The magic of integration: Exploring the construction of dithienylethene-based infinite coordination polymers and their synergistic effect for gaseous ammonia probe applications

Article abstract of DOI:10.1016/j.cclet.2016.01.056

Infinite coordination polymers are recognized as excellent platform for functionalization. Dithienylethene motifs, which are one of the most attractive functional moieties, were incorporated into an infinite coordination polymer, to deliver a "smart" porous material that can response to external stimuli. The obtained dithienylethene-based infinite coordination polymers (named Cu-DTEDBA) share the advantages of both infinite coordination polymers (porosity and stability) and dithienylethene motifs (photochromism). The physical and chemical properties of Cu-DTEDBA were characterized by FTIR, TEM, SEM, XRD, TGA, UV-vis, EDX and BET. Moreover, the combination of dithienylethene and infinite coordination polymers gives rise to a synergistic effect, which induces functional behaviors of ammonia sensor applications. Both open and closed forms of Cu-DTEDBA exhibit distinct colorimetric change upon exposure to gaseous ammonia, which is not observed in dithienylethene free molecules.

Full text of DOI:10.1016/j.cclet.2016.01.056

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CCLET 3584 1–5
Chinese Chemical Letters xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
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The magic of integration: Exploring the construction of
dithienylethene-based infinite coordination polymers and their
synergistic effect for gaseous ammonia probe applications
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b,1,
a,c
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Q1 Yan-Kai Li , Jun-Ji Zhang *, Zi-Jun Bian , You-Xin Fu , Fei Liu , Chen-Hui Wang ,
b
a,
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Xiang Ma , Jun Hu *, Hong-Lai Liu
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Key Laboratory for Advanced Materials and Department of Chemistry, East China University of Science and Technology, Shanghai 200237, China
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237, China
Xi’an Thermal Power Research Institute Co., Ltd. (Suzhou Branch), Suzhou 215153, China
b
c
A R T I C L E I N F O
A B S T R A C T
Article history:
Infinite coordination polymers are recognized as excellent platform for functionalization. Dithieny-
lethene motifs, which are one of the most attractive functional moieties, were incorporated into an
infinite coordination polymer, to deliver a ‘‘smart’’ porous material that can response to external stimuli.
The obtained dithienylethene-based infinite coordination polymers (named Cu-DTEDBA) share the
advantages of both infinite coordination polymers (porosity and stability) and dithienylethene motifs
Received 23 December 2015
Received in revised form 18 January 2016
Accepted 25 January 2016
Available online xxx
(photochromism). The physical and chemical properties of Cu-DTEDBA were characterized by FTIR, TEM,
Keywords:
SEM, XRD, TGA, UV–vis, EDX and BET. Moreover, the combination of dithienylethene and infinite
coordination polymers gives rise to a synergistic effect, which induces functional behaviors of ammonia
sensor applications. Both open and closed forms of Cu-DTEDBA exhibit distinct colorimetric change upon
exposure to gaseous ammonia, which is not observed in dithienylethene free molecules.
ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
Dithienylethene
Photochromism
Infinite coordination polymers
Synergistic effect
Gaseous ammonia probe
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1. Introduction
to extent their applications. Specifically, the employment of 25
functional ligand precursors can afford ‘‘smart’’ materials which 26
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As an emerging class of inorganic–organic hybrid materials,
infinite coordination polymers (ICPs) have spurred flourishing
research interests in the past decade [1–4]. The structure of ICPs, in
which repeating organic ligands are linked together by metal
nodes, are highly appealing because the numerous choices of
transitional metal nodes and predefined organic linkers give rise to
a high degree of tailorability for ICPs [5–9]. The merits of
tailorablility, together with the presence of porosity that often
enjoyed by ICPs provide researchers with versatile network
structures which can be deliberately designed for a varieties of
applications, such as catalysis [10], gas adsorption [11], bio-
sensing [12] and drug delivery [13]. Apart from the above
properties, ICPs still have huge potency to be further exploited
can carry out multiple tasks under different external stimuli 27
[14]. However, the fabrication of such functional ICPs have been 28
rarely reported and remains a challenging subject.
