly efficient catalytic organic transformations using visible light remains a key challenge. Herein, we report the “bottom-up” strategy to facilely sy

Full text of DOI:10.1039/c6ra25123d

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Eosin Y Dye-based Porous Organic Polymers for Highly Efficient
Heterogeneous Photocatalytic Dehydrogenative Coupling
Reaction
Received 00th January 20xx,
Accepted 00th January 20xx
Chang-An Wang
*
, Yan-Wei Li, Xue-Li Cheng, Jian-Ping Zhang, and Yin-Feng Han
*
DOI: 10.1039/x0xx00000x
Construction of porous organic polymers (POPs) as metal-free heterogeneous organic photocatalysts for highly efficient
catalytic organic transformations using visible light remains a key challenge. Herein, we report the “bottom-up” strategy to
facilely synthesize two Eosin Y dye-based POPs frameworks (EY-POPs) for highly efficient heterogeneous organic-
photocatalysis. Owing to the high BET surface area and the built-in character of the covalently linked catalytic sites of EY-
POPs, these photoactive polymers shows excellent catalytic activity in photocatalyzing aza-Henry reaction. The superior
utility of EY-POP-1 polymer in catalysis was demonstrated by the broad scope of the reactants and the high yield of the
reaction products. Moreover, the EY-POP-1 polymer shows robust recycling capability with good retention of photoactivity
over at least twelve cycles without any significant loss of the catalytic activity (94-98% yield).
www.rsc.org/
based on these homogeneous photocatalysts7. The ability to
recover and reuse such heterogeneous photocatalysts can
both eliminate the contamination of organic products by trace
Introduction
Organic transformations driven by visible light offers a
sustainable alternative to many ever-pressing environmental
issue. In the aim to exploit photons for synthetic purposes,
visible-light photoredox catalysis has recently proven to be a
powerful method to perform several organic reactions1.
Because of the majority of organic substrates in these
reactions do not readily absorb photons in the visible region,
photocatalysts are often required in visible light driven organic
reactions. To date, transition-metal-systems, such as
ruthenium(II), mainly [Ru(bpy)3Cl2], or iridium(III) complexes
have been applied to photoredox reactions2 such as radical
addition and cycloaddition reactions3, aza-henry reactions4,
asymmetric alkylation of aldehydes5, and other reactions.
Recently, organic dyes have been also successfully applied as
effective visible light metal-free photoredox organocatalysts6.
However, like other precious homogeneous catalysis, these
homogeneous photocatalysts are generally considered of low
efficiency due to the high catalyst loading and the difficulty in
separation from the products, which restricts their practical
application in large scale. Furthermore, their potential toxicity
could lead to detrimental effects on public health and the
environment. Accordingly, it is highly desirable to develop
robust and reusable heterogeneous photocatalytic systems
amounts of heavy metals, and also reduce processing and
waste disposal costs in large scale reactions.
In recently, Porous organic polymers (POPs), such as
conjugated microporous polymers (CMPs)8, polymers of
intrinsic microporosity (PIMs)9, hyper-cross-linked polymers
(HCPs)10, and covalent organic frameworks (COFs)11, can be
construct from well-designed organic monomers, have
attracted significant scientific attention in the area of gas
storage/separation12,
organic
photoelectric13,
and
heterogeneous catalysis14. In particular, conjugated
microporous polymers (CMPs) can serve as an ideal platform
for incorporating photosensitive monomers into highly stable,
recyclable, and reusable heterogeneous photocatalyst systems
by taking advantage of their extended π-conjugation structure
and the ability to tune their compositions and properties at the
molecular level15. For example, Lin et al. reported the highly
stable and porous cross-linked polymers with phosphorescent
[Ru(bpy)3]2+ and [Ir(ppy)2(bpy)]+ building blocks for efficient
photocatalysis7a. Son et al. reported benzodifuran-based CMPs
via post modification, and the resulting polymer showed high
photocatalytic activity for the oxidative conversion of primary
amines into imines15d. Wang and Zhang et al. synthesized
conjugated polybenzodiazoles as organic heterogeneous
photocatalyst for visible-light-promoted H2 evolution15i, and
so on. Remarkable progress has been made in the
development of photosensitive monomers based CMPs
frameworks for efficient heterogeneous photocatalysis.
