Porous Organic Polymer from Aggregation-Induced Emission Macrocycle for White-Light Emission

Article abstract of DOI:10.1021/acs.macromol.8b01632

A tetraphenylethylene-based oxacalixarene macrocycle (TOM) with high fluorescence quantum yield (70%) was used as monomer to construct a fluorescent macrocycle-based porous organic polymer (pTOM). With high surface area, specific pore size, and emissive p

Full text of DOI:10.1021/acs.macromol.8b01632

Article
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Cite This: Macromolecules XXXX, XXX, XXX−XXX
Porous Organic Polymer from Aggregation-Induced Emission
Macrocycle for White-Light Emission
Zhen Wang,† Sen Yan,† Huang-Chen Cui,† Guang Cheng,‡ Hui Ma,† Qing-Mei Zhang,†
Qing-Pu Zhang,† Jun-Min Liu,*,§ Bien Tan,*,‡ and Chun Zhang*,†
†College of Life Science and Technology, National Engineering Research Center for Nanomedicine, and ‡School of Chemistry and
Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
§School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, China
S
* Supporting Information
ABSTRACT: A tetraphenylethylene-based oxacalixarene
macrocycle (TOM) with high fluorescence quantum yield
(70%) was used as monomer to construct a fluorescent
macrocycle-based porous organic polymer (pTOM). With
high surface area, specific pore size, and emissive properties,
the blue-greenish fluorescent pTOM can be developed into
white-light-emission materials by adsorbing guests of tris-
(bipyridine)ruthenium with complementary emission color by
̈
the Forster resonance energy transfer (FRET) effect.
frameworks and cause the radiative decay process to become
predominant and emit strong fluorescence, could be a high
quality porous fluorescent materials. Moreover, with the
property of porosity, the fluorescence of these materials could
be tuned through adsorbing appropriate guest dyes, even for the
full wavelength white light. However, such materials are rarely
reported.
INTRODUCTION
■
Porous organic polymers (POPs),1,2 new-generation porous
materials with salient advantages including high surface area, low
mass density, and high stability, exhibit unique advantages in the
field of gas storage, recognition, or catalysis using diverse
functional building blocks. Undoubtedly, the property of
functional building blocks is considered to be a crucial element
to influence the pore performance and potential applications of
POPs.3−11 Supramolecular macrocycles,12 a kind of artificial
macrocyclic compound including rotaxanes,13 calixarenes,14
cucurbiturils,15 pillararenes,16 and cyclophanes,17 may be a good
candidate for the building block of POPs. Owing to the intrinsic
cavities and shape-persistent property, macrocyclic molecules
display favorable selectivity toward various kinds of organic
guest molecules, which give rise to a considerable increase in
research of molecular recognition and self-assembly processes
over the past few decades. Recently, several macrocycle-based
POPs have been reported,18−23 utilizing macrocyclic molecules
as monomers, which exhibit excellent performance in gas
storage, guest recognition, and pollutant separation.
