Synthesis of 1,6-disubstituted pyrene-based conjugated microporous polymers for reversible adsorption and fluorescence sensing of iodine

Article abstract of DOI:10.1039/c9nj05509f

Here we present detailed evidence of highly efficient iodine capture and sensing in 1,6-disubstituted pyrene-based fluorescent conjugated microporous polymers, which were synthesized by a Sonogashira-Hagihara polycondensation reaction (TDP), trimerization

Full text of DOI:10.1039/c9nj05509f

View Article Online
View Journal
NJC
New Journal of Chemistry
Accepted Manuscript
A journal for new directions in chemistry
This article can be cited before page numbers have been issued, to do this please use: T. Geng, C.
Zhang, C. Hu, M. Liu, Y. Fei and H. Xia, New J. Chem., 2020, DOI: 10.1039/C9NJ05509F.
Volume 42
Number
March 2018
Pages 3963-4776
This is an Accepted Manuscript, which has been through the
6
21
Royal Society of Chemistry peer review process and has been
accepted for publication.
NJC
New Journal of Chemistry
rsc.li/njc
A journal for new directions in chemistry
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
rsc.li/njc

Page 1 of 10
New Journal of Chemistry
1
2
3
4
View Article Online
DOI: 10.1039/C9NJ05509F
New journal of chemistry
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
PAPER
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
The synthesis of 1,6-disubstituted pyrene-based conjugated
microporous polymers for reversible adsorbing and fluorescent
sensing to iodine
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
a
a
a
a
a
a
www.rsc.org/
Tong-Mou Geng *, Can Zhang , Chen Hu , Min Liu , Ya-Ting Fei , and Hong-Yu Xia
on pyrene derivatives have been widely used as fluorescence
Abstract Here we present detailed evidence of highly efficient
iodine capture and sensing in 1,6-disubstituted pyrene-based
fluorescent conjugated microporous polymers, which were 12
synthesized by a Sonogashira–Hagihara polycondensation reaction
TDP), trimerization reaction of bi-cycano compound (CPP)
catalyzed using trifluoromethanesulfonic acid (PCPP), and Friedel-
Crafts reaction catalyzed with CH SO H (TTPDP and TDTPAP),
respectively. TDP, PCCP, TTPDP, and TDTPAP have specific surface
areas of 261.9, 43.0, 187.5, and 695.2 m g , and display reversible
guest uptake of 0.61, 3.07, 3.49, 4.19 g g in iodine vapor. The four
CMPs exhibit high sensitivity and selectivity to iodine via
fluorescence quenching. Furthermore, PCPP exhibited extremely
9
sensors in many applications. The derivatives of pyrene were
,10-
also used for building various CMPs used as gas adsorbents
13,14
photocatalysts, fluorescence materials,
and fluorescence
Nevertheless, in spite of the study of pyrene-
15-17
sensors.
(
based CMPs for iodine adsorption, the adsorption capacity is
14,18,19
not high.
In the last few years, the built blocks used in
9-28
3
3
CMPs are most 1,3,6,8-tetrasubstituted pyrene, but there
are a few 1,3,6,8-tetrasubstituted pyrene-based CMPs used as
2
-1
15-17,20-28
fluorescent sensing materials,
as well as a small
-1
15
29
amount of 2,7-disubstituted, 1,3-disubstituted pyrene. To
the best of our knowledge, the CMPs containing 1,6-
disubstituted pyrene have not been reported yet. Because the
asymmetric structure of the 1,6-disubstituted pyrene can
increase the free volume, prevent the fluorescence quenching
caused by stacking, we speculate that the CMPs containing
5
-1
high detection sensitivity to I with K of 1.40×10 L mol and
2
sv
-13
-1
detection limit of 3.14×10 mol L . To the best of our knowledge,
it displays the highest reported Ksv value and the lowest detection
limit value to iodine to date.
1
,6-disubstituted pyrene should possess excellent adsorptive
and fluorescent sensing properties.
Introduction
Porous organic polymers (POPs) have attracted considerable1
attention due to their many exciting potential applications.
Up to present, a variety of POPs have been developed,
2
including polymers of intrinsic microporosity (PIMs), porous
3
aromatic frameworks (PAFs), hypercrosslinked polymers
4,5
6
(
HCPs), covalent triazine-based frameworks (CTFs), covalent
7
organic frameworks (COFs), and conjugated microporous
polymers (CMPs) and so on.
Pyrene is an efficient chromophore with excellent
fluorescent quantum yield and efficient excimer emission that
makes it useful as a fluorescence sensor. Many polymers based
8
a.
AnHui Province Key Laboratory of Optoelectronic and Magnetism Functional
Materials; School of Chemistry and Chemical Engineering, Anqing Normal
University, Anqing 246011.
Electronic Supplementary Informa(on (ESI) available: Synthesis of three
monomers, FT-IR, PXRD, TGA, UV-Vis, SEM,HOMO-LUMO energy levels, and Raman
spectra of the four CMPs, Recycling percentage, Effects of solvents, response time,
and NACs on fluorescent spectra. See DOI:10.1039/x0xx00000x
†
Scheme1. Synthesis of the TDP, PCPP, TTPDP, and TDTPAP.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 2 of 10
COMMUNICATION
Journal Name
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
In this context, we report the synthesis and shift: ppm): 82, 90, 124, 129. Theoretical: C, 96.19; H, 3.81.
characterization of four 1,6-disubstituted pyrene-based CMPs. Found: C, 93.67; H, 4.335.
They were synthesized by Sonogashira–Hagihara reaction
View Article Online
DOI: 10.1039/C9NJ05509F
Trifluoromethanesulfonic acid (CF SO H, 3.04 mL, 23.16
3 3
(
TDP), trimerization reaction of bi-cycano compound (CPP) mmol) and 30 mL of anhydrous CHCl was charged into a pre-
3
catalyzed with trifluoromethanesulfonic acid (PCPP), and dried 3-neck round bottom flask under N atmosphere. The
Friedel-Crafts reaction catalyzed with CH SO H (TTPDP and mixture was cooled to 0 °C, and the solution of CPP (1.4302
TDTPAP), respectively (Scheme 1). Their performance of mmol) and CHCl (60 mL) was dropwisely added into the
adsorbing and fluorescence sensing to iodine have been mixture over 30 min. The mixture was stirred at 0 °C for 2 h,
2
3
3
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
comparatively studied.
and then left overnight at 40 °C, which was poured into 100 mL
of water containing 12 mL of ammonia solution and stirred for
another 2 h. The solid precipitate was filtered and washed with
water, chloroform and then extracted Soxhlet extractor with
chloroform, methanol, and acetone, successively. The product
was dried in vacuum at 50 °C for 24 h to give brown-yellow
(
a)
PCPP
–
1
powder (yield: 73.80 %). FT-IR (KBr, cm ): 1670, 1606, 1502,
13
1
1
3
390, 1315, 1182, 1004, 845, 815. ss C NMR (δ: ppm): 170–
62; 143, 135; 127, 111. Theoretical: C 89.086, N 6.926; H
.987. Found: C 88.31, N 7.656, H 4.031.