However, most of these photosensitive monomers either
require tedious experimental procedures to prepare or
College of Chemistry and Chemical Engineering, Taishan University, Tai’an,
Shandong 271021, P. R. China. E-mail: wangcha_chem@163.com.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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rigid structure
COONa
Br
Br
NaO
O
O
without any further synthetic
elaboration for functionalization
Eosin Y (organic photoredox catalyst)
Br
Br
easy for reacting with the structural building blocks
"Bottom-Up" Construction of Photoactive Porous Organic Polymers
COONa
O
Pd(PPh3)2Cl2/CuI
NaO
O
2
DMF/Et3N, N2, 80 oC, 72 h
EY-POP-1
COONa
Br
Br
NaO
O
O
Br
Br
1
COONa
O
Pd(PPh3)2Cl2/CuI
DMF/Et3N, N2, 80 oC, 72 h
NaO
O
EY-POP-2
3
Scheme 1. Design and synthesis of Eosin
Y
dye-embedded porous organic polymers
(
EY-POPs
)
via the bottom-up strategy.
expensive, that limit low-cost preparation of the polymers on a contribute to the construction of rigid POPs frameworks; 2)
large scale. In this context, the bottom-up construction of The bromine or iodine atoms on the benzene ring (without any
heterogeneous photocatalyst directly from the high activity further synthetic elaboration) could be easily reacted with the
and low cost monomers which without any further synthetic structural building blocks; 3) high effective photocatalytic
elaboration, may possibly overcome these drawbacks.
activity, low cost, and low toxicity. Herein, we report the
Organic dyes have been studied widely in the fields of dye- bottom-up construction of robust photoactive porous organic
sensitized solar cells16and homogeneous catalysis6. Eosin Y polymers (EY-POPs) embedded with Eosin Y dye for highly
(Scheme 1) and Rose Bengal, the most commonly used organic efficient heterogeneous photocatalytic dehydrogenative
dyes, are demonstrated to be effective noble metal-free coupling reaction (Scheme 1). Very recently, Jiang and Cooper
photo-organic-catalysts, and have been studied in the area of et al. reported conjugated microporous polymers with Rose
homogeneous photocatalysis due to their low cost and low Bengal dye as heterogeneous organic-photocatalyst for highly
toxicity6a-d. Eosin Y and Rose Bengal are the ideal candidates to efficient aza-Henry reaction15c. Unlike the significant work of
construct photoactive porous organic polymers, the main Jiang and Cooper et al., we synthesized two Eosin Y-
reasons lie in that: 1) The structural rigidity of the monomers functionalized POPs frameworks with different π-conjugation
are readily offered by the benzene ring, which could
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structure, and preliminary investigated the influence of the
extended π-conjugation structure on the catalytic activity.
Results and discussion
Design, Synthesis and Characterization of Eosin Y dye-based
Porous Organic Polymers (EY-POPs).