White-light-emission materials have attracted increased
interest over the past decade due to their potential applications
in display technologies and fluorescent sensors.35−40 Because of
the growing demand for white-light-emission materials in
industry, employing organic material instead of the traditional
phosphors would be an efficient method to avoid the costly rare-
earth-containing materials.41−45 Currently, various organic
porous materials explored developed for white-light emission
are mainly based on π-conjugated polymers46 and metal−
organic frameworks (MOFs).44−47 But the π-conjugated
polymers easily lost their fluorescence because of the ACQ
effect, and the white-light-emission MOFs are usually
constructed by rare-earth metals (for example, Eu3+, Tb3+, and
Dy3+), which limit their practical application. On the contrary,
the AIE-based pure organic POPs, exhibiting strong fluores-
cence in the solid state without containing rare-earth metal,
would be promising materials for illumination. Up to now, one
of the most exploited strategies to develop white-light-emission
Among various kinds of POPs, the fluorescent POPs not only
exhibited unique advantages in gas storage but also possessed
potential application in chemosensors and illuminating materials
because of their high porosity and strong fluorescence, like
conjugated microporous polymers (CMPs).24−27 However, the
π−π stacking interactions in CMPs easily trigger the thermal
decay of photoexcited states and result in less or no fluorescence
because of the aggregation-caused quenching (ACQ) mecha-
nism. To construct fluorescent POPs, utilization of fluorescent
monomer with the aggregation-induced emission (AIE) effect
might be a promising strategy.28−34 The POPs, constructed
from AIE monomers which were effectively fixed by the
̈
materials is carefully tuning of partial Forster resonance energy
transfer (FRET) between the donor−acceptor chromo-
phores.46,51,52 To obtain a bicomponent white-light-emission
Received: July 30, 2018
Revised: September 16, 2018
© XXXX American Chemical Society
A
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Scheme 1. Graphical Representation of Synthesis of TOM and pTOM
energy transfer system, the colors of host POPs and guest dyes
must be the two complementary colors (for example, blue and
EXPERIMENTAL SECTION
■
General Information. The raw materials of zinc powder, K2CO3,
Cs2CO3, TiCl4, BBr3, benzophenone, 4,4′-dihydroxybenzophenone,
4,4′-dimethoxybenzophenone, 2,3,5,6-tetrachloropyridine, 2,2′-bipyr-
idyl, bis(1,5-cyclooctadiene)nickel, and 1,5-cyclooctadiene were
orange) in required intensities that cover the visible wavelength
range from 400 to 700 nm.53 Taking advantage of permanent
porosity, the POPs can encapsulate suitable guest dyes to form a
bicomponent energy donor−acceptor system that exhibits
distinct photoluminescent properties which can be easily
tuned to various colors by regulating the proportion between
the host POPs and the encapsulated guest dyes. Thus, to
develop a bicomponent fluorescent POP for energy transfer
white-light-emission materials, the key problem is constructing a
host POP with specific pore size and emission wavelength which
allows the guest dye penetrating into so that the energy transfer
could proceed.
Recently, we synthesized a tetraphenylethylene (TPE)-based
emissive oxacalixarene macrocycle (TOM) by one-pot
nucleophilic aromatic substitution (SNAr) reaction.54−58 Con-
sidering the AIE effect of TPE moiety which exhibits strong
fluorescence at wavelength of 480 nm in aggregation state, we
predicted that if the TOM is polymerized, the rotation and
vibration of phenyl rings in TPE units may be restricted,
resulting in an emissive porous framework, and may offer an
alternative approach to develop an energy transfer white-light-
emission material after adsorbing a specific guest dye. Herein, we
synthesized a macrocycle-based polymeric framework (pTOM)
by nickel(0)-catalyzed Yamamoto-type Ullmann cross-coupling
reaction (Scheme 1).59,60 The strategy of networking macro-
cycles by covalent coupling not only overcame the interlaced
mode of macrocycles to turn on their pores and displayed
significantly enhanced Brunauer−Emmett−Teller (BET) sur-
face area and CO2 capture capacity compared with that of TOM
monomers but also exhibited strong blue-greenish fluorescence.
1
purchased from Aladdin or J&K and used as received. H NMR and
13C NMR spectra were recorded on a DMX600 NMR. MALDI-TOF
mass spectra were obtained on a BIFLEXIII mass spectrometer. UV
spectra were recorded on SHIMADZU UV-2041PC spectrometer.
Emission spectra were obtained on a HITACHI F-4500 spectrometer.
The X-ray intensity data were collected on a standard Bruker SMART-
1000 CCD area detector system equipped with a normal-focus
molybdenum-target X-ray tube (λ = 0.71073 Å) operated at 2.0 kW
(50 kV, 40 mA) and a graphite monochromator. The structures were
solved by using direct methods and were refined by employing full-
matrix least-squares cycles on F2 (Bruker, SHELXTL-97). Surface areas
and pore size distributions were measured by nitrogen adsorption and
desorption at 77 K using a Micromeritics ASAP 2020 volumetric
adsorption analyzer. Sample was degassed at 120 °C for 10 h under
vacuum before analysis. N2 isotherms were measured at 77 K up to 1.0
bar using a Micromeritics ASAP 2020 volumetric adsorption analyzer
with the same degassing procedure. CO2 isotherms were measured at
273 and 298 K up to 1.0 bar using a Micromeritics ASAP 2020
volumetric adsorption analyzer with the same degassing procedure.