,4,6-Trichloro-1,3,5-triazine (TCT) (1.6 mmol) and TPDP
1.2 mmol) were dissolved in 12 mL of dry o-dichlorobenzene,
CH SO H (16.8 mmol) was added the solution, then heated at
DTP
2
2
50 200 150 100
50
0
-50
(
Chemical shift (ppm)
3
3
o
1
40 C for 48 hours. The precipitate was filtered off from the
(b)
hot reaction mixture was soxhlet extracted overnight with
methanol, THF and acetone and dried in vacuum. The target
product (TTPDP) was obtained as a black colored solid with
TDTPAP
-1
yield of 84.85 %. FT-IR ( KBr, cm ): 343, 1622, 1595, 1564,
1
3
1
473, 1383, 813, 749. ss C NMR: 127, 136, 171. Theoretical
calcd.: C 82.48, H 4.40, N 13.12. Found: C 79.92, H 4.575, N
1.088.
TDTPAP was obtained as brownish red colored powder
1
TTPDP
-
1
using the same procedures (yield: 82.17 %). FTIR (KBr, cm ):
2
50 200 150 100
50
0
-50
13
3
1
421, 1628, 1542, 1468, 1383, 797, 697. ss C NMR (ppm):
12, 136, 147, 174. Anal. calcd.: C 84.83, N 10.06, H 4.58.
Chemical shift (ppm)
13
Fig. 1. The ss C NMR spectra of the four CMPs.
Found: C 80.25, N 8.186, H 4.975.
Experimental
Results and discussion
3
1
mmol of 1,6-dibromopyrene, 0.159 mmol of CuI, 3 mmol of
,3,5-triethynylbenzene (TEB), and 0.0516 mmol of Tetrakis(-
The efficient synthesis and characterization of the monomers
CPP, TPDP, and DTPAP were seen in S3-S5 and Fig. S1-S6. The
synthesis routes for the four CMPs with 1,6-disubstituted
pyrene as core are displayed in Scheme 1. TDP was directly
synthesized through Sonogashira–Hagihara coupling reaction
catalyzed by palladium and using a 1.5:1 molar ratio of ethynyl
to bromo functionalities, since this was found to maximize
surface areas in the CMPs. Moreover, DMF as a solvent might
triphenylphosphine) palladium (Pd(PPh ) ) were placed in a
3
4
round-bottom flask with a magnetic stirring rod and a reflow
condenser. The solids were dissolved in a mixture of N,N-
dimethylformamide (DMF) (12 mL) and anhydrous
triethylamine (TEA) (12 mL). After degassing the mixture for 30
min, the reaction was carried out at 90 °C for 3d under a
nitrogen atmosphere with stirring. We cooled the mixture for a
while and eventually reached normal room temperature. The
brown powder was collected by filtration and they are washed
four times with chloroform, water, methanol and acetone (25
mL×4) for each to remove any catalyst or unreacted substance.
Then, the powder was further washed with methanol,
chloroform and tetrahydrofuran (THF) for 24 h using a Soxhlet
extractor. Ultimately, the product was dried at 50 °C under
vacuum for 24 h to afford brown powder (Abbreviation as TDP)
30
give rise to higher surface area materials. CPP with 1,6-
disubstituted pyrene and two aromatic nitriles was selected as
31
the precursor for the synthesis of PCPP. The CF SO H rather
3
3
than zinc chloride was applied to catalyze the cross-linking
trimerization reaction at a much lower temperature (40 °C) for
32,33
a shorter time,
which offers a significant advantage,
avoiding many undesired decomposition and condensation
34
reactions such as C-H bond cleavage and carbonization, as
well as avoid remaining metallic species. After extensive
washing, the insoluble polymer was collected as fine powders
-
1
to (95 %). FTIR (cm ): 3447, 2192, 1628, 1574, 1383, 872, 840.
13
13
Solid state CP/MAS C NMR (ss C NMR) of TDP (chemical
31
in colors form brown-yellow with a yield about 73.80 %.
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 10
Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Journal Name
Unlike the black materials obtained via ionothermal synthesis,
the polymer received after TFMSA catalyzed condensation is various aqueous conditions, implying DthOeI:i1r0.1g0o3o9d/C9cNhJe0m55i0c9aFl
fluorescent powder. TTPDP and TDTPAP were prepared by a stability. Thermogravimetric analysis (TGA) revealed that the
Friedel–Crafts reaction of TCT with TPDP and DTPAP with decomposition temperature of the CMPs in nitrogen are 140,
COMMUNICATION
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
The CMP networks were insoluble in organicVsieowlvAertincltesOanlninde
31,34
CH SO H as a catalyst, which were well-defined para- 352/581, 350/563, and 573 °C , respectively (Fig. S9).
3
3
substituted inferred via the model product, simple and Powder X-ray diffraction measurements (XRD) (Fig.S10)
convenient, including moderate processing temperature, the showed that the CMP networks were amorphous, and no
inexpensive catalysts relatively low toxicity, and commercially evidence for characteristic reflections from a crystalline phase
available TCT and the building blocks without special or layered sheets was observed. SEM images showed that TDP
functional groups are used, preferably in a metal-free shows a series of aggregated particles, while other three CMPs
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
35
38
regime.
are made up of blocks. (Fig. S11).