One of the key concerns for constructing functional POPs is the
rational design of the functional building blocks (FBBs). The
desired FBBs candidates should be rigid in structure, suitable in
size, easy to prepare, ready to react with the structural
building blocks. With these considerations in mind, we
accordingly select the skeleton of Eosin Y as the FBB candidate
to construct the photoactive porous organic polymers. As
illustrated in Scheme 1, the main reasons lie in that: 1) The
structural rigidity of organic photoredox catalyst is readily
offered by the benzene ring, which could contribute to the
construction of rigid POPs frameworks; 2) The bromine atoms
on the benzene ring could be easily reacted with the structural
building blocks; 3) Eosin Y is demonstrated to be effective
noble metal-free photo-organic-catalyst, together with low
cost and low toxicity. The polymer networks were easily
prepared through palladium-catalyzed Sonogashira-Hagihara
cross-coupling reaction of Eosin Y dye (EY) with different
structural building blocks (see the experimental section for
experimental details). Reaction of 1,3,5-triethynylbenzene (2)
with Eosin Y gave the polymer EY-POP-1 with extended π-
conjugation structure; and the equivalent reaction of tetra(4-
ethynylphenyl)methane (3) with Eosin Y gave the copolymer
EY-POP-2 with no extended π-conjugation structure. All the
constructed POPs networks are expected to be three-
dimensional with varied porosity due to the three-pronged
aryleneethynylene linkages and the rigid tetrahedral structure.
After the Sonogashira-Hagihara coupling reactions (see
Experimental Section), the desired Eosin Y-embedded POPs
networks were readily precipitated from the solution as red
colored solids, both of these polymers are insoluble in all
organic solvents tested due to their highly cross-linked
structures. The thermogravimetric analysis (TGA) revealed that
The EY-POPs networks were stable up to 350 oC under a
nitrogen atmosphere (Figure 1a). Power X-ray diffraction
measurements indicate that the EY-POPs networks are
amorphous in nature, as for other reported POPs networks in
our laboratory17. The UV-visible absorption spectra of EY-POPs
networks recorded for solid state powders demonstrates that
both polymers show broad absorption in the range from 250
to 600 nm (Figure 1b), which is similar to that of the Eosin Y
monomer, indicating that the EY-POPs networks can absorb
light across a wide range of the visible spectrum.
Figure 1. (a) Thermogravimetric analysis (TGA) curves for EY-POPs networks. (b)
UV-visible absorption spectra for the monomer of EY and the EY-POPs networks
as solid state powders. (c) FT-IR comparison of monomer 1 (in black), monomer 2
(in red), EY-POP-1 (in green), and EY-POP-2 (in blue). (d) SEM image for the EY-
POP-1 network.
Figure 2. Nitrogen adsorption/desorption isotherms of EY-POP-1 (a) and EY-POP-
2
(b). Pore size distribution (PSD) for EY-POP-1 (c) and EY-POP-2 (d), calculated
with non-local density functional theory (NLDFT).
Figure 3. Solid-state 13C CP/MAS NMR spectra for EY-POP-1 and EY-POP-2. The
assignments for the 13C MAS NMR signals are indicated (top).
The absence of the carbon-hydrogen stretching peak of the C
≡C-
H group around 3280 cm-1 in the IR spectra of the EY-
POPs suggested that most of the alkyne group in the starting
materials have been consumed to form groups in the
-C≡C-
POPs networks. The high degree of spectral similarity of EY-
POP-1 and EY-POP-2 also demonstrates the structural
consistency of these materials (Figure 1c). The SEM image of
EY-POPs displayed rather rough surfaces and the particles
were on the order of micrometer in size (Figure 1d).
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The permanent porosity of EY-POPs networks were Henry reaction, the reaction proceeded smoothly and gave the
investigated by nitrogen adsorption/desorption measurements desired product in moderate yield after 36 h (Table 1, entries 1
at 77 K, and the obtained results are listed in Table S1. As and 2). Strikingly, we found that the reaction proceeded much
shown in Figure 2(a) and 2(b), both of the EY-POPs networks faster by increasing the catalyst loading of EY-POPs polymers
showed similar adsorption and desorption isotherms, and gave (10 mg), giving the product in high yield after 24 h (Table 1,
rise to type I nitrogen gas sorption isotherms according to the entries 3 and 4). Amongst the EY-POPs polymers tested, the
IUPAC classification18. The adsorption shows a steep nitrogen EY-POP-1 polymer with the extended π-conjugation structure
gas uptake at low relative pressure, indicating that the showed the best reactivity, catalysing almost a complete
materials are microporous. The application of the Brunauer- conversion after 24 h with 10 mg catalyst (entry 3). A number
Emmett-Teller (BET) modal resulted in the surface areas of 587 of control experiments were carried out to demonstrate the
and 718 m2g-1 for EY-POP-1 (Figure S1, SI) and EY-POP-2 heterogeneous and photocatalytic nature of the reaction.