Atomistic Simulations. Molecular models were generated from X-
ray crystallographic data structure using Materials Studio 7.0
(Accelrys). Connolly surfaces were calculated by rolling a probe
molecule across the substrate, the interface taken from the contact point
of the probe molecule.
Experimental Details. Synthesis of 1,1-Bis(4-hydroxyphenyl)-
2,2-diphenylethene (1). Benzophenone (1.82 g, 10 mmol), 4,4′-
dihydroxybenzophenone (2.14 g, 5 mmol), and zinc powder (5.24 g, 80
mmol) were added to a 250 mL round-bottom flask with THF (100
mL). The mixture was cooled under an ice−water bath, and titanium
tetrachloride (4.4 mL, 40 mmol) was added dropwise and then
recovered to room temperature and reflux overnight. The reaction was
then quenched by 50.0 mL of saturated K2CO3 (5.0 M), and the
supernatant solution was collected after stirring for 30 min. The organic
B
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Figure 1. (a, b) Fluorescence spectra of TOM in THF after the addition of various amounts of water at the concentration of 5.0 × 10−6 M (excitation
wavelength: 310 nm) and variations of fluorescent intensity at 480 nm. (c) Photos under UV irradiation of TOM with water fractions (v/v) in THF/
water mixture.
extracted with DCE and dried over anhydrous sodium sulfate. After
filtration and solvent evaporation, the residue was purified by silica gel
column chromatography with petroleum ether/ethyl acetate (5:1 v/v)
as eluent to afford 1 as a white solid in 38% yield. 1H NMR (600 MHz,
CDCl3), δ (ppm): 7.17−6.96 (m, 10H), 6.94−6.83 (t, 4H), 6.62−5.51
(m, 4H). 13C NMR (100 MHz, CDCl3), δ (ppm): 153.3, 143.5, 139.0,
135.9, 132.1, 130.7, 127.0, 126.9, 125.6, 114.0, 113.9.
the reaction solution and stirred for 0.5 h. The precipitated polymer was
collected by filtration and washed with a large amount of water, the
products were successively washed with excess THF and CH2Cl2 and
then sequentially purified by Soxhlet extraction with methanol, and the
purified products were dried in a vacuum oven at 60 °C for 12 h to
obtain the final pTOM (200 mg, 92%).
Synthesis of TOM. 1,1-Bis(4-hydroxyphenyl)-2,2-diphenylethene 1
(400 mg, 1.10 mmol), 2,3,5,6-tetrachloropyridine 2 (238 mg, 1.10
mmol), and Cs2CO3 (1.08 g, 3.30 mmol) were added to a 100 mL
round-bottom flask. DMSO (25 mL) was added, and then the
combined mixture was stirred vigorously at 120 °C overnight. After the
raw materials were consumed, the reaction was allowed to cool to RT;
the mixture was partitioned between CH2Cl2 (40 mL) and H2O (40
mL) and separated, and the aqueous layer was extracted twice with
CH2Cl2 (20 mL). The combined organics were dried over anhydrous
Na2SO4, filtered, and concentrated under vacuum. Products were
simply isolated by recrystallized from CH2Cl2/MeOH (220 mg, 40%).
1H NMR (600 MHz, CDCl3): δ 7.75 (s, 2H), 7.11−7.09 (t, J = 12 Hz,
RESULTS AND DISCUSSION
■
The tetraphenylethylene (TPE)-based emissive oxacalixarene
macrocycle TOM was synthesized by one-pot (SNAr) reaction
of dihydroxytetraphenylethylene 1 with 2,3,5,6-tetrachloro-
pyridine 2 in the presence of Cs2CO3 in DMSO at 120 °C for
overnight resulted in the formation of TOM in yields of 40% as
depicted in Scheme 1. Products were simply isolated by
recrystallized from CH2Cl2/MeOH. The FT-IR, NMR,
MALDI-TOF MS, elemental analysis, and X-ray single crystal
diffraction analysis were used to characterize the structures of
TOM.