350
Their structures were characterized by Fourier transform
infrared (FT-IR) spectroscopy. In Fig. S7a, the characteristic-
terminal C≡C–H triple bond vibration peaks at about 3298 cm
(a)
300
250
200
TDP
TDP
PCPP
PCPP
TTPDP
TTPDP
TDTPAP
TDTPAP
1
had very lower intensity for TDP, while the peaks at around
-
1
2
192 cm , which were characteristic of substituted acetylene,
36
150
were easily detected. The strong absorption peak situated at
8
absorb summits at circa 1628, 1574, and 1383 cm belonged
to the benzene and pyrene. The spectra of PCPP in Fig. S7b
show significant decrease in the intense of carbonitrile band
around at 2228 cm along with the emergence of strong peaks
of triazine rings at 1502, 1390, and 800 cm , indicative a high
degree of reaction.
-1
40 cm was assigned to the substituted phenylene, while the
100
50
0
-1
37
0.0
0.2
0.4
0.6
0.8
1.0
–
1
Relative Pressure (p/p0)
–
1
0.10
0.08
0.06
0.04
0.02
31,32,34
(b)
Fig. S7cd show the FT-IR spectra of
the TTPDP and TDTPAP networks. The stretching vibration
TDP
PCPP
TTPDP
TDTPAP
-1
summit of C-Cl located at 847 cm almost disappears,
35
indicating the complete conversion of C–Cl. The emerging of
-1
the absorption bands at 1602, 1563, and 1468 cm prove the
existence of the triazine ring (Fig. S7bcd). In Fig. S7, the
characteristic peaks at 1574, 1606, 1595, 1542 and 1383, 1390,
-
1
0.00
1
380, 1383 cm should be put down to benzene ring. Further
0
2
4
6
8
10 12 14 16
evidence of the formation of the target networks are given by
Average Diameter (nm)
-1
the intense bands at 1627, 1670, 1622 and 1628 cm , which
3
6,37
Fig. 2. (a) Nitrogen adsorption-desorption isotherms measured at 77 K for●
TDP, ▲ PCPP, ◆ TTPDP, and ★ TDTPAP; (b) BJH pore size distribution
profile of TDP, PCPP, TTPDP, and TDTPAP. ●▲◆★ Adsorption isothermal
curves, ○△◇☆ Desorption isothermal curves.
are attributed to pyrene ring.
The CMPs were further
13
characterised at the molecular level by ss C NMR. As shown
in Fig. 1, the peaks at around 174–162 ppm are from the C=N-
31-34
in the s-triazine rings.
The signal at 143 ppm belongs to the
carbon atom of the phenyl or pyrene ring connecting the
triazine ring and pyrene ring or phenyl ring. The peak at 135
ppm is assigned to the carbon in pyrene. Wide peak center at
Porosity of the resulting CMPs were studied by means of
nitrogen adsorption–desorption measurement at 77.3 K (Fig.
). TDP, PCPP, TTPDP, and TDTPAP perform Type II, Type III,
Type I, and Type II gas sorption isotherms as well as some
hysteresis phenomenon, which might be attributed to the
2
1
27 ppm correspond to the unsubstituted phenyl and pyrene
31,33
carbon.
The low intensity peaks at 111-110 ppm are
31-34
ascribed to the SP carbon from residual -CN.
Elemental
existence of a mesoporous structure and interparticulate voids
analysis of forementioned CMPs show some deviations
common for microporous materials due to incomplete
combustion and adsorbed water and gases in the pore
31,33,34
of the samples.
The four CMPs showed a significant low-
pressure hysteresis, which are diffusional limitations by pore
blocking influences arised as a consequence of the micropore
31,34
structure.
UV-Vis absorption spectra were used to compare
39
morphology and connectivity rather than swelling effects. If
the electronic properties of the CMPs against the starting
materials (Fig. S8). The broad absorption between 200 and 800
nm observed in the four CMPs are the result of
complementary absorption of the pyrene-based building block.
The absorption of the pyrene moiety were shifted from 385,
low pressure adsorption-desortion isotherms would have been
recorded, there would not be a closure of the isotherms. This
behavior was associated with the irreversible uptake of gas
40
molecules in the pores (or through pore entrances). Pore size
distribution curves for the CMPs calculated using nonlocal
density functional theory (NL-DFT) are shown in Fig. 2b. The
polymer networks exhibited the micropore diameter centering
2
(
67/357, 537, and 429 nm for the four micropore materials
TDP, PCPP, TTPDP, as well as TDTPAP) to 464, 411/561, 598,
and 535 nm in relative monomers. These results indicate the
13,14,16,20
around 1.22, 1.22, 1.88, and 1.22 nm, respectively, in
extended conjugation in the CMPs.
34
agreement with the shape of the N isotherms (Fig. 2a). As
2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 4 of 10
COMMUNICATION
Journal Name
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
shown in Table 1, PCPP has the lowest apparent BET surface that the adsorptive capacity of PCPP, TTPDP, and TDTPAP are
View Article Online
DOI: 10.1039/C9NJ05509F
2
-1
area with 43.0 m g , whereas other CMPs possess not only higher than that of TDP, which indicated that s-triazine ring
2
-
high apparent BET surface areas (261.9, 187.5, and 695.2 m g plays a vital role in increasing iodine capture, because
1
for TDP, TTPDP, and TDTPAP, respectively), but also large introducing of the electron-deficient s-triazine may enhance
micropore volume at p/p =0.1 (V ) with 0.23, 0.30, 0.049, and the dipole-dipole interaction between sorbate molecule and
0
0.1
3
-1
46
0
.26 cm g . In accordance with calculating from single point adsorbent. In addition, there was only the nonpolar
measurements (p/p =0.97), the pore volumes are 0.31, 0.30, interaction of π-surfaces of triple bonds and pyrene with I2
0
3
-1 31,34
0.10, and 0.49 cm g .