(Figure S2, SI), respectively. As calculated by non-local density Nature light gave low yield (35%) and there was no reaction in
functionaltheory (NLDFT), the pore size distribution (PSD) of the dark (Table 1, entries 5 and 6), indicating that light is
EY-POP-1 and EY-POP-2 mainly distributed around 0.7 and 1.3 necessary to promote the electron transfer. On the other hand,
nm, respectively (Figure 2(c) and (d)). This demonstrates a the background reaction in the absence of EY-POPs polymers
significant proportion of micropores in the EY-POPs networks.
but in the presence of light showed only around <5% yield
The chemical composition of EY-POPs networks were after 36 h (Table 1, entry 7), verifying that the EY-POPs
characterized by solid-state 13C cross-polarization magic-angle polymers played a catalytic role in the reaction. The effect of
spinning (CP/MAS) NMR spectroscopy. Figure 3 shows the 13C oxygen on the reaction was also examined. The reaction
CP/MAS NMR spectra recorded for EY-POP-1 and EY-POP-2
.
proceeded much slower under an N2 atmosphere excluding
The signals at δ = 168, 156, 147, 129 and 102 ppm confirmed oxygen, giving the product in moderate yield (60%) after 36 h
that the Eosin Y monomer skeleton has well been embedded (Table 1, entry 8). For the purpose of comparison, we also
into the polymer networks, while the peak at approximately 82 investigated the catalytic performance of the homogeneous
and 93 ppm represent the alkynyl groups in the EY-POPs Eosin Y catalyst under the same reaction condition, it can be
networks. The peak at about 129 and 125 ppm confirm that seen that the efficiency of EY-POP-1 polymer compares well to
the 1,3,5-triethynylbenzene skeleton has been successful that of the homogeneous Eosin Y catalyst (Table 1, entry 9).
embedded into the EY-POP-1 network, and the peak at about
Table 1. Screening condition for the Aza-Henry reactiona
65, 129 and 147 ppm also confirm that the tetra(4-
ethynylphenyl)methane skeleton has been successful
embedded into the EY-POP-2 network. All of the results
verified the bottom-up construction of the photoactive EY-
POPs networks with the Eosin Y skeleton embedded into the
Yieldb
65
frameworks.
Entry
Catalyst (x mg)
EY-POP-1 (5)
EY-POP-2 (5)
EY-POP-1 (10)
EY-POP-2 (10)
EY-POP-1 (10)
Light source
14 W bulb
14 W bulb
14 W bulb
14 W bulb
natural light
dark
Time (h)
36
1
2
3
4
5
6
7
8c
9
Photocatalytic Activity of EY-POPs in the Heterogeneous
Photocatalytic Aza-Henry Reaction.
36
54
24
98
24
87
36
35
The dehydrogenative coupling reactions, performed under
oxidative conditions, are an important C-C bond formation
methodology19. Significant progress has been made recently in
EY-POP-1 (10)
___________
36
trace
<5
14 W bulb
14 W bulb
14 W bulb
36
EY-POP-1 (10)
36
60
achieving
visible-light-promoted
photocatalytic
Eosin Y (5 mol%)
24
98
dehydrogenative coupling reactions with transition metal
complexes4 or organic dyes6b,6d as the homogeneous
photoredox catalysts. However, the practical application of
homogeneous photoredox catalysis is generally hindered due
to the requirement for high catalyst loadings and the difficulty
in separating the catalyst from the product. To address these
limitations, heterogenization of the homogeneous catalyst is a
promising option. We investigated the aza-Henry reaction of 2-
phenyl-1,2,3,4-tetrahydroisoquinoline with nitromethane as a
modal reaction to estimate the photocatalytic activities of the
EY-POPs networks (Table 1). In an initial experiment, the
oxidative coupling of 2-phenyl-1,2,3,4-tetrahydroisoquinoline
(0.20 mmol) with nitromethane (1.0 mL) in the presence of EY-
POPs (5 mg), visible light (14 W fluorescent lamp) and air was
investigated. Both of the EY-POPs polymers (5.0 mg) showed
approximately similar photocatalytic activities for this aza-
a
Reaction condition: 2-phenyl-1,2,3,4-tetrahydroisoquinoline (41.8 mg, 0.2
b
mmol), nitromethane (1.0 mL), and EY-POPs, r.t., 14 W household bulb, in air.