29
Among the external stimuli, light is one of the most attractive 30
way to manipulate molecular functions, due to its superiority in 31
spatial, temporal and energetic resolutions and the minimum of 32
side reactions [15–20]. One of motifs are known as photochro- 33
mism, which stars the marvellous photo-isomerizable molecules, 34
including azobenzenes [21–24], spiropyrans [25,26] as well as 35
dithienylethenes (DTE) [27–29]. Among these photochromic 36
molecules, DTE derivatives, which undergo photo-induced 37
isomerization involving ring-opening/closing reactions [30,31], 38
are one of the most appealing classes of molecules, due to their 39
excellent thermal stability, rapid response, and fatigue resistance 40
[
29,32,33]. Moreover, the geometry of DTE derivatives undergoes 41
*
Corresponding authors.
limited change under isomerization, which favors their involve- 42
ment in the construction of ICPs, for the isomerization exhibits 43
negligible effect to the stability of coordination polymer 44
E-mail addresses: zhangjunji@ecust.edu.cn (J.-J. Zhang),
junhu@ecust.edu.cn (J. Hu).
1
These authors contributed equally to this work and should be considered
structure.
45
co-first authors.
http://dx.doi.org/10.1016/j.cclet.2016.01.056
1
001-8417/ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: Y.-K. Li, et al., The magic of integration: Exploring the construction of dithienylethene-based infinite
coordination polymers and their synergistic effect for gaseous ammonia probe applications, Chin. Chem. Lett. (2016), http://dx.doi.org/
1
0.1016/j.cclet.2016.01.056

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In spite of limited reports of functional ‘‘smart’’ ICPs, their
counterpart inorganic–organic hybrid materials (for example,
metal–organic frameworks) have found themselves more and
more involved in the construction of functional porous materials
[34–36], which gave us inspiration for designing DTE-based photo-
controllable ICPs. The amazing structure of ICPs, that an infinite
scaffold being assembled by repeating ligands and metal nodes,
gives rise to a synergistic combination of both merits of photo-
switchable ligands and coordination polymer network. The
synergistic effects, which induces unique performances occurred
in the hybrid structures while not available in ‘‘free’’ molecules,
results in an enhanced efficiency of both functional motifs and
coordination polymer structure. Herein, not only have we
fabricated photochromic DTE-based ICPs, but also have fully
utilized the synergistic effect of DTE motifs and ICPs to deliver
unique properties that are not applying to DTE-based small
molecules. The synergistic combination of photochromic moieties
and porosity would provide more space to transduce the host–
guest interaction to a colorimetric probe for gaseous ammonia.
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2. Experimental
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Materials and methods: DMF, Cu(NO
from Sinopharm Chemical Reagent Co., Ltd., China. The preparation
of DTEDBA was described in supporting information. H NMR
spectra were collected on a Bruker Avance DPS-300 spectrometer
3
)
2
ꢀ3H
2
O were purchased
1
using CDCl
internal reference. Thermogravimetry analysis (TGA) were per-
formed under N on a NETZSCH STA449F3, with a heating rate of
3 6
or DMSO-d as solvent and tetra-methylsilane as an
Scheme 1. Photoisomerization and ammonia responsibility of DTEDBA (a) and
2
Cu-DTEDBA (b) under UV and visible light.
ꢁ1
10 8C min . The morphology of the samples were characterized
on a JEOL JEM-2100 transmission electron microscopy (TEM).
Scanning electron microscopy (SEM) pictures was conducted on a
JEOL JSM-6360LV. Powder X-ray diffraction (XRD) measurements
were carried out on a D/Max-2550 VB/PC diffractometer (40 kV,
ꢁ1
around 1432 cm certified the presence of DTE moieties in the ICP
skeleton. Coordination of the carboxylate groups of DTEDBA to
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+
Cu ions was proved by a shift in the CO stretching frequency to
ꢁ
1
ꢁ1
200 mA), using Cu K
a
radiation. Nitrogen adsorption isotherms
1532 cm
and 1608 cm .