The V /V value which is the rather than chemical bond formation between I and acetylene
0.1 tot 2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
8
micropore volume divided by the total pore volume gives an bonds. As shown in Fig. S7 and Table S3, the center or
indication of the percentage microporosity in the materials, intensity of the peaks of pyrene and benzene units have more
which are higher than 0.40 (Table 1), meaning that micropores changes after introducing triazine. Moreover, the iodine
are dominant in the networks. Their highly rigid and contorted adsorption capacity of TTPDP and TDTPAP are greater than
molecular structure based on the connatural structure of 1,6- that of PCPP, which means that the triphenylamine (TPA) units
disubstituted pyrene should prohibit space-efficient packing in can enhance the iodine adsorption ability. This is because TPA
31,32
the solid state.
are provided with electron-rich, propellerlike geometry, and
central electroactive nitrogen atom. These results are of
great significance for the design iodine adsorbed porous
4
7
Table 1. Pore and surface properties of CMPs.
a
a
c
c
CMPs
S
BET
2
S
Langmuir
V
total
V
micro
3
V
micro
/
S
micro
2
organic polymers. TGA was also conducted on I
@CMPs to
2
-
2
-1
b
-
-
(m g
(m g )
(tpv)
(cm g
V
total
(m g
calculate the I loading (Fig. S9). The TGA curves revealed the
2
1
3
-1
1
1
)
(cm g )
0.3051
0.3036
0.0999
0.4913
)
)
significant weight loss of the iodine-loaded CMPs in the range
of 90 to 350 °C. The mass loss of iodine were thus estimated to
be 0.53 (86.43 %), 2.66 (86.54 %), 3.32 (95.15 %), and 3.86
TDP
PCPP
261.9
43.0
-
0.2292
0.2977
0.0493
0.2659
0.7512
0.9729
0.4932
0.5412
123.9
4.3
51.8
-
1
(
92.12 %) g g relative to the mass of TDP, PCPP, TTPDP, and
TTPAP
TDTPAP
187.5
695.2
-
-
56.6
214.6
4
8,49
TDTPAP.
The subtle differences may be caused by some
50
a
incomplete release of iodine at the calculated temperature.
Specific surface area calculated from the adsorption branch of the nitrogen
isotherm using the BET method in the relative pressure (p/p ) range from
.01 to 0.10.
0
4.5
0
(a)
4.0
b
c
0
Total pore volume is obtained from BET data up to p/p =0.99 and is
3.5
defined as the sum of micropore volume and volumes of larger pores.
Micropore volume calculated from nitrogen adsorption isotherm using the
t plot method.
3
.0
2.5
TDP
PCPP
TTPDP
TDTPAP
2
1
1
0
0
.0
.5
.0
.5
.0
Recently, the development of porous absorbents for
efficient I2 capture has attracted considerable attention
because I is a dangerous radioisotope in nuclear waste, such
2
129
as I, which is an important radioisotope in nuclear waste
7
40,41
0
10
20
30
40
50
60
with a very long half-life of 1.57×10 years.
was conducted under typical fuel reprocessing conditions (350
K and ambient pressure, the as-loaded materials are denoted
The I capture
2
Time (h)
Fig. 3. Gravimetric uptake of iodine as a function of time at 350 K.
as I @CMPs). For each measurement, the dried CMP powder
2
was placed in a pre-weighted glass vial. The vial and excess
solid iodine were put together in a closed system at ambient cyclohexane (CHA), ethanol (EtOH), and dioxane (DOX) at 350
pressure and 350 K.
PCPP, and TDTPAP changed from russetish, brown yellow, and TDTPAP decreased with the increase of a solvent's polarity.
brown to almost black (Fig. S12).
is deep black, hence, the color change of the sample could not very low, which leads to a high iodine–water selectivity.
be found with the time progressed. Fig. 3 shows the weight of Therefore, TDP, TTPDP, and TDTPAP could sorption iodine over
the samples at various time intervals during the iodine uptake. water which is advantageous for the actual industrial
The iodine adsorption increased significantly with prolonged application of the iodine sorption process under humid
contact time. In the initial 12 h, the adsorption capacities of condition.
CMPs were relatively quick. No further change in the iodine
The strong interactions expected to exist between the π-
The adsorption selectivity has been carried out with water,
41-43
As time progressed, the color of TDP, K for 60 h (Fig. 4). The uptake capacity of TDP, TTPDP, and
41-45
Due to the color of TTPDP Delightedly, the water sorption values of the three CMPs are
45
loading amounts was observed after 48 h, suggesting that the electron systems and iodine in the CMPs could be considered
systems were basically saturated. The equilibrium iodine using modern analytical instruments. The UV-Vis spectra of
uptakes of TDP, PCPP, TTPDP, and TDTPAP were 0.61, 3.07,
I
2
@CMPs (Fig. S13) showed that no additional peaks at about
The iodine adsorption capacity of TTPDP 731 nm resulting from pristine iodine crystals were observed in
and TDTPAP are the highest values in that of the pyrene-based the iodine-loaded sorbents. Moreover, powder XRD
POPs (Table S1) and are comparable to that of triazine-based measurement (Fig. S14) revealed that @CMPs were
POPs and triphenylamine-based POPs (Table S2). It can be seen amorphous in nature without any prominent crystalline
-1 41-45
3.49, 4.19 g g .
I
2
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 10
Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Journal Name
COMMUNICATION
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
-1
diffraction peaks, indicating that the adsorbed iodine solutions of 300 mg L , the adsorption equilibrium only need 1
View Article Online
DOI: 10.1039/C9NJ05509F
molecules were completely transformed into polyiodide hour, and the removal efficiency of 99.92 % was obtained.
51
anions. The structure of the iodine inside the pores of the
CMPs were revealed by Raman spectroscopy (Fig. S15). The
-1
-
strong peak located at about 165 cm belonged to I . The
laboratorial results indicate that the charge transfer occurred
between the guest iodine molecules and the electron-rich host
5
44,52
networks at high extent .
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
TDP
TTPDP
TDTPAP
I2 Water CHA EtOH DOX
Fig. 4. The adsorption selectivity of TDP, TTPDP, and TDTPAP for I
CHA, EtOH, and DOX
2
, water,
.
When the I -loaded TDP, PCPP, TTPDP, and TDTPAP were
heated at 398 K under ambient pressure and air atmosphere
for 120 min, iodine release efficiency was as high as 99.72 %,
2
4
4,51
9
5.21 %, 97.13 %, and 96.26 % (Fig. S16).
The excellent
iodine release encouraged us to exploit the recyclability of the
adsorbents. Recycling were performed by taking iodine-loaded
PCPP, TTPDP, and TDTPAP samples (after exposure of as-
synthesized CMPs to iodine for 24 h at 350 K) and heating at
3
98 K for 120 min. The samples were then reused for iodine
uptake again at same conditions. After reusing three times, the
iodine uptake percentage of PCPP, TTPDP, and TDTPAP were
9
3.06 %, 95.88 %, and 88.65 %, while recycling percentage
were found to be 95.89 %, 86.52 %, and 91.51 %, respectively
Fig. S17). These very high values make our CMPs to be
attractive materials for use as the robust recyclable and
(
51,53
reversible iodine adsorbents.
