A thermally stable and reversible microporous hydrogen-bonded organic framework: aggregation induced emission and metal ion-sensing properties

Article abstract of DOI:10.1039/c5tc02790j

A microporous hydrogen-bonded organic framework (HOF) derived from a polyhedral oligomeric silsesquioxane (POSS) intermediate and an aggregation-induced emission (AIE) luminogen tetraphenylethene (TPE) derivative has been synthesized and structurally char

Full text of DOI:10.1039/c5tc02790j

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A Thermally Stable and Reversible Microporous Hydrogen-Bonded
Organic Framework: Aggregation Induced Emission and Metal Ion-
sensing Properties†
Received 00th January 20xx,
Accepted 00th January 20xx
Hui Zhou,a Qun Ye,a Xiangyang Wu,b Jing Song,a Ching Mui Cho,a Yun Zong,a Ben Zhong Tang,*c T. S.
DOI: 10.1039/x0xx00000x
Andy Hor,a,d Edwin Kok Lee Yeow,b and Jianwei Xu*a,d
www.rsc.org/
A
microporous hydrogen-bonded organic framework (HOF) derived from a polyhedral oligomeric
silsesquioxane (POSS) intermediate and an aggregation-induced emission (AIE) luminogen tetraphenylethene
(TPE) derivative has been synthesized and structurally characterized by various methods. This unique HOF
exhibits a permanent porosity with the Brunauer-Emmett-Teller (BET) surface area of 101.9 m2/g. This HOF
could be well dispersed in organic solvents in a form of nanoparticles with a size of a few hundred
nanometers. These nanoparticles are highly fluorescent in organic solution, and exhibit a high fluorescence
quenching selectivity towards copper ion. Furthermore, the fluorescence of this HOF could be recovered by
removal of copper ion upon addition of cyanide and, more interestingly, this process could be repeated
several times without considerably sacrificing the sensing activity towards copper ion.
host molecules can form strong hydrogen bonds and π-π stacking
each other.5 Therefore, it is still challenging to obtain porous HOFs,
which are stable enough for their potential applications as storage
Introduction
Recently, porous hydrogen bonded organic frameworks (HOFs)
have attracted increasing interest as stimuli sensitive materials,1
but HOFs have lagged significantly behind metal-organic
frameworks in terms of framework design, topological
rationalization and functionalization. This is because hydrogen
bonds are weaker and more flexible in conformation when
compared to coordination interactions in other frameworks, such as
zeolites and metal-organic frameworks (MOFs),2 leading to lower
stabilities.3,4 Thousands of HOFs have been prepared during the last
decades, but HOFs with permanent porosity are rarely offered, as
HOFs easily collapse once the guest molecules are removed from
the super-molecular network system. To the best of our knowledge,
only very limited HOFs display high thermal stability and exhibit
permanent porosity after removal of guest molecules, in which the
and separation, heterogeneous catalysis, sensing and so on.
Aggregation-caused quenching (ACQ) of fluorescence is
commonly observed in fluorescent materials in solid state, which
has undermined its potential for solid-state sensors or probes.6
Recently, AIE materials have attracted increasing interest in the
areas of optoelectronics and sensory systems due to the absence of
ACQ effect.7 However, the stimuli sensitive HOFs materials with AIE
properties have been rarely reported, and their sensing application
was not found mainly due to the lack of suitable processable HOFs
materials with AIE activity, which is tolerant to solvents, moisture,
temperature, etc.8
Herein, we report on a feasible method without using any guest
molecules to prepare AIE active HOF, which responds to the
external stimuli. This HOF (POSS-T8A) was prepared by the
condensation of AIE precursor 4-(1,2,2-triphenylvinyl)benzoic acid
and octa(amino)-substituted POSS derivative (Scheme 1). For
comparison, another analogue POSS-T8B with ester linkages was
prepared as well. POSS have been demonstrated as effective
building blocks to generate porous materials through thermolysis,9
hydrosylation,10 coupling reactions,11 as well as free radical
copolymerization with other monomers.12 Several porous materials
derived from octa(vinyl)-POSS exhibit BET surface area as high as
700 m2/g and maximum tunable mesopore volume of 2.0 cm3/g.13
In this paper, POSS-T8A molecules show enhanced AIE properties,
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and display high sensitivity (Stern-Volmer co-efficient Ksv = 30305 form of nanoparticles. This indicates that POSS-T8A molecules form
M-1) and fluorescence quenching selectivity for Cu2+ ion due to the hydrogen-bonded aggregates, which limits the solubility in organic
presence of amide linkages, which is effectively able to bind with solvents. Good solubility in pyridine is due to the fact that pyridine
Cu2+ ion, leading to the conformation change of TPE units in the can act as electron acceptors to form hydrogen bonds with amide
POSS-T8A molecules and eventually resulting in fluorescence turn- linkages and hence dissociate the self-aggregation of the POSS-T8A
off (Scheme 1). This is the first demonstration for the fluorescence molecules. This is confirmed by the 1H NMR study of POSS-T8A in
signaling via conformational changes of pendent luminogen pyridine-d5 and DMSO-d6. The proton signals of POSS-T8A in
moieties in HOFs materials.
