Conjugated microporous polymers based on biphenylene for CO2 adsorption and luminescence detection of nitroaromatic compounds

Article abstract of DOI:10.1039/c8nj01306c

Conjugated microporous polymers have shown great potential applications in chemosensors, gas storage/separation, light-harvesting, and organic electronic materials. In this study, three novel conjugated microporous polymers based on biphenylene have been

Full text of DOI:10.1039/c8nj01306c

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

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ARTICLE
Conjugated microporous polymers based on biphenylene for CO2
adsorption and luminescent detection of nitroaromatic
compounds†
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
a,b
DOI: 10.1039/x0xx00000x
Shun Wang, Yuchuan Liu, Yue Yu, Jianfeng Du, Yuanzheng Cui, Xiaowei Song * and Zhiqiang
Liang *
a
www.rsc.org/
Conjugated microporous polymers have shown great potential applications in chemosensors, gas storage/separation,
light-harvesting and organic electronic materials. In this paper, three novel biphenylene-based conjugated microporous
polymers have been synthesized by the palladium-catalyzed Suzuki and Sonogashira-Hagihara cross-coupling reactions of
3
1
2
,4’,5-tribromobiphenyl. N adsorption studies indicate that these polymers are porous, and the BET surface areas are 493,
2
-1
576 and 643 cm g for CMP-LS1–3, respectively. Amongst these synthesized CMPs, CMP-LS2 exhibits the highest CO
2
3
-1
adsorption capacity of 87.4 cm g and reasonable CO
2
/N
2
selectivity (27.9) and CO
2
/CH
4
selectivity (5.6) at 273 K/1 bar.
CMP-LS1 and CMP-LS2 exhibit blue luminescence in ethanol suspension. Furthermore, the fluorescence of CMP-LS1 and
4
4
-1
CMP-LS2 can be effectively quenched by PA with the KSV constants of 5.05 × 10 and 3.70 × 10 M , respectively. They can
be used as luminescent sensor for detecting nitroaromatic compounds.
2
5-27
28
evolution
and energy storage.
Introduction
In recent years, the excessive emission of CO generated by
2
burning fossil fuels brings about global climate change, thus,
Porous organic polymers (POPs), which are composed of light
elements (C, H, O, N, B, etc.), have attracted tremendous
attention owing to the distinguished features of diverse
synthetic methods, high chemical/thermal stability, low
skeletal density, easy modification, and high surface area.
Large numbers of POPs have been reported including
the capture technology of CO has been garnered increasing
2
interest both in academia and industry. The former process for
2
9
CO capture is the adsorption based on amine solutions,
2
however, this process suffers from heavy toxicity and high
expenditure. Nowadays, adopting solid adsorbents to capture
1
,2
CO
their mild operating conditions and lower energy penalty.
More and more porous materials including zeolites, functional
mesoporous SiO , metal-organic frameworks (MOFs) and
porous organic polymers have been applied into capture and
2
has been proved to be an efficient method on account of
conjugated microporous polymers (CMPs), covalent organic
3
3
0
,4
frameworks (COFs),
5
polymers of intrinsic microporosity
7,8
,6
(PIMs),
porous aromatic frameworks (PAFs),
9
covalent
,10
2
triazine-based frameworks (CTFs),
1-13
polymers (HCPs),
of porous materials, have been widely used in the applications
and hypercrosslinked
1
etc. POPs, emerging as a promising class
3
1-34
storage of CO2.
Besides, stability would be important in
1
4-16
17,18
19-21 many real-life applications. Since first reported in 2007 by
1
Copper et al., CMPs with permanent porous structures have
of gas storage/separation,
2
and proton conductions . Among porous organic polymers,
CMPs combine permanent porosity and high surface areas
luminescence,
catalysis
2
been extensively investigated for capturing CO . The surface
2
2
3
area and pore size have a large effect on the gas adsorption
and storage performance of CMPs, and it has been proved that
the pore properties of CMPs could be adjusted by tuning the
with conjugated frameworks. Due to their high surface areas
and chemical functionality, CMPs have shown great potential
for gas adsorption and separation. On the other hand, the
extended π-conjugated frameworks of CMPs endow them
highly efficient luminescent properties, which have been
3
5-37
monomer length and geometry.