In addition, the CMPs are capable of trapping iodine in
solution. To estimate the adsorption kinetics of CMPs for
iodine-CHA solution, the UV-Vis spectra were employed to
measure the change of the maximum adsorption at 523 nm
(
Fig. S18 and S19). It can be seen that two stages of adsorption
kinetic were obtained: the adsorption capacity for iodine
increased quickly during the first 12, 12, 1, and 12 h for TDP,
PCPP, TTPDP, and TDTPAP, respectively, and after these the
slow increases were observed until equilibrium were reached.
Removal efficiency of PCPP and TTPDP with 86.80 % and 99.92 %
were acquired for iodine solutions in 300 mg L , while removal
efficiency of TDP and TDTPAP with 87.71 % and 90.91 % were
achieved in iodine solutions of 100 mg L .
the colors of the solution of iodine in cyclohexane became
paler, which indicated that the iodine was encapsulated into
the CMP networks to successively generate I @CMPs. It is
important to note that the adsorption rate of TTPDP is the
fastest and the removal efficiency is the highest. Even in iodine
-1
-1 40,42,44
Furthermore,
Fig. 5. Fluorescence spectra of CMPs dispersed in different solvents [(a)TDP:
λ ex=400 nm, (b) PCPP: λ ex=400 nm, (c) TTPDP: λ ex=350 nm, (d) TDTPAP:
λ ex=380 nm]. Inserts: The fluorescence photographs of CMPs dispersed in
different solvents, where fluorescence is excited under 365 nm using a
53
2
portable UV lamp
.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 6 of 10
COMMUNICATION
Journal Name
The encapsulated iodine could be facilely eliminated from
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
1
0
.0
.8
(
a)
the frameworks upon immersion of
DO
I
@
2
I:
CM
10
.10
Ps
3
9/Cin9N
o
J0rg55
anic
0
9F
solvents. The iodine-loaded CMPs were soaked in fresh
ethanol, the color of the ethanol solution deepened from
colorless to dark brown, which clearly indicates that the guests
are dissociated from the CMP frameworks (Fig. S20 and S21
[
I ]
0
2
0.6
43
0
0
0
.4
.2
.0
Inserts). To investigate the kinetics of iodine delivery by
CMPs, the UV-Vis spectra were recorded at room temperature.
The iodine release rates become slower after 8, 4, 8, and 4 h
owing to the fact that the concentration of iodine in ethanol
increased with time. After 12 h, however, about 75.14 %,
-
3
-1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2.5*10 mol L
4
50
500
550
600
650
700
750
8
4.82 %, 55.47%, and 64.10 % of the initial iodine had been
Wavelength (nm)
released from I @CMPs, indicating the reversibility of the
2
41,51
iodine adsorption process.
1.0
(b)
The TDP, PCPP, TTPDP, and TDTPAP possess high absolute
fluorescence quantum yields with 78.32 %, 63.45 %, 51.57 %,
and 70.45 %, which encouraged us explored their fluorescence
sensing properties for iodine. The four CMPs were dispersed in
common organic solvents, such as ACN, acetone, DMF, DOX,
chloroform, THF, and EtOH. As shown in Fig. 5, their
0.8
0.6
0.4
0.2
[I2]
0
-
3
-1
2.5*10 mol L
54,55
fluorescence spectra showed remarkable difference.
Among these solvents, the most explicit fluorescence
enhancement in THF, DMF, DOX to CMPs, and low emission
0.0
55-57
450 500 550 600 650 700 750 800
were observed in ACN, EtOH, and acetone.
Another
Wavelength (nm)
interesting phenomenon was observed, upon exciting under
the UV light at 365 nm, TDP transmits blue fluorescence in the
dispersions of DMF, chloroform, and THF. PCPP emitted
various colored fluorescence in the dispersions of these
solvents except for ACN. TTPDP emitted blue fluorescence only
in the dispersion of DMF. TDTPAP emitted bright cyan
fluorescence in the dispersions of DMF, DOX, and THF (Fig. 5.
1
0
0
0
.0
(c)
[
I2] 0
.8
.6
.4
-
4
-1
2
.5*10 mol L
56,57
Inserts).
The sensing performance of CMPs to I solusion
2
have been reported. When I was added into the dispersion of
2
the CMPs (Fig. S22), we observed that the fluorescence
0.2
.0
58,59
emission were almost instantaneously reduced.
These
0
results indicated that the microporous architecture facilitates
the sensing process and improves the response to NACs and
4
00
450
500
550
600
650
Wavelength (nm)
60
I .
2
-1
When quantitative I was added into the 1.0 mg mL of
2
1
.0
.8
0.6
the four CMPs dispersions, respectively, it was found that
(d)
fluorescence of the dispersions could be readily quenched by I
2
0
16,31
(
Fig. 6).
the four CMPs in various solvents were different.
further use the Stern-Volmer equation to calculate the
Obviously, the fluorescence quenching degrees of
[
I2] 0
15,17,54
We
I2
0
0
0
.4
.2
.0
quenching coefficients: I /I=1+K [I ], where I is the
0 sv 2
-
3
-1
1
.5*10 mol L
fluorescence intensity after adding the I of concentration, and
2
Ksv is the quenching coefficient. There are good linear Stern–
Volmer relationships of the four CMPs for sensing to I2.
Delightfully, the Ksv and limits of detection (LOD) of the four
4
00 450 500 550 600 650 700 750
3
5
-1
-13
-9
CMPs reach from 10 to 10 L mol and from 10 to 10 mol
Wavelength (nm)
-1
15,16,31,54,55
L , respectively (Fig. S23 and Table S4).
To the best
of our knowledge, PCPP is one of the highest sensitivity for
60
Fig. 6. Fluorescence spectral changes of (a) TDP (
DMF), (b) PCPP ( ex=400 nm, in DMF), (c) TTPDP (
DMF), and (d) TDTPAP( ex=380 nm, in DOX) upon addition of I
λ
ex=400 nm, in fluorescence sensing to iodine (Table S5). Although the TPA
λ
λ
ex=350 nm, in units can improve the adsorption performance of iodine, the
61
λ
2
.
improvement of the sensing performance is not significant.