pyridine-d5 are readily identified, while its protons in DMSO-d6 were
not observed under the same condition (Fig. S10). In contrast, the
ester linkages do not facilitate to form any strong hydrogen-bonded
networks and no hydrogen-bonded self-aggregation was observed
for POSS-T8B molecules. Therefore, POSS-T8B shows very good
solubility in many organic solvents. The nanoparticle structure of
POSS-T8A was characterized by dynamic light scattering and it forms
nanoparticles with an average size of 291.4 nm in DMSO, which was
supported by transmission electron microscope (TEM) analysis (Fig.
1a and 1b). Both POSS-T8A and POSS-T8B (Fig. 1c and S1) exhibited
good thermal stability in air with a decomposition temperature of
more than 370 °C.
HO
HO
O
B
NaOH-H2
O
O
Br
OH
Pd(PPh3
)4-K2CO3
O
O
1
O
2
R
O
R
Si
Si
O
O
R
O
O
Si
O
Si
R
O
O
R
O
Si
Si
R
O
O
Si
Si
R
O
R
POSS
NH3Cl
R =
Si
OH
R =
O
1.0
O
b
a
R1
Si
R2=
O
R1
=
O
O
Si
0.8
0.6
0.4
0.2
0.0
R1
Si
O
O
Si
O
O
R1
N
H
Si
O
R1 O
O
O
R1
O
Si
Si
Si
R1
O
O
Si
R1
R1
POSS-T8A
O
POSS-T8B
POSS-T8
A
HOF formation
HOF formation
X
0
200
400
600
800 1000 1200 1400 1600 1800 2000
Diameter (nm)
c
d
100
200
POSS-T8A (CO2)
POSS-T8A Cu2+ (CO2
)
.
5% weight loss
T
d = 415 o
C
OctaAmmonium POSS (CO2
POSS-T8A (N2)
)
80
60
40
20
150
100
50
Cu2+
CN-
0
0
100
200
300
400
500
600
0
200
400
600
800
1000
ON
Temperature (oC)
Absolute pressure (mbar)
OFF
Cu2+
:
POSS;
:
: Hydrogen bonding;
Fig. 1 (a) Particle size distribution of POSS-T8A in DMSO. (b) TEM
image of POSS-T8A particles prepared in the DMSO; scale bar is 0.5
µm. (c) TGA thermogram of POSS-T8A recorded at a heating rate of
20 oC/min in air. (d) Gas absorption isotherms for POSS-T8A, POSS-
T8A•Cu2+ and Octa(NH2)-POSS (CO2 at 0 oC, N2 at -196 oC).
Scheme 1 Synthetic route leading to POSS-T8A, POSS-T8B, and
structural illustration of POSS-T8A for Cu2+ sensing.