Currently, detecting nitroaromatic explosives such as 2,4,6-
trinitrotoluene (TNT) and 2,4,6-trinitrophenol (PA) have
become one of the most critical issues concerning national
24
applied in chemosensors,
photocatalysis for hydrogen
2
security, military applications and environmental safety.
a
During commercial use and production, PA is a non-
biodegradable environmental pollutant, which is one kind of
strong irritants. Exposed to the air for a long time, PA can
cause harm to human health. Luminescent detection method
of nitroaromatic explosives came into being owing to its
State Key Lab of Inorganic Synthesis and Preparative Chemistry, College of
chemistry, Jilin University, Changchun, 130012, P. R. China,
E-mail: liangzq@jlu.edu.cn; xiaoweisong@jlu.edu.cn
b
Department of Physical and Macromolecular Chemistry, Faculty of Science,
Charles University in Prague, 128 43 Prague 2, Czech Republic
Electronic Supplementary Informaꢀon (ESI) available: H NMR spectra, IR, PXRD,
1
†
TGA, SEM, UV-vis and fluorescence spectra, gas adsorption and selectivity for
CMP-LS1 . See DOI: 10.1039/x0xx00000x.
3
8
potential merits. In comparison to traditional analysis
–
3
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methods, such as gas chromatography, liquid chromatography- instrument. The samples were degassed at 100 °C under
mass spectrometry and spectrophotography, luminescence- vacuum for 10 h.
based detection possesses a plenty number of nonnegligible
Synthesis of 3,4',5-tribromobiphenyl (TBBP)
advantages, including high sensitivity, simplicity, short
response time, low expense, as well as it can be tested in both A mixture of 1-bromo-4-iodobenzene (2.83 g, 10 mmol), 3,5-
3
9
solution and solid phase.
fluorescent conjugated polymers have been successfully (578 mg, 0.5 mmol) and anhydrous K
synthesized and reported as chemosensors, especially, was placed into a Schlenk reaction tube (200 mL) equipped
luminescent CMPs are widely employed in detection of with a magnetic stirring bar under N atmosphere. Then 100
mL DMF was added to the reaction tube. The resulting solution
In this paper, we report the synthesis of three was degassed and purged with nitrogen three times. After
polyphenylene conjugated microporous polymers (CMP-LS1 being heated at 85 °C for 12 h under a nitrogen atmosphere,
via Pd-catalyzed Suzuki and Sonogashira-Hagihara cross- the reaction mixture was quenched with water, extracted with
coupling reactions of 3,4',5-tribromobiphenyl and ethyl acetate, washed with brine, dried over MgSO . The
Numbers of π-electron-rich dibromobenzeneboronic acid (2.80 g, 10 mmol), Pd(PPh
3 4
)
2
CO (8.28 g, 60 mmol)
3
2
4
0,41
nitroaromatic compounds.
–3)
4
comonomers such as 1,3,5-tris(4,4,5,5-tetramethyl-1,3,2- collected organic phase was concentrated by a rotary
dioxaborolan-2-yl)benzene, 1,4-phenylenediboronic acid and evaporator and the crude product was purified by silica-gel
1
,3,5-triethynylbenzene (Scheme 1). Of all the polymers column with petroleum ether as eluent. TBBP was obtained as
1
3
investigated, CMP-LS2 exhibits high Brunauer–Emmett–Teller a white solid in 53% yield (2.07 g). H NMR (CDCl , 300 MHz): δ
2
-1
13
(BET) surface areas up to 1576 m g and good CO
2
uptake up (ppm) 7.68–7.55 (m, 5H), 7.42–7.36 (m, 2H). C NMR (CDCl
selectivity of 75 MHz): δ (ppm) 143.4, 137.1, 132.9, 132.1, 128.7, 128.5,
was calculated to be 4.5, 5.6, 4.5 at 273 K 123.3, 122.9 (Fig. S1 and S2).