The order of sensitivity of fluorescence sensing to iodine is:
5
4
4
PCPP(1.40×10 )> TDP(6.10×10 )> TTPDP(2.02×10 )> TDTPAP
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 10
Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Journal Name
COMMUNICATION
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3
(
1
4.65×10 ). This result means that the distorted structure of four CMPs. As shown in Fig. 7, there are overlaps between the
View Article Online
,6-pyrene is enough to prevent the fluorescence quenching two spectra of PA and the four CMPs, asDOwI:e1l0l .a10s3b9e/Ct9wNeJe0n55t0h9eF
caused by pyrene aggregation. The introduction of the TPA spectra of I with the TDP, TTPDP, and TDTPAP, which means
units into the CMP networks can reduce their sensitivity to that there are energy transfer between PA, I and some CMPs,
iodine.
2
2
suggesting that they are the both energy transfer mechanism
1
5
To better study the effects of nitroaromatic compounds and electrons transfer mechanism. The calculated the
NACs), such as o-nitrophenol (o-NP), PA, 2,4-dinitrotoluene lowest-unoccupied molecular orbital (LUMO) energy level of I2
DNT), nitrobenzene (NB), m-dinitrobenzene (m-DNB), p- is -4.988 eV, which is much lower than that of the four CMPs
(
(
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
dinitrobenzene (p-DNB), p-nitrotoluene (NT), as well as phenol (TDP: -2.224, PCPP: -2.062, TTPDP: -2.026, and TDTPAP: -2.060
PhOH), o-dichlorobenzene (DClB) on the sensing property of eV), thus providing a strong driving force for the electron
(
TDP, TTPDP, and TDTPAP for I , we performed a series of transfer (Table 2 and Fig. S25). Upon excitation, electrons are
selectivity and competition experiments by testing the transferred from the conduction band of CMPs to the LUMO of
fluorescence changes in the presence of I . It can be seen from the I , which result in the formation of complex of polyiodide
2
2
2
Fig. S24 (red bars) that TDP and TTPDP have high selectivity for anion and CMP skeleton, leading to the quenching and
6
1
I , the PCPP has high selectivity for PA, and TDTPAP has high adsorption phenomenon. In addition, the of electrovalent
2
1
5,54
selectivity for I and o-NP.
The introduction of the TPA units bonds between polyiodide anion and CMP skeleton, as well as
2
into the CMP networks can reduce their selectivity to iodine. the hydrogen bonds of PA, o-NP and CMP networks can also
The competition of CMPs toward the I or PA detection were greatly enhance adsorption and fluorescence sensing.
then investigated by testing the fluorescence change in the
presence of CMPs (1.0 mg mL ) and I or PA adding equal
equivalent of other NACs and I . It showed that the fluorescent
intensity of PCPP almost has no appreciable influence on PA
after added NACs, while the fluorescent intensity of TDP,
TTPDP, and TDTPAP almost has also no obvious influence on I
after added NACs except for PA and o-NP.
28,62
2
-
1
2
2
Table 2. HOMO and LUMO calculations for the four CMPs, I and the NCAs.
2
All the molecular orbital calculations were performed with the Gaussian 09
D 0.1 program at the B3LYP/6-31G* level.
MO energy (eV)
LUMO
TDP
-2.224
-5.114
p-NT
PCPP
-2.062
-5.278
DNT
TTPDP
-2.026
-5.311
NB
TDTPAP
-2.060
-5.271
p-DNB
-3.495
-8.350
I
2
2
-4.988
-7.553
m-DNB
-3.135
-8.413
1
5
HOMO
MO energy (eV)
LUMO
1.0
0.8
0.6
1.0
(
a)
TDP
PCPP
-2.318
-7.364
PA
-2.977
-8.1131
o-NP
-2.428
-7.591
PhOH
-0.3331
-6.566
TTPDP 0.8
HOMO
DNT
NB
o-NP
p-NT
PA
MO energy (eV)
LUMO
0.6
-3.898
-8.237
-2.711
-6.797
0.4
m-DNB 0.4
PhOH
HOMO
p-DNB
I2
0
.2
.0
0.2
Conclusions
0
0.0
3
00
400
500
600
700
800
In conclusion, four 1,6-disubstituted pyrene-based
fluorescent conjugated microporous polymers with
amorphous structure were successfully designed and
synthesized by different polymerization reactions, such as a
Sonogashira–Hagihara polycondensation reaction (TDP),
trimerization reaction of bi-cycano compound catalyzed using
trifluoromethanesulfonic acid (PCPP), and Friedel-Crafts
reaction catalyzed by CH SO H (TTPDP and TDTPAP). The
performance of adsorb and fluorescence sensing to iodine for
the four CMPs have been comparatively studied. It is found
that the four CMPs display reversible guest uptake in iodine
vapor. The four CMPs exhibit high sensitivity to iodine via
fluorescence quenching. In especial, PCPP exhibited extremely
Wavelength (nm)
3
.0
2.5
.0
1.5
.0
0.5
.0
3.0
2.5
2.0
1.5
1.0
0.5
0.0
(b)
TDTPAP
m-DNB
DNT
NB
o-NP
p-NT
PA
p-DNB
PhOH
I2
2
3
3
1
0
300
400
500
600
700
800
Wavelength (nm)
high detection sensitivity to I . To the best of our knowledge, it
Fig. 7. The absorption spectra of I
2
and NACs (o-NP, PA, PhOH, DNT, p-NT, m-
2
displays the highest reported KSV value and lowest detection
limit to iodine to date. Although the introduction of the TPA
units into the CMP networks can improve the adsorption
performance of iodine, it can reduce their fluorescence sensing
sensitivity and selectivity to iodine.
DNB, p-DNB, and NB) and fluorescence spectra of (a) TDP (λ ex=400 nm),
PCPP (λ ex=400 nm) and TTPDP (λ ex=350 nm) in DMF; (b) TDTPAP (λ
-
1
ex=380 nm) in DOX (1.0 mg mL ).
We also investigated the adsorbing and quenching
mechanism by measuring the absorption spectra of I , NACs
(o-NP, PA, PhOH, DNT, p-NT, p-DNB, m-DNB, and NB), PhOH,
DClB, and made a comparison with the emission spectra of the
2
Acknowledgements
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 8 of 10
COMMUNICATION
Journal Name
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
This work was supported by Natural Science Foundation 23 G. Cheng, T. Hasell, A. Trewin, D. J. Adams, A. I. Cooper,
of Anhui Education Department (under Grant No.