Results and Discussion
POSS-T8A and POSS-T8B were prepared using a similar method as
shown in Scheme 1. POSS-T8B was easily purified by column
chromatography. In contrast, POSS-T8A was first purified by
precipitating diluted POSS-T8A CHCl3 solution in methanol. Then
resulting material was isolated by centrifugation, and then collected
solid residue was washed with hexane and methanol followed by
Soxhlet extraction with Et2O. Both POSS-T8A and POSS-T8B were
well characterized by 1H, 13C and 29Si nuclear magnetic resonance
(NMR), matrix-assisted laser desorption ionization time of flight
(MALDI TOF) mass spectrometer and elemental analysis. POSS-T8B
shows very good solubility in most organic solvents such as
chloroform, tetrahydrofuran (THF), ethyl acetate (EA); however,
POSS-T8A is only fully soluble in pyridine but well-dispersed in other
common organic solvents such as THF, chloroform, EA, etc., in a
Physical gas adsorption is widely used to study the pore
characteristics of solid materials.14 The porosity of POSS-T8A was
studied by CO2 gas adsorption and desorption at 273 K (Fig. 1d).
POSS-T8A shows type II isotherms with a significant amount of CO2
adsorbed at low pressure (P/P0 < 0.03), followed by a much
increased adsorption at higher pressure (P/P0 > 0.9) attributable to
gas condensation into voids among particles. The CO2 adsorption
capacity was measured by CO2 isothermal adsorption at 273 K. The
micropore BET surface area is calculated to be 101.9 m²/g in terms
of Dubinin–Astakhov method. The pore size distribution was
evaluated by applying a non-local density functional theory (NLDFT)
model. The NLDFT model was applied under the assumption that
the slit-shaped pores have uniformly dense carbon walls and that
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the adsorbate is a fluid of hard spheres. Additionally, the interaction the restricted intra- and inter-molecular rotation blocks the non-
between adsorbent and adsorbate was considered on their radiative channel and further enhances the light emission. The
elemental species by a soft program installed on the BET apparatus. time-resolved fluorescence spectrum of POSS-T8A was examined
The pore width was distributed mainly in the micropore range, and it exhibited dual exponential decay with a life-time of 2.09 and
especially in the range of 0.5-0.9 nm (Fig. S2).
5.00 ns (Fig. 2b).
1
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
UV POSS-T
A
B
b
a
τ1 = 2.09 (34.30%) ns
τ2 = 5.00 (65.70%) ns
8
800
600
400
200
0
UV POSS-T
FL POSS-T8A
FL POSS-T8B
8
0.1
0.01
20
25
30
35
40
45
50
55
60
65
70
75
300
350
400
450
500
550
600
Time (ns)
Wavelength (nm)
100
80
60
40
20
0
1 x 10-6 M POSS-T8B
160
140
120
100
80
d
c
+ 1 x 10-5 M Cu2+
+ 5 x 10-5 M Cu2+
+ 1 x 10-4 M Cu2+
+ 2 x 10-4 M Cu2+
+ 4 x 10-4 M Cu2+
+ 6 x 10-4 M Cu2+
+ 8 x 10-4 M Cu2+
+ 1 x 10-3 M Cu2+
60
40
20
0
400
450
500
550
600
Wavelength (nm)
Fig. 3 Enlarged image (a) and fluorescent image (b) of POSS-T8A
nanoparticles. Enlarged image (c) and fluorescent image (d) of
Fig. 2 (a) UV-Vis and fluorescence spectra of POSS-T8A and POSS-T8B
in THF. Insert is the photographs of samples under UV in THF taken
under UV illumination (λex = 365 nm), [C] = 1.0 × 10-5 M. (b) The
time-resolved fluorescence lifetimes of POSS-T8A in THF under
POSS-T8A•Cu2+ nanoparticles. Photography is taken under
a
fluorescence microscope with a 337 nm excitation. Scale bar is
100.0 µm.
excitation of
a femtosecond pulsed laser at 375 nm. (c)
The fluorescence titration of POSS-T8A with Cu2+ in DMSO
showed a progressive decrease in fluorescence intensity of POSS-
T8A upon addition of Cu2+ ion (Fig. 2c). It was known that Cu2+ ion is
able to coordinate with nitrogen atoms of the amide groups15 and
quench the fluorescence.16 In our case, Cu2+ ion can quench the
fluorescence in different organic solvents and it shows the highest
quenching efficiency in DMSO (Fig. 2d). The fluorescence
microscopy also clearly showed that the fluorescent nanoparticles
appeared non-fluorescent upon addition of enough Cu2+ ion (Fig. 3b
and 3d).