/CH , 5/95), and CMP-LS1 exhibits the
selectivity of 23.2, 27.9, 19.8 at 273 K and 1.0 bar
, 15/85). Besides, the resulting two luminescent A mixture of TBBP (391 mg, 1 mmol), 1,4-phenylenediboronic
polymers (CMP-LS1 and CMP-LS2) show high selective and acid (249 mg, 1.5 mmol), anhydrous K CO (827 mg, 6 mmol)
(19 mg, 0.05 mmol) were dissolved in DMF
40 mL). The reaction mixture was heated at 120 °C and stirred
for 60 h under N atmosphere. The mixture was cooled to
3
,
3
-1
to 87.4 cm g at 273 K and 1.0 bar. The CO
CMP-LS1 over CH
and 1.0 bar (CO
CO /N
CO /N
2
–
3
4
2
4
–3
Synthesis of CMP-LS1
2
2
(
2
2
2
3
sensitive detection ability of PA in suspension of ethanol.
2 2
and Pd(PhCN) Cl
(
2
Experimental Section
room temperature, and quenched by addition of water. The
precipitated polymer was collected by filtration and washed
several times with water, methanol, and acetone to remove
Materials
Unless otherwise noted, all reagents were purchased from any unreacted monomers or catalyst residues. Then further
commercial suppliers and used without further purification. purification of the polymer was washed by Soxhlet extraction
3,4',5-Tribromobiphenyl was synthesized via Pd-catalyzed with methanol and THF for 24 h each. The solid was dried in a
Suzuki reaction of 1-bromo-4-iodobenzene and 3,5- vacuum oven for 12 h at 50 °C to obtain CMP-LS1 as gray-black
dibromobenzeneboronic acid.
powder (218 mg, yield: 82%).
Characterization
Synthesis of CMP-LS2
Powder X-ray diffraction (PXRD) patterns were collected on a CMP-LS2 was synthesized employing the similar steps as
Rigaku D-Max 2550 diffractometer using Cu-Kα radiation (λ = described for CMP-LS1
TBBP (391 mg, 1 mmol), 1,3,5-
.15418 nm) in a 2θ range of 4–40° at room temperature. tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (456
Fourier transform infrared (FTIR) spectra were recorded in the mg, 1 mmol) were used for this polymerization. CMP-LS2 was
.
0
-1
range of 400–4000cm on a Nicolet 6700 FT-IR spectrometer collected as gray-black powder (178 mg, yield: 79%).
with KBr pellets. Thermogravimetric analyses (TGA) were
performed on
a Perkin-Elmer TGA-7 thermogravimetric
analyzer from room temperature to 800 °C in air atmosphere
with a heating rate of 10 °C/min. Scanning electron microscopy
(SEM) was performed on a JSM-6700F electron microscope.
Fluorescence spectra were recorded on a FLUOROMAX-4
1
13
fluorescence spectrophotometer. H NMR and C NMR
spectra were recorded at room temperature using a Varian
Mercury spectrometer operating at frequencies of 300 and 75
1
13
13
MHz for H and C, respectively. The solid-state C cross-
polarization/magic-angle spinning (CP/MAS) NMR spectra
were collected a Bruker AVANCE III 400 WB spectrometer. All
gases adsorption-desorption measurements at different
temperature were carried out on a Micromeritics ASAP 2020
Scheme 1 Synthetic routes of CMP-LS1–3.