c
Isolated yield after silica gel column chromatography. The reaction was carried
out under N2.
The substrate scope of the aza-Henry reaction catalyzed by
EY-POP-1
was
examined
with
a
variety
of
tetrahydroisoquinolines and nitromethane/nitroethane (Table
2). As shown in Table 2, good to excellent isolated yields (90-
99%) were obtained for all of the aza-Henry reaction of a
variety of N-Aryltetradroisoquinolines with nitromethane
(Table 2, entries 1-8) and nitroethane (Table 2, entries 9-12)
catalyzed by the EY-POP-1 polymer, which are comparable to
those using the Ir- or Ru-loaded PCPs7a, the RB-CMP network15c
and the homogeneous organic dye counterpart6b,6d. These
results identified that the EY-POP-1 nanoporous polymer
4 | J. Name., 2012, 00, 1-3
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the products by centrifugation and decantation of the reaction
solution. The recycled catalyst was further washed with EtOAc
to remove residual product, and simple dried in vacuum
overnight before reuse. As in figure 4, the EY-POP-1 polymer
could be reused at least twelve times without any significant
loss of the photocatalytic activity (94-98% yield), which is
attributed to the built-in character of the covalently linked
catalytic sites of EY-POP-1 polymer. However, in the recycling
experiments, the reaction time was prolonged after five cycles,
which could be due to the impurities blocking the polymeric
nanopores. We found that the BET surface area of EY-POP-1
from 587 m2g-1 decrease to 347 m2g-1 after the sixth recycle
use (Figure S3).
Table 2. Investigating the substrate scope of the Aza-Henry reaction catalyzed by EY-
POP-1.
EY-POP-1 (10 mg)
N
+
Ar
R1
NO2
N
14 W bulb light
r.t. air
Ar
R1
NO2
Yield (%)b
Entry
1
Substrate
N
Product
Time (h)
N
24
36
72
12
20
72
72
24
24
17
50
24
98
NO2
N
N
2
3
94
91
98
99
99
97
94
94
90
91
92
CH3
NO2
N
CH3
N
N
NO2
F
Cl
F
Cl
N
4
NO2
N
N
5
NO2
Br
Br
N
N
6
NO2
N
OMe
OMe
OMe
OMe
N
7
Figure 4. Recycling experiment of EY-POP-1 for the Aza-Henry reaction of 2-(4-
chlorophenyl)-1,2,3,4-tetrahydroisoquinoline and nitromethane.
NO2
N
CH3
N
CH3
8
Conclusions
NO2
In conclusion, the Eosin Y, an organic dye, has been
successfully embedded into a nanoporous network EY-POPs
through a bottom-up strategy. The resultant framework
materials are stable in various solvents and are thermally
stable. Owing to the high BET surface area and the built-in
N
N
9
NO2
N
N
10
11
12
character of the covalently linked catalytic sites of EY-POPs
,
NO2
Br
F
Br
F
these photoactive polymers were shown to be highly active,
recyclable and reusable heterogeneous photocatalysts in aza-
Henry reaction. Catalyzed by the EY-POP-1 catalyst, the aza-
N
N
NO2
Henry
reaction
of
tetrahydroisoquinolines
to
nitromethane/nitroethane gives the desired products in good
to excellent yield (90-99%). The heterogeneous photocatalyst
could be reused at least twelve times without any significant
loss of the photocatalytic activity (94-98% yield). This work
highlights the potential of using POPs polymers as a stable and
molecularly platform for developing heterogeneous
photocatalysts for other important organic transformations.