20H), 6.98−6.99 (d, J = 6 Hz, 8H), 6.79−6.80 (d, J = 6 Hz, 8H). 13
C
The 1H NMR spectrum of TOM in CDCl3 (Figure S1) shows
one singlet at δ = 7.75 ppm for the proton of the pyridine moiety,
and the 13C NMR (Figure S2) shows 13 signals for the different
carbons in TOM. The TOM adopts the conformation of the 1,3-
alternate as only one set of proton and carbon signals were
observed, which was further confirmed by X-ray single crystal
diffraction analysis as discussed below. With TPE units in their
scaffolds, the fluorescent properties of TOM were investigated
in solution. As we expected, TOM shows typical AIE properties
(Figure 1). It is almost nonfluorescent when excited at λ = 310
nm (see Figure S3 for the UV/vis absorption spectrum) in THF
(good solvent), but the fluorescent intensity begins to enhance
after increasing the fraction (v/v) of water (bad solvent) in THF
to 80%. When the fraction of water was increased up to 95%, the
solution of TOM showed a strong green fluorescence with a
quantum yield (Φf) of 70%, which was similar to our precursor
TPE-based calixarenes.61,62
NMR (100 MHz, CDCl3): 154.28, 151.18, 143.96, 141.77, 141.22,
140.26, 139.28, 132.30, 131.38, 127.89, 126.74, 121.12, 110.55.
MALDI-TOF-MS: m/z 1016.3 (M+). Anal. Calcd for
C62H38Cl4N2O4: C, 73.24; H, 3.77; N, 2.76. Found: C, 73.12; H,
3.95; N, 3.02. Crystallographic data for TOM: Mr = 1016.74,
orthorhombic, space group C2, a = 35.279(5), b = 12.2498(16), c =
12.5944(16) Å, α = 90°, β = 94.960°, γ = 90°, V = 5422.4(13) Å3, Z = 4,
ρcalcd = 1.245 g/cm3, μ = 0.267 mm−1, reflections collected 20200, data/
restraints/parameters 10114/1/6496, GOF on F2 1.088, final R1 =
0.0587, wR2 = 0.1566, R indices (all data): R1 = 0.0767, wR2 = 0.1763,
largest difference peak and hole: 0.994 and −0.251 e/Å3, CCDC-
1525730.
Synthesis of pTOM. Under a dry argon atmosphere, TOM (250 mg,
0.25 mmol), 2,2′-bipyridyl (230 mg, 1.5 mmol), and bis(1,5-
cyclooctadiene)nickel (405 mg, 1.5 mmol) were added to a 100 mL
two-neck round-bottom flask, followed by a solution of 1,5-cyclo-
octadiene (160 mg, 1.5 mmol) in 30 mL of DMF added by a syringe.
The combined mixture was stirred at 85 °C for 5 days before the
reaction was allowed to cool to RT. 40 mL of 2 M HCl was added into
C
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Figure 2. Top view (a) and side view (b) of X-ray crystal structures of TOM. The layered structure formed by the open-chain of TOM (the
neighboring open chains of TOM structures were presented by different colors) (c). The cross-sectional images of the packing structures with (d) and
without (e) the oxacalixarene framework show that cTOM has nonconnective lattice voids, as illustrated by the gray Connolly surface (probe radius =
1.82 Å) applied to the crystal structure for the desolvated material.
Figure 3. (a) 13C CP-MAS NMR spectrum. (b) TEM image (bar = 0.2 μm). (c) SEM image (bar = 2 μm). (d) Powder X-ray diffraction (PXRD) of
pTOM.