2
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Synthesis of CMP-LS3
TBBP (313 mg, 0.8 mmol), 1,3,5-triethynylbenzene (118 mg,
.8 mmol), Pd(PPh Cl (28 mg, 0.04 mmol), copper(I) iodide
15 mg, 0.08 mmol) and PPh (21 mg, 0.08 mmol) were
dissolved in a mixture of anhydrous DMF (20 mL) and Et N (20
mL). Then the following steps were same to the synthesis of
CMP-LS1 CMP-LS3 was obtained as brown powder (213 mg,
0
3
)
2
2
(
3
3
.
yield: 90%).
Results and Discussion
Synthesis of CMP-LS1–3
As shown in Scheme 1, CMP-LS1–3 were synthesized from
3,4',5-tribromobiphenyl through palladium catalyzed Suzuki
and Sonogashira-Hagihara coupling reactions. For CMP-LS1
and CMP-LS2, the Suzuki reactions of 3,4',5,-tribromobiphenyl
with 1,4-phenylenediboronic acid or 1,3,5-tris(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)benzene were conducted
13
Fig. 1 The solid-state C CP/MAS NMR spectra of CMP-LS1–3.
in the catalytic system of Pd(PhCN)
for 60 h. While for CMP-LS3, the Sonogashira-Hagihara
reaction of 3,4',5,-tribromobiphenyl with 1,3,5-
triethynylbenzene was performed in the catalytic system of
Pd(PPh Cl /CuI/PPh /DMF/Et N at 120 °C for 60 h. All these
polymers are formed as fine powder and insoluble in the
2 2 2 3
Cl /K CO /DMF at 120 °C
3
)
2
2
3
3
general organic solvents such as DMF, DMSO, CH
2
2
Cl and THF.
Characterization of CMP-LS1
–3
Thermogravimetric analyses (TGA) of CMP-LS1
–
3
show their
excellent thermal stability and high decomposition
temperatures under air atmosphere. As shown in Fig. S3, CMP-
LS1–3 are stable up to 320–400 °C, respectively. It should be
mentioned is that the high stabilities make many potential
applications available. Powder X-ray diffraction measurements
show that their textures are amorphous (Fig. S4). Meanwhile,
scanning electron microscopy (SEM) was carried out to collect
the morphology information of CMPs (Fig. S5). The SEM
images indicate that all the polymers have irregular shapes.
The formation of the CMPs skeleton was initially
characterized through Fourier transform infrared (FT-IR)
spectroscopy (Fig. S6). In the FT-IR spectrum of TBBP, the
characteristic vibration of C-Br band is obviously observed at
2 2
Fig. 2 (a) N sorption isotherms at 77 K and CO sorption isotherms of CMP-LS1 (b),
CMP-LS2 (c), CMP-LS3 (d) collected at 273 K (cycle) and 298 K (square).
Table 1 Porosity properties of CMP-LS1-3
Isosteric
heats/kJ
a
S
BET
V
total
3
V
micro
2
CO Uptake
Sample
2
-1
-1
3
-1
3
-1
(m g )
(cm g )
(cm g )
(cm g )
-1
mol
-1
around 560 cm , while it became very weak in the FT-IR CMP-LS1
spectra of CMP-LS1
Furthermore, the typical -C≡C- CMP-LS2
stretching mode at about 2200 cm is observed in CMP-LS3
These results indicate that the desired polymers have been
obtained. The frameworks of CMP-LS1 were further
investigated by solid-state C CP/MAS NMR spectroscopy (Fig. aromatic carbon signals of CMP-LS1 and CMP-LS2 than those
493
1576
643
0.32
1.06
0.37
0.12
0.36
0.17
31/17
87/47
42/24
30.2
31.6
30.4
–3.
-1
CMP-LS3
.
a
Measured at a pressure of 1 bar at 273/298 K.
–
3
1
3
1
3
1
). For CMP-LS1 and CMP-LS2, the solid-state C CP/MAS of CMP-LS3 indicate the higher symmetry of benzene rings in
NMR spectra exhibit only two main peaks at around 141 and the frameworks of CMP-LS1 and CMP-LS2
27 ppm, which could be assigned as the substituted and non-
substituted aromatic carbons, respectively. While for CMP-LS3
.