Currently, research into the bottom-up construction of chiral
porous organic photocatalysts for asymmetric catalysis is
underway in our laboratory.
N
N
CH3
NO2
CH3
a Reaction conditions: 0.2 mmol substrate; 1.0 mL of nitroalkyl; 10 mg EY-
POP-1; room temperature; 14 W household bulb; in air. b Isolated yield
after silica gel column chromatography.
works as a high efficient heterogeneous organic-photocatalyst
for the aza-Henry reaction.
We further investigated the recyclability of EY-POP-1
catalyst in the aza-Henry reaction of 2-(4-chlorophenyl)-
1,2,3,4-tetrahydroisoquinoline with nitromethane (Table S2,
SI). After the reaction, EtOAc was added to dilute the reaction
mixture, and the EY-POP-1 catalyst was easily separated from
Experimental section
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Materials
temperature under irradiation with visible light using a cool
daylight energy-saving bulb (14 W) until all starting material
All reagents were purchased from commercial sources. Et3N had been consumed. After the reaction was completed
and DMF were dried through the standard procedures. (monitored by TLC), the mixture was centrifugated and the
Tetra(4-ethynylphenyl)methane and 1,3,5-triethynylbenzene solid was washed with EtOAc (3 x 5 mL). The combined organic
were prepared according to the literature procedure20. phase was then concentrated and purified by flash column
Pd(PPh3)2Cl2 , PdCl2 and Eosin Y were purchased from J&K. A chromatography with petroleum ether/EtOAc = 10:1 as the
range of substrates were synthesized according to the eluent to give the pure product.
literature procedure 21. All catalytic reactions were performed
in a 15 mL glass tube.
Typical recycling procedure for the aza-Henry reaction
catalyzed by EY-POP-1
Synthesis of EY-POP-1
The recycling experiment was performed by recovering the EY-
Eosin Y (692 mg, 1.0 mmol), 1,3,5-triethynylbenzene (200 mg, POP-1 catalyst using the centrifugation method. The recovered
1.33 mmol), bis-(triphenylphosphine)palladium(II) dichloride EY-POP-1 catalyst was washed with EtOAc to remove the
(30 mg) , and copper (I) iodide (20 mg) were added into a dried residual product and simply dried before resuse. We chose the
round-bottom flask under nitrogen atmosphere. Anhydrous aza-Henry
reaction
of
2-(4-chlorophenyl)-1,2,3,4-
DMF (10 mL) and Et3N (10 mL) were added to the mixture via a tetrahydroisoquinoline to nitromethane to investigate the
o
syringe. The resulting mixture was heated to 80 C and stirred recyclability of EY-POP-1 catalyst, and the results are
for 72 h under nitrogen atmosphere. After cooling to room summarized in Table S2.
temperature, the precipitate network polymer was filtered and
washed four times (once each) with chloroform, water, Physical characterization
methanol and acetone to remove any unreacted monomer or
catalyst residues. Further purification of the polymer was Thin-layer chromatography (TLC) plates were visualized by
carried out by soxhlet extraction with methanol for 48 h. The exposure to ultraviolet light. Flash column chromatography
o
product was dried at 70 C under vacuum for 6 h to give a red (FCC) was carried out with silica gel (200
1
−300 mesh). H and
powder. Yield: 465 mg (82%). Anal. Calcd for C36H10Na2O5: C, 13C liquid NMR spectra were recorded on a Bruker Avance III
76.06; H, 1.76. Found: C, 62.38, H, 1.25.