Energy dispersive X-ray (EDX)
were measured at 77 K using Micromeritics Tristar 3020 static
volumetric analyzer. Before adsorption measurements the poly-
mer was degassed at 100 8C under vacuum. The Brunauer–
Emmett–Teller (BET) surface area was calculated within the
relative pressure range 0.05 to 0.30 and the pore diameters were
calculated by non-local DFT method. The adsorption spectra for
ethanol suspension of Cu-DTEDBA (0.1 mg mL ) were measured
on a Shimadzu, UV-2550 spectrophotometer. To examine the
absorption spectral change upon the addition ammonia, 2
spectroscopy, in which the peaks of C, O, S, Cu were found, was
conducted to confirm the chemical composition of the sample (Fig.
S1 in Supporting information). Cu-DTEDBA was found to be
thermally stable up to approximate 300 8C by the thermogravi-
metric analysis (TGA) (Fig. 1e). The DTE moieties began to
decompose above 300 8C and degradation of framework occurs
at 500 8C. As evident from scanning electron microscopy (SEM) and
transmission electron micrographs (TEM) images (Fig. 1b and c),
Cu-DTEDBA exhibited the morphology of crystalline structure to
some extent rather than completely amorphous morphology. The
powder X-ray diffraction (PXRD) pattern (Fig. 1f) also suggested
the presence of long range order for Cu-DTEDBA. The adsorption
and desorption isotherm of nitrogen gas were collected under 77 K
to examine the permanent porosity (Fig. 1d), from which the
ꢁ
1
mL aqua
ammonia was added into 2 mL above suspension, and then the
absorption spectra was measured (Fig. S4). FT-IR data were
obtained using a Nicolet Magna-IR 550 spectrometer.
Synthesis of Cu-DTEDBA: A mixture of DTEDBA (20 mg,
0.04 mmol), Cu(NO
3
)
2
ꢀ3H
2
O (9.6 mg, 0.04 mmol), DMF 6 mL and
2
ꢁ1
water 2 mL were sealed into a glass vial and heated at 80 8C for
36 h. After cooling to room temperature, the mixture was filtered.
The solid was collected, washed with DMF for 3 times and dried at
80 8C to afford Cu-DTEDBA (12.3 mg, yield 57%).
surface area of Cu-DTEDBA was calculated to be 203 m g by
using the Brunauer–Emmett–Teller (BET) model. Hysteresis loops
between adsorption and desorption branches indicated the
presence of mesopores of Cu-DTEDBA [37,38], which is of interest
for applications that require rapid mass transfer process through
so-called transport pores [39].
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3. Results and discussion
Similar as discovered in small molecules of DTE derivatives, the
DTE moieties was also able to undergo rapid photochromic
reaction in Cu-DTEDBA. When the light green solid of Cu-DTEDBA
powder was irradiated by low density ultraviolet (UV) light, it
turned to deep blue within 5 min. Whereas the exposure of these
blue powder to visible light (>470 nm) led to the recovery of the
light green sample in around 30 min (Fig. 2a). The photochromic
mechanism for DTE derivatives that the transformation between
the strong UV-absorption in the open-ring form and the strong
visible light absorption in the closed-ring form is also applicable in
Cu-DTEDBA, which results in the distinguishable colors [34] (the
0
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To fabricate DTE-based ICP, the DTE derivative of DTEDBA [4,4 -
0
(4,4 -(cyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-
00
01
02
03
04
05
06
07
diyl))dibenzoic acid] that containing carboxylic groups were
designed and synthesized to deliver ligand for the coordination
with metal ion species (Scheme 1a). As illustrated in Scheme 1b, an
ICP named Cu-DTEDBA was prepared from heating the mixture of
DTEDBA and Cu(NO
3
)
2
ꢀ3H
2 2
O in DMF/H O at 80 8C. Cu-DTEDBA was
obtained as light green solid. Fourier transform infrared spectros-
copy (FTIR) was conducted to confirm the chemical structure of the
Cu-DTEDBA (Fig. 1a). The stretching vibration of thiophene rings
Please cite this article in press as: Y.-K. Li, et al., The magic of integration: Exploring the construction of dithienylethene-based infinite
coordination polymers and their synergistic effect for gaseous ammonia probe applications, Chin. Chem. Lett. (2016), http://dx.doi.org/
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Fig. 1. (a) Fourier transform infrared spectroscopy (FTIR) of DTEDBA and Cu-DTEDBA; (b) scanning electron microscopy (SEM) image of Cu-DTEDBA; (c) transmission electron
microscopy (TEM) image of Cu-DTEDBA; (d) the N adsorption isotherms of Cu-DTEDBA measured at 77 K. (e) Thermogravimetric analysis (TGA) of DTEDBA and Cu-DTEDBA.