Fluorescence titration spectra of POSS-T8A upon addition of
Cu(NO3)2 in DMSO. λex = 314 nm, [POSS-T8A] = 1.0 × 10-6 M. (d)
Fluorescence quenching efficiency of POSS-T8A with Cu2+ ion in
various solvents, [POSS-T8A] = 1.0 × 10-6 M, [Cu2+] = 1.0 × 10-3 M.
POSS-T8A shows strong blue-white emission both in solid state
and organic solvents (Fig. 2). POSS-T8A could be dispersed in organic
solvents, such as THF, chloroform and DMSO, to form
macroscopically homogeneous but visually transparent solutions
without observing any precipitates. Taking the mixture of POSS-T8A
in THF as an example, no tendency towards agglomeration was
observed when the dispersion was stored at 4 oC for 6 months.
Typically, most of TPE-containing materials are non-emissive in
good solvents, such as THF. However, as shown in Fig. 2a,
dispersion of POSS-T8A displays strong fluorescent emission with an
emission maximum at 458 nm and a wide of spectrum ranging from
375 nm to 600 nm, which can be seen even by naked eyes under
the bright light when UV illuminated when the concentration is as
low as 1.0 × 10-5 M. On the contrary, POSS-T8A is not fluorescent in
pyridine as it is completely soluble in it without forming any
nanoparticles like in other organic solvents (Fig. S3). Similarly, POSS-
T8B displays normal AIE properties, as shown in Fig. S4, and its
fluorescence would be turned on in the mixture of THF/H2O, when
the water volume fraction is increased up to 60%. Considering
enhanced AIE property and morphology of POSS-T8A particles,
together with the amides’ nature to form hydrogen bonds, it is
therefore confirmed that the amide groups of POSS-T8A form the
hydrogen-bonded networks (Scheme 1). Within this HOFs structure,
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160
120
80
40
0
100
POSS-T8A recovered by CN-
a
a
b
80
60
40
20
0
2+
.
POSS-T8A Cu
POSS-T8A
5
10
15
20
θ (deg.)
25
30
35
40
.
.
2
25
20
15
10
5
100
c
100
d
80
80
60
40
20
0
Quenching (%)
I0/I - 1
60
40
20
0
0
Fig. 4 (a) PXRD pattern of POSS-T8A, POSS-T8A•Cu2+ and POSS-T8A
recovered by CN-. (b) TEM image of POSS-T8A particles recovered by
CN-. Electron diffraction (ED) patterns of POSS-T8A (c), POSS-
T8A•Cu2+ (d), and POSS-T8A recovered by CN- (e).
2.0x10-4
4.0x10-4
6.0x10-4
8.0x10-4
1.0x10-3
0.0
1
2
3
4
5
[Cu2+] (mol/L)
Cycles
Wide angle X-ray diffractograms of POSS-T8A and POSS-T8A•Cu2+
are illustrated in Fig. 4a. A very weak broad scattering at 9.48°
corresponding to d-spacing of 9.33 Å is observed for POSS-T8A,
which is due to the Si-O clusters in the POSS core.17 The POSS-T8A is
crystalline as evidenced by a group of the sharp reflection peaks
from 2θ = 19.04° (4.66 Å, 2nd order diffraction, 200), to 38.66° (2.33
Å). Upon addition of Cu2+ ion, the diffraction profile of POSS-
T8A•Cu2+ completely differs from the POSS-T8A; however recovered
POSS-T8A goes back to the same diffraction pattern as the pristine
POSS-T8A after Cu2+ ion is removed by CN-1, which is also supported
by the similar TEM image (Fig. 4b), revealing the excellent
reversibility of this HOF structure.
Fig. 5 (a) Fluorescence quenching efficiency of POSS-T8A upon
addition of various metal ions. λex = 314 nm. (b) Fluorescence
intensity changes during sensing and recovering by CN-. (c)
Concentration-dependent fluorescence quenching of POSS-T8A by
Cu2+. (d) The fluorescence recovery of POSS-T8A on addition of CN-.
(e) Photographs of samples with and without addition of metal ions
under UV illumination (365 nm). [POSS-T8A] = 1.0 × 10-6 M, [ion] =
1.0 × 10-3 M. (f) Photographs of POSS-T8A, POSS-T8A•Cu2+ and POSS-
T8A•Cu2+ with tetrabutylammonium cyanide under UV illumination
(365 nm). [POSS-T8A] = 1.0 × 10-6 M, [Cu2+] = 1.0 × 10-3 M, [CN-] = 1.0
× 10-2 M.