The suitable single crystals of TOM for X-ray single crystals
analysis were obtained by diffusing Et2O into the TOM solution
of dichloromethane. Similar to most reported oxacalixarenes,
TOM adopts 1,3-alternate conformation in the solid state as
shown in Figures 2a and 2b. In the solid state, TOMs formed 1-
D infinite open-chain structure by the interaction of C−H···π
(dC−H···π = 2.665 Å) (Figure S4) that are reversely interdigitated
to form layered structures (Figure 2c and Figure S5) by
D
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Figure 4. N2 sorption isotherms of pTOM at 77 K (a), pore size distributions of pTOM calculated using the NLDFT method (b), and CO2 sorption
isotherms of cTOM and pTOM at 273 K (c) and 298 K (d). In (a), (c), and (d), filled symbols denote gas adsorption, and empty symbols denote
desorption.
interaction of C−H···Cl (dH···Cl = 2.908 Å, θC−H···Cl = 161.93°
and 2.868 Å, θC−H···Cl = 134.36°) and π···π stacking (dπ···π
the results of transmission electron microscopy (TEM) (Figure
3b) and scanning electron microscopy (SEM) (Figure 3c), the
pTOM formed rough particles, which further was confirmed by
the powder X-ray diffraction (PXRD) experiment that pTOM is
noncrystalline (Figure 3d). The thermogravimetric analysis
(TGA) showed that pTOM is thermally stable without
significant mass loss below 500 °C under a nitrogen atmosphere
(Figure S8).
The pTOM was desolvated at 120 °C for 10 h under vacuum
before the gas adsorption and desorption properties were
investigated. From the results of nitrogen sorption analysis, the
Brunauer−Emmett−Teller (BET) surface areas and pore
volumes are 268 m2 g−1 (the Langmuir surface area is 375 m2
g−1) and 0.273 cm3 g−1 for pTOM (Figure S9), which can
demonstrate that pTOM formed porous frameworks from
nonporous frameworks. As shown in Figure 4a, pTOM showed a
steep nitrogen uptake at low relative pressure which implies the
presence of macropores in their frameworks. The phenomenon
that low-pressure hysteresis is extending to the lowest attainable
pressures is associated with the irreversible uptake of gas
molecules in the pores (or through pore entrances), which hints
at a swelling of the polymer matrix at 77 K by nitrogen. Based on
nonlocal density functional theory (NLDFT) (Figure 4b), the
pore size distribution was calculated that confirmed the
existence of micropores and mesopores in pTOM, which may
result from expanded networks.
=
2.369 Å). Moreover, by the virtue of π···π stacking (dπ···π = 2.330
Å) and C−H··π (dC−H···π = 2.893 Å) (Figure S6), the layered
structure was extended into a three-dimensional framework.
However, as shown in Scheme 1, the crystalline structure of
TOM (cTOM) was a nonporous framework even after
removing the solvent because the interlaced mode give rise to
the formation of nonconnective lattice voids, which is illustrated
by the gray Connolly surface (probe radius = 1.82 Å) (Figures
2d and 2e). The N2 sorption experiment of cTOM after
desolvation at 120 °C for 10 h under vacuum showed no N2
uptake without significant BET surface area and confirmed the
crystallographic measurements and atomistic simulations.
Considering functional groups of chlorine in the outside of the
macrocycle which gave a chance to ameliorate the nonporous
framework of cTOM, Yamamoto-type Ullmann cross-coupling
reactions were used to polymerize the TOM into a novel
macrocycle-based emissive porous polymer pTOM (Scheme 1).