f) Powder X-ray diffraction (PXRD) pattern of Cu-DTEDBA.
2
(
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open form and the closed form of Cu-DTEDBA are denoted as Cu-
DTEDBA(o) and Cu-DTEDBA(c), respectively). The UV–vis absorp-
tion spectra of Cu-DTEDBA in EtOH suspension confirmed the
reversible ring open/close reaction (Fig. 2b). The absorption peak
centered at 580 nm grew while the peak of 330 nm decreased
significantly with the inceasing time of UV-irrdiation, compared
with similar transformation of the EtOH solution of DTEDBA
molecules upon exposure to UV irradiation (Fig. S2 in Supporting
information).
The porosity of Cu-DTEDBA ensures the accommodation of
guest molecules, while the functionalization with smart ligands
enables the modulation of host–guest interactions with various
external stimuli. As mentioned before, the reported hybrid
materials are mainly based on the ligand motifs, while the
functions originated form inherent synergistic effects between
ligands and ICPs structures are rarely discussed. Accordingly, we
hypothesized that the host–guest interactions in Cu-DTEDBA
would affect the optical properties of DTE moieties in the skeleton,
thus making it favorable to be a chemical sensor to transduce intra-
molecular interactions to detectable color change. As prove-of-
principle, we selected gaseous ammonia as the target guest
molecule. In our experiment, gaseous ammonia was produced by
heating aqua ammonia. After dried by a pad of soda lime, the
generated gaseous ammonia flowed to solid sample of Cu-DTEDBA.
Upon exposure to gaseous ammonia, Cu-DTEDBA(o) exhibited a
quick colorimetric change from light green to dark cyan (within
3 s), indicating an interaction between ammonia and Cu-DTED-
BA(o). Interestingly, after the adsorption of ammonia, the solid
sample of Cu-DTEDBA(o)ꢀNH
behavior and underwent photo-induced isomerization to form
(vice versa) with an even faster conversion rate
3
maintained its photochromic
Fig. 2. (a) Visual changes of Cu-DTEDBA upon exposure to low-intensity ultraviolet
Cu-DTEDBA(c)ꢀNH
3
light and alternate visible light; (b) absorption spectral changes of Cu-DTEDBA
than their pristine counterparts (Cu-DTEDBA(o) and Cu-DTED-
BA(c)) (Table S3 in Supporting information). Moreover, the
ꢁ1
(
0.1 mg mL , EtOH suspension) upon irradiation with 365 nm. (For interpretation
of the references to color in this figure legend, the reader is referred to the web
version of this article.)