KJ2018A0319).
View Article Online
DOI: 10.1039/C9NJ05509F
Angew. Chem., 2012, 124, 12899–12903.
24 M. G. Rabbani, A. K. Sekizkardes, O. M. El-Kadri, B. R.
Kaafarani, H. M. El-Kaderi, J. Mater. Chem., 2012, 22
5409–25417.
,
2
References
2
5 M. G. Rabbani, A. K. Sekizkardes, Z. Kahveci, T. E. Reich, R.
Ding, H. M. El-Kaderi, Chem. Eur. J., 2013, 19, 3324– 3328.
6 V. C. University, T. T. Zhang, H. T. Wang, H. P. Ma, F. X. Sun,
X. Q. Cui, G. S. Zhu, Acta Chim. Sinica, 2013, 71, 1598–
1
X. Feng, X. S. Ding, D. L. Jiang, Chem. Soc. Rev., 2012, 41
010–6022.
,
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
6
2
N. B. McKeown, B. Gahnem, K. J. Msayib, P. M. Budd, C. E.
Tattershall, K. Mahmood, S. Tan, D. Book, H. W. Langmi,
Angew. Chem. Int. Ed., 2006, 45, 1804–1807.
1602.
2
2
2
3
7 K. V. Rao, R. Haldar, T. K. Maji, S. J. George, Phys. Chem.
Chem. Phys., 2016, 18, 156–163.
3
4
5
6
7
D. Yuan, W. Lu, D. Zhao and H. C. Zhou, Adv. Mater., 2011,
8 S. Dalapati, S. Jin, J. Gao, Y. Xu, A. Nagai, D. Jiang, J. Am.
Chem. Soc., 2013, 135, 17310–17313.
9 G. Cheng, B. Bonillo, R. S. Sprick, D. J. Adams, T. Hasell, A. I.
Cooper, Adv. Funct. Mater., 2014, 24, 5219–5224.
0 J. X. Jiang, F. Su, A. Trewin, C. D. Wood, H. Niu, J. T. A. Jones,
2
3
, 3723–3725.
Z. A. Qiao, S. H. Chai, K. Nelson, Z. H. Bi, J. H. Chen, S. M.
Mahurin, X. Zhu, S. Dai, Nat. Commun., 2014, , 3705.
5
Z. H. Li, D. C. Wu, Y. R. Liang, R. W. Fu, K. Matyjaszewski, J.
Am. Chem. Soc., 2014, 136, 4805–4808.
M.J. Bojdys, J. Jeromenok, A. Thomas, M. Antonietti, Adv.
Mater., 2010, 22, 2202–2205.
J. W. Colson, A. R. Woll, A. Mukherjee, M. P. Levendorf, E.L.
Spitler, V. B. Shields, M. G. Spencer, J. Park, W. R. Dichtel,
Science, 2011, 332, 228.
Y. Z. Khimyak, A. I. Cooper, J. Am. Chem. Soc., 2008, 130
710–7720.
,
7
3
1 X. Y. Wang, C. Zhang, Y. Zhao, S. J. Ren, J. X. Jiang,
Macromol. Rapid Commun., 2016, 37, 323–329.
2 C. Y. K. Chan, J. W. Y. Lam, C. K. W. Jim, H. H. Y. Sung, I. D.
Williams, B. Z. Tang, Macromolecules, 2013, 46, 9494–
3
8
9
X. Liu, Y. Xu, D. Jiang, J. Am. Chem. Soc., 2012, 134, 8738–
9
506.
8
741.
J. X. Jiang, A. Trewin, D. J. Adams, A. I. Cooper, Chem. Sci. ,
011, , 1777–1781.
3
3 X. Zhu, C. C. Tian, S. M. Mahurin, S. H. Chai, C. M. L. Wang, S.
Brown, Veith, G. M. Luo, M. H, H. L.Liu, S. Dai, J. Am. Chem.
Soc., 2012, 134, 10478–10484.
2
2
10 K. V. Rao, S. Mohapatra, T. K. Maji, S. J. George, Chem. Eur.
J., 2012, 18, 4505–4509.
3
4 R. Gomes, P. Bhanja, A. Bhaumik, Chem. Commun., 2015,
5
1
, 10050–10053.
5 S. H. Xiong, X. Fu, L. Xiang, G. P. Yu, J. G. Guan, Z. G. Wang,
Y. Du, X. Xiong, C. Y. Pan, Polym. Chem., 2014, , 3424–
431.
6 J. L. Novotney, W. R. Dichtel, ACS Macro. Lett., 2013,
23–478.
7 J. Brandt, J. Schmidt, A. Thomas, J.D. Epping, J. W. Tunable,
Polym. Chem., 2011, , 1950–1952.
8 S. Ren, M. J. Bojdys, R. Dawson, A. Laybourn, Y. Z. Khimyak,
D. J. Adams, A. I. Cooper, Porous, Adv. Mater., 2012, 24
357–2361.
9 J. Jeromenok, J. Weber, Langmuir, 2013, 29, 12982–12989.
0 H. Ma, J. J. Chen, L. X. Tan, J. H. Bu, Y. H. Zhu, B. E. Tan, C.
Zhang, ACS Macro. Lett., 2016, , 1039–1043.
1 Q. Q. Dang, X. M. Wang, Y. F. Zhan and X. M. Zhang, Polym.
Chem., 2016, , 643–647.
11 Z. J. Yan, H. Ren, H. P. Ma, R. R. Yuan, Y. Yuan, Xi. Q. Zou, F.
X. Sun, G. S. Zhu, Micropor. Mesopor. Mat., 2013, 173, 92–
3
5
9
8.
2 M. Yu, X. Y. Wang, X. Yang, Y. Zhao, J. X. Jiang, Polym.
Chem., 2015, , 3217–3223.
3 R. S. Sprick, J. X. Jiang, B. Bonillo, S. J. Ren, T. Ratvijitvech, P.
Guiglion, M. A. Zwijnenburg, D. J. Adams, A. I. Cooper, J.
Am. Chem. Soc., 2015, 137, 3265–3270.