1
Porosity properties and gas adsorption studies of CMP-LS1–3
,
there are several signals between 140 and 124 ppm The nitrogen gas adsorption and desorption isotherms at 77 K
corresponding to the aromatic carbons of different benzene were performed to investigate the porosity properties of CMP-
rings in the framework. The additional broad peak at about 90 LS1
–
3. As shown in Fig. 2a, these CMPs exhibited rapid uptake
ppm corresponds to ethynylene bonds of CMP-LS3. The less
of N at a relatively low pressure (P/P < 0.05) and followed by
2
o
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a slow increase. According to the IUPAC classification, they
exhibit Type I nitrogen gas sorption isotherms with H4 type
hysteresis loops. The BET surface areas were calculated within
the relative pressure (P/P
generates apparent surface areas of 493, 1576 and 643 m g
for CMP-LS1 , respectively. The pore size distributions (PSDs)
of CMPs based on the non-local density functional theory
NLDFT) method display the main peaks at 0.4–1.4 nm,
o
) range from 0.05 to 0.20, which
2
-1
–
3
(
confirming their predominant microporous structures (Fig. S7).
In addition, CMP-LS2 shows some mesoporous, which is
consistent with the N
2
sorption isotherm. The total pore
volume (Vtotal) estimated from the single point measurement
3
-1
of the N
2
uptake at P/P
o
= 0.97 is 0.32, 1.06 and 0.37 cm g
for CMP-LS1
–
3
, and the micropore volume (Vmicro) is 0.12, 0.36
-1
3
and 0.17 cm g , respectively. Detailed porosity data for the
CMPs in this study are compiled in Table 1.
Furthermore, we measured the CO
CMP-LS1 from low pressure to 1.0 bar at 273 K and 298 K to
further study their potential application in CO capture. As
shown in Fig. 2b–d. Of all the polymers investigated, CMP-LS2
2
sorption isotherms of Fig. 3 CO
2
, CH
c) at 273 K. CO
and 15/85 at 273 K.
4
, and N
2
adsorption isotherms of CMP-LS1 (a), CMP-LS2 (b) and CMP-LS3
(
2
/CH and CO /N selectivity of CMP-LS1-3 (d) for a molar ratio of 5/95
4 2 2
–
3
2
3
-1
Luminescent properties
and 46.7 cm g at 298 K, respectively, which are comparable The UV-vis absorption spectra of CMP-LS1
to most of the reported POPs under similar conditions (Table absorption peaks at 335 and 271 nm (Fig. S10). Due to the
S1). The CO uptakes of CMP-LS1 and CMP-LS3 are 30.7 and presence of full π-conjugated skeleton derived from the
2
exhibited the highest CO uptake up to 87.4 cm g at 273 K
3
-1
–2 in ethanol show
2
-1
3
3
-1
4
1.6 cm g CO
respectively. Generally, sorbents with high surface areas also strong luminescence in ethanol suspension at 413 nm and 385
have relatively high CO adsorption under the same conditions. nm (λ = 345 and 332 nm (Fig. S11).
2
at 273 K, 16.7 and 23.7 cm g at 298 K, connection of all phenyl rings, CMP-LS1 and CMP-LS2 exhibit a
2
ex
Moreover, the structure and special groups also have an effect
The strong luminescence of CMP-LS1 and CMP-LS2 inspired
on the capture capacity of CO To investigate the binding us to explore their potential applications in the detection of
2
affinity of CMP-LS1 towards CO , we calculated the isosteric nitroaromatic compounds. The luminescent sensing properties
4
2
.