3
ammonia adsorbed Cu-DTEDBA(c)ꢀNH also displayed a detectable
Please cite this article in press as: Y.-K. Li, et al., The magic of integration: Exploring the construction of dithienylethene-based infinite
coordination polymers and their synergistic effect for gaseous ammonia probe applications, Chin. Chem. Lett. (2016), http://dx.doi.org/
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Fig. 3. (a) Color change of Cu-DTEDBA(o) and Cu-DTEDBA(c) upon exposure to gaseous ammonia; (b) FTIR of Cu-DTEDBA and Cu-DTEDBAꢀNH
3
(c) cycling tests of Cu-
DTEDBA(o) and Cu-DTEDBA(c) for ammonia sensing. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
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colorimetric change compared to the pristine Cu-DTEDBA(c) (from
dark blue to violet), demonstrating that both open/closed isomer
constructed ICPs can be used as gas probes (Fig. 3a). The ability to
adsorb gas into the pores allows the guest molecules to be
immobilized in intimate proximity to the active adsorption sites,
which favors the application of gas probe. To gain some elucidation
of the possible mechanism of the current probe for the ammonia
detection, FTIR was conducted to exploit the interactions between
ammonia and the framework of Cu-DTEDBA (Fig. 3b). A shift in the
adsorbed ammonia from the pores (Fig. 3c). Only minute
deterioration of response time and sensing abilities were discov-
ered after 10 cycles of regeneration, due to the excellent stability of
the coordination polymer. As a result, the synergistic effect of DTE
motifs and ICPs may be a new strategy to design functional
materials with novel properties, which may broaden the design
and application of functional materials.
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FTIR absorption from 1608 cm to 1647 cm and a significant
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decrease for the absorption at 772 cm
were detected in Cu-
DTEDBA after the exposure to ammonia, which was ascribed to the
alternation of the frequency of stretching vibration for carbonyl
group as well as the intensity of the vibration for Cu–O bond,
respectively. This alternation suggested the occurrence of the
complexation between the ammonia and Cu–O clusters or the
coordination effect is able to affect the interaction between the
carboxylic ligand and Cu nodes. It is worth mentioning that the
color change induced by gaseous signal could be difficult to
observe for DTEDBA small molecules in solution (Fig. S5 in
Supporting information), due to the absence of porosity and metal
sites to accommodate and interact with ammonia. This indicates
that the sensing behavior of DTE-based ICPs is indeed originated
from the synergistic effects of DTE motifs and ICP structures, rather
than from the simple free DTE molecules. Furthermore, cycling
tests were conducted to examine the stability and reversibility of
Cu-DTEDBA as the chemical sensor. Upon the exposure to
ammonia, almost the same color change were observed for each
cycle. After heating at 120 8C for about 5 min, the regenerated Cu-
DTEDBA exhibits recovered color, indicating the removal of
We used carboxylic DTE derivatives as the organic ligand to
construct novel Cu-DTEDBA with rigid structure and porosity.
Rapid photochromic reaction successfully occurred for Cu-
DTEDBA, in consistent with the obvious change in color. More
importantly, Cu-DTEDBA exhibit detectable colorimetric change
after exposure to gaseous ammonia, indicating a synergistic effect
between ICPs and DTE motifs. This would lead to unique
functionalities of resulting materials, thus broadening the design
and application of smart functional materials. Currently, the design
of more sophisticated synergistic photochromic porous materials
based on various interactions are under further investigation in our
lab.
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Acknowledgments
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This work was financially supported by National Basic Research
Program of China (No. 2013CB733501), National Natural Science Q2 229
Foundation of China (Nos. 91334203, 21376074, 21402050) and Q3 230
project WK1314008.
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Please cite this article in press as: Y.-K. Li, et al., The magic of integration: Exploring the construction of dithienylethene-based infinite
coordination polymers and their synergistic effect for gaseous ammonia probe applications, Chin. Chem. Lett. (2016), http://dx.doi.org/
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Please cite this article in press as: Y.-K. Li, et al., The magic of integration: Exploring the construction of dithienylethene-based infinite
coordination polymers and their synergistic effect for gaseous ammonia probe applications, Chin. Chem. Lett. (2016), http://dx.doi.org/
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0.1016/j.cclet.2016.01.056