400 MHz NMR spectrometer. The chemical shifts δ are given in
ppm (parts per million) relative to tetramethylsilane (TMS) and
the coupling constants J are given in Hz. All the spectra were
recorded in CDCl3 as solvent at room temperature. TMS served
Synthesis of EY-POP-2
Eosin Y (296 mg, 0.43 mmol), tetra(4-ethynylphenyl)methane as the internal standard (δ = 0.00 ppm) for 1H NMR, while
(178 mg, 0.43 mmol), bis-(triphenylphosphine)palladium(II) CDCl3 as the internal standard (δ = 77.0 ppm) for 13C NMR. FT-
dichloride (15 mg) , and copper (I) iodide (10 mg) were added IR spectra were recorded on a Nicolet NEXUS 670 instrument.
into a dried round-bottom flask under nitrogen atmosphere. N2 adsorption and desorption isotherms were measured at 77
Anhydrous DMF (5.0 mL) and Et3N (5.0 mL) were added to the K using a Micromeritics ASAP 2020M system. The pore-size-
mixture via a syringe. The resulting mixture was heated to 80 distribution curves were obtained from the adsorption
oC and stirred for 72 h under nitrogen atmosphere. After branches using non-local density functional theory (NLDPT)
cooling to room temperature, the precipitate network polymer method. Solid-state NMR experiments were performed on a
was filtered and washed four times (once each) with Bruker Avance II WB 400 MHz NMR spectrometer. The 13C
chloroform, water, methanol and acetone to remove any CP/MAS NMR spectra were recorded with the contact time of
unreacted monomer or catalyst residues. Further purification 3 ms (ramp 100) and the recycle delay of 2 s on a 2.5 mm
of the polymer was carried out by soxhlet extraction with double resonance probe. The thermal properties of the
methanol for 48 h. The product was dried at 70 oC under polymer networks were evaluated using a thermogravimetric
vacuum for 6 h to give a red powder. Yield: 299 mg (89%). analysis (TGA)-differential thermal analysis instrument
Anal. Calcd for C53H22Na2O5: C, 81.12; H, 2.81. Found: C, (METTLER, TGA/DSC 1/1100) over the temperature range 25 to
69.94, H, 2.20.
800 °C under nitrogen atmosphere with a heating rate of 10
°C/min. Powder X-ray diffraction (PXRD) data were collected
General procedure for the aza-Henry reaction catalyzed by with a Rigaku D/MAX-2400 X-ray diffractometer operated at
EY-POP-1
40 kV and 100 mA with Cu Kα radiation at a scan rate of
15°/min. Field emission scanning electron microscopy (SEM)
In a typical run of catalytic activity test of EY-POP-1, N- observations were performed on Hitachi S-4800 microscope
Aryltetradroisoquinolines (0.2 mmol), nitroalkane (1.0 mL), operated at an accelerating voltage of 5.0 kV. The UV-Visible
and EY-POP-1 (10 mg) were added into a 15-mL glass tube. The absorption spectra of the Eosin Y monomer and the EY-POPs
tube was sealed with a rubber stopper and the reaction networks were recorded on UV-Vis spectrometer (U-4100) in
mixture was connected to the air through a needle in the solid state powder at room temperature. Elemental analysis
stopper. The tube was subsequently stirred at room
6 | J. Name., 2012, 00, 1-3
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15853; (f) S. Yi, X. Ma, I. Pinnau and W. J. Koros, J. Mater.
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was performed on an Elementar Analysensysteme GmbH
VarioEL V3.00 elemental analyzer.
3
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This work was supported by the National Natural Science
Foundation of China (No. 21502136, 21571137), Higher
Educational Science and Technology Program of Shandong
Province (No. J15LC18), and the Promotive Research Fund for
Excellent Young and Middle-aged Scientists of Shandong
Provine (No. BS2014CL035).
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Eosin Y, an organic dye, has been successfully embedded into a nanoporous network EY-POPs through a bottom-up strategy. The
obtained polymers could be used as highly effective and reusable heterogenous organo-photocatalyst for the dehydrogenative
coupling reaction.
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