2
–
3
heats of adsorption (Qst) using adsorption data measured at of CMP-LS1 and CMP-LS2 were investigated in ethanol
73 K and 298 K by the Clausius–Clapeyron equation. As suspensions. 2,4-Dinitrotoluene (DNT), 4-nitrotoluene (NT), 4-
shown in Fig. S8, the isosteric heats of CMP-LS1 CMP-LS2 and nitrobenzaldehyde (NBA), 4-chloronitrobenzene (ClNB), 1-
CMP-LS3 at zero coverage are 33.6, 36.6 and 35.3 kJ mol , chloro-2,4-dinitrobenzene (ClDNB), 4-nitrophenol (NP) and
respectively.
picric acid (PA) were added to ethanol suspensions of CMP-LS1
The separation abilities of these three CMPs for different and CMP-LS2 to explore luminescent quenching percentage.
gases at 273 K have also been studied. N and CH sorption The luminescent quench percentage (QP) was calculated with
isotherms were recorded at 273 K (Fig. 3). The CH and N
the equation of QP = [(I – I)/I ] × 100% (Fig. 4). The two
uptakes at 273 K and 1 bar are 10.38 and 2.47 cm g for CMP- polymers display low sensing ability towards DNT, NT, NP, NBA,
2
,
-1
2
4
4
2
o
o
3
-1
3
-1
3
-
LS1, 27.22 and 6.54 cm g for CMP-LS2, 15.70 and 2.82 cm g ClNB and ClDNB in the systems (Fig. S12 and S13). However,
1
for CMP-LS3, respectively. These values are much lower than they show highly sensitive sensing ability towards PA, and the
3
-1
those of CO
2
(30.7, 87.4 and 41.6 cm g ). To evaluate the fluorescence emission maximum was nearly instantaneously
/N selectivities of CMP-LS1 under mixture reduced upon the addition of PA in a relatively short time. The
CO /CH and CO
2
4
2
2
–3
gas conditions with single component isotherms at 273 K, the fluorescence intensities of CMP-LS1 and CMP-LS2 suspensions
ideal adsorbed solution theory (IAST) could be used to predict were quenched to 81% and 83% by increasing the
the multicomponent adsorption behaviors under the concentration of PA to 47.6 μM and 56.6 μM (Fig. 5a and 5b)
conditions of 5% CO
adsorption selectivity for CMP-LS1
.6, 4.5 at 273 K and 1.0 bar (Fig. 3d, Fig. S9 and Table S2). S–V plots for PA of CMP-LS1 and CMP-LS2 are almost linear at
Furthermore, the CO selectivity of CMP-LS1 over N was low concentrations (Fig. 5c and 5d). The quenching constants
also calculated. Under simulated flue gas conditions (CO
for PA are found to be 5.05 × 10 M and 3.70 × 10 M for
2
balanced with 95% CH
4
, the IAST (Fig. S14). The quenching efficiency of PA can be analyzed
–
3
is calculated to be 4.5, using the Stern-Volmer (SV) equation: I /I = 1 + K × [M]. The
o
SV
5
2
–
3
2
4
-1
4
-1
2
/N
selectivity of 23.2, CMP-LS1 and CMP-LS2, respectively, which are comparable to
7.9, 19.8 at 273 K and 1.0 bar (Fig. 3d). In addition, the other reported polymers chemosensors in the literatures
for CO /CH and CO /N are (Table S4). In addition, the recyclability of CMP-LS1 and CMP-
comparable to other POPs (Table S3). These performances LS2 for PA detection have been carried out. The used samples
exhibit that CMP-LS1 can be used as promising materials in can be regenerated after simple centrifugation and washing
gas storage and separation.
three times with ethanol (Fig. 6).
2
,
1
2 2
5/85), CMP-LS1–3 exhibit the CO -over-N
2
selectivities of CMP-LS1
–
3
2
4
2
2
–
3
4
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4
4
fluorescence quenching.
the fluorescence quenching
phenomenon can be explained by the resonance energy
4
5,46
transfer mechanism.