The amount of Ni residue in pTOM was measured as low as 0.10
wt % by inductively coupled plasma mass spectrometry (ICP-
MS). The successful construct of pTOM from monomers TOM
was confirmed unambiguously by Fourier transform infrared
(FT-IR) analysis and 13C cross-polarized magic angle spinning
solid-state (CP-MAS) NMR spectroscopy. By comparing the
FT-IR spectra of TOM and pTOM (Figure S7), the aromatic
C−Cl bending vibrations at 1091 cm−1 disappeared after the
monomers were polymerized. Furthermore, the results of 13C
CP-MAS NMR shows that the resonance peaks at δ = 156, 141,
and 103 ppm can be assigned to the aromatic carbon in the
pyridine rings and 152, 141, 139, 130, 126, and 119 ppm for the
carbons of for the carbons in the TPE moiety (Figure 3a). From
The CO2 capture experiments were performed at 273 and 298
K. As shown in Figures 4c and 4d, although the cTOM shows no
BET surface area, it can uptake CO2 15.4 cm3 g−1 at 273 K/1.0
bar and 9.4 cm3 g−1 at 298 K/1.0 bar. That can be explained by
two reasons: (1) the size of the N2 molecule (3.64 Å) is larger
than the CO2 molecule (3.3 Å); (2) the electron-rich properties
E
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Figure 5. (a)Fluorescence spectrum of pTOM (black) and absorption spectrum of Ru(bpy)3Cl2. (b) Fluorescence spectra of pTOM. (c) Photos
under UV irradiation. (d) CIE chromaticity diagram that shows the luminescent color changes after adding different amounts of Ru(bpy)3Cl2.
of nitrogen and oxygen atoms in pTOM skeleton facilitate local-
dipole/quadrupole interactions with CO2 which could be
adsorpted on the surface of cTOM, while the pTOM showed
much better CO2 uptake capacities of 33.6 cm3 g−1 at 273 K/1.0
bar and 19.6 cm3 g−1 at 298 K/1.0 bar. According to the CO2
adsorption isotherms at 273 and 298 K, the isosteric enthalpy
(Qst)63 of pTOM for CO2 was calculated to be 31.5 kJ/mol,
which is higher than that of cTOM (23.9 kJ/mol) using the
Clausius−Clapeyron equation (Figure S10). The selectivity of
CO2/N2 for pTOM was found to be 19, which was calculated
from analysis of initial of slopes of the adsorption isotherms by
one single gas adsorption experiments at 273 K (Figure S11).
Tris(bipyridine)ruthenium (Ru2+) is one of the best standard
model luminophores that always has high quantum efficiency in
both an aqueous and a nonaqueous medium. It exhibits visible-
light absorption, strong emission, and a long lifetime and is thus
widely used as redox photosensitizers for various photo-
reactions.64 One application here is obvious: using the pTOM
and Ru(bpy)3Cl2 as fluorescent donors and receptors to develop
a new light-harvesting luminescent material which could
potentially generate white-light emission, a property that is of
great importance for the lighting industry. There are two
prerequisites for the fluorescence resonance energy transfer: (1)
As shown in Figure 5a, the excitation wavelength of Ru(bpy)3Cl2
overlapped with the emission wavelength of pTOM; (2) the
main pore size distribution (11.7 Å) of pTOM is in accordance
Ru(bpy)3Cl2 to the solutiong of pTOM (2 mL, 0.25 mg/mL),
emission spectroscopy studies revealed that the fluorescent
intensity of the Ru(bpy)3Cl2at 600 nm increased gradually at
the expense of the fluorescent intensity of the pTOM at 430 nm
(Figure 5b). The fluorescent color changes from greenish blue
to orange that can be distinguished by the naked eye illuminated
with a UV lamp (excitation wavelength λ = 365 nm), which are
consistent with the coordinates on the chromaticity diagram
(CIE 1931), as shown in Figures 5c and 5d. Of particular interest
is the observation that an intense white-light emission solution
(CIE coordinates (0.30, 0.33)) is established upon adding
Ru(bpy)3Cl2 to 35 ppm, which is very close to that of the pure
white (0.33, 0.33) light. This white-light emission solution
exhibited good stability, which can keep white light without
significant variation after being placed for 1 week (Figure S13).