3
1
1
3
3
3
2,
6
4
2
14 K. C. Park, J. Cho, C. Y. Lee, RSC Adv., 2016, 6, 75478–75481.
,
1
1
1
1
1
5 L. Guo, D. P. Cao, J. Yun, X. F. Zeng, Sensor. Actuat. B–-
Chem., 2017, 243, 753–760.
2
3
4
6 D. X. Wang, S. Y. Feng, H. Z. Liu, Chem. Eur. J., 2016, 22
4319–14327.
,
1
5
7 G. Q. Lin, H. M. Ding, D. Q. Yuan, B. S. Wang, C. Wang, J.
Am. Chem. Soc., 2016, 138, 3302–3305.
8 D. Shetty, J. Raya, D. S. Han, Z. Asfari, J. C. Olsen, A. Trabolsi,
Chem. Mater., 2017, 21, 8968–8972.
9 G. Das, T. Skorjanc, S. K Sharma, T. Prakasam, C. Platas-
Iglesias, D. S. Han, J. Raya, J. C. Olsen, R. Jagannathan, A.
4
4
7
2 Y. F. Chen, H. Sun, R. X. Yang, T. T. Wang, C. J. Pei, Z. T.
Xiang, Z. Q. Zhu, W. D. Liang, A. Li, W. Q. Deng, J. Mater.
Chem. A, 2015, 3, 87–91.
4
3 S. A, Y.W. Zhang, Z. P. Li, H. Xia, M. Xue, X. M. Liu, Y. Mu,
Trabolsi, ChemNanoMat., 2018, 4, 61–65.
Chem. Commun., 2014, 50, 8495–8498.
2
0 M. A. Zwijnenburg, G. Cheng, T. O. McDonald, K. E. Jelfs, J.
X. Jiang, S. J. Ren, T. Hasell, F. Blanc, A. I. Cooper, D. J.
Adams, Macromolecules, 2013, 46, 7696–7704.
4
4
4
4
4 Z. J. Yan, Y. Yuan, Y. Y. Tian, D. M. Zhang, G. S. Zhu, Angew.
Chem. Int. Ed., 2015, 54, 12733–12737.
5 C. Y. Pei, T. Ben, S. X. Xu, S. L. Qiu, J. Mater. Chem. A, 2014,
2
1 L. J. Abbott, C. M. Colina, J. Chem. Eng. Data., 2014, 59
177–3182.
2 A. K. Sekizkardes, T. S. Glu, Z. F. Kahveci, H. M. El-Kaderi, J.
,
2
, 7179–7187.
3
6 S. Gu, J. Guo, Q. Huang, J. Q. He, Y. Fu, G. C. Kuang, C. Y.
Pan, G. P. Yu, Macromolecules, 2017, 21, 8512–8520.
7 T. M. Geng, S. N. Ye, Z. M. Zhu, W.Y. Zhang . J. Mater. Chem.
2
Mater. Chem. A, 2014, 2, 12492–12500.
A, 2018, 6, 2808–2816.
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 10
Pl eNa es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Journal Name
COMMUNICATION
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
48 T. Skorjanc, D. Shetty, S. K. Sharma, J. Raya, H. Traboulsi, D.
View Article Online
DOI: 10.1039/C9NJ05509F
S. Han, J. Lalla, R. Newlon, R. Jagannathan, S. Kirmizialtin,
J.C. Olsen, Chem. Eur. J., 2018, 24, 1–9.
4
5
9 M. Janeta, W. Bury, S. Szafert, ACS Appl. Mater. Interfaces,
2
018, 10, 19964–19973.
0 X.H. Guo, Y. Tian, M.C. Zhang, Y. Li, R. Wen, X. Li, X.F. Li, Y.
Xue, L.J. Ma, C.Q. Xia, S.J. Li, Chem. Mater., 2018, , 2299–
308.
1 X. Qian, Z. Q. Zhu, H. X. Sun, F. Ren, P. Mu, W. D. Liang, L. H.
Chen, A. Li, ACS Appl. Mater. Interfaces, 2016, , 21063–
1069.
7
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
8
2
5
2 Y. Z. Liao, J. Weber, B. M. Mills, Z. H. Ren, C. F. J. Fau,
Macromolecules, 2016, 49, 6322–6333.
5
3 G. Das, T. Prakasam, S. Nuryyeva, D. S. Han, A. Abdel-
Wahab, J. C. Olsen, K. Polychronopoulou, C. Platas-Iglesias,
F. Ravaux, M. Jouiad, l. Trabolsi, J. Mater. Chem. A, 2016,
5361–15369.
4 L. Guo, X. F. Zeng, D. P Cao, Sens. Actuat. B-Chem., 2016,
26, 273–278.
5 F. Ren, Z. Q. Zhu, X. Qian, W. D. Liang, P. Mu, H. X. Sun, J. H.
Liu, A. Li, Chem. Commun., 2016, 52, 9797–9800.
4,
1
5
5
5
5
2
6 X. F. Wu, H. B. Li, Y. X. Xu, H. Tong, L. X. Wang, Polym.
Chem., 2015,
7 D. X. Ma, B. Y. Li, Z. H. Cui, K. Liu, C. L. Chen, G. H. Li, J. Hua,
B. H. Ma, Z. Shi, S. H. Feng, ACS Appl. Mater. Inter., 2016,
4097–24103.
8 Y. K. Li, S. M. Bi, F. Liu, S. Y. Wu, J. Hu, L. M. Wang, H. L. Liu,
Y. Hu, J. Mater. Chem. C, 2015, , 6876–6881.
9 H. P. Ma, B. Li, L. M. Zhang, D. Han, G. S. Zhu, J. Mater.
Chem. A, 2015, , 19346–19352.
6, 2305–2311.
8
,
2
5
5
6
6
6
3
3
0 C. Gu, N. Huang, J. Gao, F. Xu, Y. H. Xu, D. L. Jiang, Angew.
Chem., 2014, 126, 4950–4955.
1 T. M. Geng, W. Y. Zhang, Z. M. Zhu, X. M. Kai, Micropor.
Mesopor. Mat., 2019, 273, 163–170.
2 Z. Chen, M. Chen, Y. L. Yu, L. M. Wu, Chem. Commun.,
2017, 53, 1989–1992.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins

New Journal of Chemistry
Page 10 of 10
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/C9NJ05509F
Graphical Abstract
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0