The resonance energy transfer could
occur from fluorophore to non-emissive analyte, if the analyte
and fluorophore are close to each other and the absorption
spectrum of the analyte has an effective overlap with the
emission spectrum of the fluorophore. The greater the spectral
spectrum overlap between the absorbance spectrum of the
analyte and the emission spectrum of the CMPs, the higher the
4
7
Fig. 4 Reduction of luminescence intensities of CMP-LS1 (a) and CMP-LS2 (b) in the
probability of energy transfer. The UV-vis absorption spectra
of these nitroaromatic compounds were compared with the
luminescent spectra of CMP-LS1 and CMP-LS2. As shown in
Fig. S15, the greatest spectral overlap is between PA and the
CMPs, and overlaps occur to some extent in NP/CMPs, while
there are no spectral overlaps between other nitro compounds
and CMPs. Thus, PA has the greatest quenching of the
fluorescence for the CMP-LS1 and CMP-LS2, which could be
promising candidates for practical PA sensing.
presence of different nitroaromatic explosives with the concentration of 47.6 and 56.6
μM.
Conclusions
In summary, three biphenylene-based CMPs have been
synthesized via palladium-catalyzed Suzuki and Sonogashira-
Hagihara polycondensation of 3,4’,5-tribromobiphenyl. These
polymers are mainly microporous materials and show better
CO
exhibits the highest CO
the polymers show good separation ability for CO
CO -over-CH . These properties suggest that CMP-LS1–3
2
absorption capacities. At 273 K and 1.0 bar, CMP-LS2
3
-1
2
uptake of 87 cm g . In addition, all of
2
-over-N
2
and
can
2
4
be adopted as promising materials in gas storage and
separation. Furthermore, owing to π-conjugated skeleton and
the rigid microporous environment, CMP-LS1 and CMP-LS2
exhibit high sensitive and selective fluorescence quenching to
Fig. 5 Emission quenching observed for the suspension of CMP-LS1 (a) and CMP-LS2 (b)
-
1
(
0.25 mg mL in ethanol, λex = 345 and 332 nm) upon addition of nitroaromatic
compounds. The relationship of I /I with PA concentration in ethanol suspensions of
CMP-LS1 (c) and CMP-LS2 (d); (insets: Stern–Volmer plots at low PA concentrations).
o
4
-1
4
-1
PA with the SV constant of 5.05 × 10 M and 3.70 × 10 M . In
terms of environment and security concerns, the present work
suggests that these materials may be fluorescence sensor of
PA.
Conflicts of interest
There are no conflicts to declare.
-
1
)
Acknowledgements
Fig. 6 The quenching and recovery test of CMP-LS1 and CMP-LS2 (0.25 mg ml
dispersed in ethanol in the presence of PA solution (the red bars represent the initial
fluorescence intensities, and the olive and blue bars represent the intensities after the
addition of PA (47.6 and 56.6 μM) for CMP-LS1 and CMP-LS2, respectively).
We thank the National Natural Science Foundation of China
(
Grants: 21471064, 21641004 and 21621001), the “111”
project of the Ministry of Education of China (B17020) and OP
VVV “Excellent Research Teams”, project NO.
Generally, the fluorescence quenching phenomenon can be
explained by the donor-acceptor electron-transfer mechanism
through the interaction between electron-rich CMPs and
CZ.02.1.01/0.0/0.0/15_003/0000417–CUCAM for support to
this work.
4
3
electron-deficient nitro analytes. The conduction band (CB)
of the electron-rich CMPs lies higher than the LUMO energies
of the nitro analytes and upon excitation the excited electron
from the CB transfers to the LUMO orbitals of the nitro
analytes, thus quenching the fluorescence intensity. However,
the electron transfer is not the only mechanism contributing to
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Table of contents
Conjugated microporous polymers based on biphenylene exhibit selective adsorption
CO over CH and N , and luminescent sensing for picric acid.
2
4
2