The efficiency of energy transfer of white-light emission solution
was 60%, which was estimated from the quenching data, using
the equation51,65
IDA
E = 1 −
ID
where E is the fractional energy transfer efficiency, ID is the
intensity of donor emission in the absence of the acceptor, and
IDA is the intensity of donor emission in the presence of the
acceptor. This efficiency is higher than the reported Pan’s42
white-light-emission porous fiber (18.06%) and Jiang’s43 POP
white-light-emission films (30%−50%). As the white-light
materials are often used in solid state, the luminescence property
of the complex pTOM and Ru(bpy)3Cl2 in the solid state has
been investigated. After evaporating the CH2Cl2 of white light
solution and being grinded into homogeneous powder, the
2+
with the size of Ru(bpy)3 (9.6 Å) (shown in Figure 4b and
Figure S12) and the nitrogen atoms on pTOM skeleton
facilitated the Ru(bpy)3Cl2 to be adsorbed, leading to the
fluorescent donors and acceptor so close to each other. As for
the fluorescense property of pTOM, it emitted strong greenish-
blue fluorescence when dispersed in CH2Cl2 solution upon
excitaton at λ = 365 nm. After adding various amounts of
F
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the solid state under UV irradiation (365 nm) (Figure S14).
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CONCLUSIONS
■
In summary, we have developed a novel emissive polymeric
framework (pTOM) based on the oxacalixarene macrocycle
(TOM) as monomer. In the solid state, it was found that pTOM
overcame the interlocking assembly mode of TOM and
performed enhanced porous properties including enhanced
BET surface area, pore volume, and CO2 capture. By the virtue
of its strong fluorescence and the macrocycle-based porous
framework, pTOM could be used to capture the luminophore of
tris(bipyridine)ruthenium (Ru2+) to achieve a new white-light-
̈
emission material through effective Forster resonance energy
transfer. Given the porous properties ameliorative behavior of
simple model emissive materials presented here, we envision
that further study of intrinsic cavity-based porous polymers will
offer not only maintained properties of the monomers such as
fluorescent property but also endowed or improved new
properties which presented here are to overcome interlocking
assembly mode of macrocycles to turn on their pores, which are
beneficial for the simultaneous illuminating and gas storage
applications.
̈
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.macro-
mol.8b01632.
■
S
Original data of all the NMR, UV, FT-IR, and X-ray single
crystals analysis of TOM, the gas adsorption experiments
of pTOM and chemical structure of tris(bipyridine)
ruthenium (Ru2+) (DOCX)
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X-ray crystallographic data of TOM (CIF)
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AUTHOR INFORMATION
Corresponding Authors
*(C.Z.) E-mail chunzhang@hust.edu.cn.
*(B.T.) E-mail bien.tan@hust.edu.cn.
*(J.-M.L.) E-mail liujunm@mail.sysu.edu.cn.
■
ORCID
Bien Tan: 0000-0001-7181-347X
Chun Zhang: 0000-0002-5190-7396
Author Contributions
Z.W., S.Y., and H.C.C. contributed equally to this work.
Notes
(17) Tang, R. Y.; Li, G.; Yu, J. Q. Conformation-Induced Remote
Meta-C-H Activation of Amines. Nature 2014, 507, 215.
The authors declare no competing financial interest.
(18) Yu, J. T.; Chen, Z.; Sun, J. L.; Huang, Z. T.; Zheng, Q. Y.
Cyclotricatechylene Based Porous Crystalline Material: Synthesis and
Applications in Gas Storage. J. Mater. Chem. 2012, 22, 5369.
(19) Yang, H. S.; Du, Y.; Wan, S.; Trahan, G. D.; Jin, Y. H.; Zhang, W.
Mesoporous 2D Covalent Organic Frameworks Based on Shape-
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ACKNOWLEDGMENTS
■
This work is supported by the National Natural Science
Foundation of China (21672078 and 21875079), the Natural
Science Foundation of Hubei Province (2016CFB372), and the
Applied Basic Research Program of Wuhan City
(2016010101010017). We thank the Analytical and Testing
Center of Huazhong University of Science and Technology for
related analysis. We also thank Dr. Yao Yu and Wuhan National
High Magnetic Field Center for analysis of solid-state NMR.
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