The fluorescence response of POSS-T8A to other metal ions was
also studied. As shown in Fig. 5a, transition metal ions, such as
Mn2+, Co2+, Ni2+, and Fe3+ exhibited limited fluorescence quenching
with 10 - 26% efficiency. In contrast, almost no fluorescence
quenching was observed for alkaline-earth metal ions, such as Mg2+
and Ca2+ ions. In contrast, the Cu2+ ion shows the highest quenching
efficiency (97%). Specifically, the quenching effect of metal ions was
quantified by the Stern-Volmer equation (Table 1).16 The largest
quenching coefficient (Ksv) value was obtained for Cu2+ ion to be
30305 M−1 (Fig. 5c), which is much higher than 7847 M-1 of MOFs
material CPP-16.18 The selective response to metal ions was
visualized in Fig. 5e. The influence of interrupting Cu2+ ion sensing
by other metal ions was studied by conducting Cu2+ sensing in the
presence of many other metal ions. Emission spectra (Fig. S5)
described no disturbance on selective Cu2+ sensing by any of the
other metal ions. It is worthy to note that the quenched
fluorescence
could
be
recovered
by
addition
of
tetrabutylammonium cyanide (Fig. 5b and 5f), and the recovered
HOFs material still displayed sensing ability to Cu2+ ion. After 4 off-
on cycles (Fig. 5d), the fluorescence quenching towards to Cu2+ ion
still remained around 80%, suggesting high reversibility and
responsiveness of POSS-T8A based HOFs structure.
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rate of 20 oC/min and on a TA Instruments Differential Scanning
Table 1 Fluorescence Quenching Coefficients (Ksv) of POSS-T8A on
o
Different metal Ions
Calorimetry (DSC) 2920 at a heating rate and a cooling rate of 5 C
min-1 in nitrogen. Dynamic light scattering experiments were
Metal ions
Ca2+
Ksv [M-1]
11
20
30305
346
Metal ions
Fe3+
Ksv [M-1]
111
17
43
33
performed on
a Brookhaven 90 plus spectrometer with a
Mg2+
Cu2+
Ag+
temperature controller. An argon ion laser operating at 633 nm was
used as light source. ASAP 2020 surface area analyzer was used to
Pd2+
Co2+
Mn2+
measure gas adsorption isotherms. To have
a guest-free
Ni2+
206
framework, the sample was purified by successive Soxhlet
extraction with methanol, ethyl acetate, 1,4-dioxane and
chloroform. The result product was vacuumed at room temperature
for 24 hours followed by 100 oC until the outgas rate was 5
mmHg/min prior to measurements. A sample of 187.9 mg was used
for the sorption measurement and was maintained at 77 K with
Conclusions
In conclusion, we reported on two AIE-active POSS based
molecules. POSS-T8B with ester linkages did not form HOF and only
showed a normal AIE property. Being different from usual HOF
materials,1,5 POSS-T8A with amide linkages enables to form very
stable super-molecular HOF structure without the assistance of any
guest molecules. This HOF showed enhanced AIE activity in
solutions. Specific response of POSS-T8A to Cu2+ ion led to the
dissociation of HOFs structure and subsequent release of the
restricted intramolecular rotation of TPE moieties so as to activate
their non-radiative channel and as a result turn off the emission.
The fluorescence of POSS-T8A and HOF structure could be
recovered by removal of Cu2+ ion by addition of CN- ion to form
liquid nitrogen, at 273
K with an ice–water bath. The CO2
adsorption capacity was measured by CO2 isothermal adsorption at
273 K. Furthermore, the parameters of the Dubinin–Astakhov
equation:
ꢊ
ꢊ
ꢅꢆ
ꢌꢃ
ꢀ ꢂ
ꢀ ꢂ
ꢃ
log ꢁ = log ꢁ − ꢄ
ꢉ ꢄlog ꢋ ꢍꢉ
ꢇꢈꢃ
ꢌ
were obtained from CO2 adsorption. P, P0, V, V0, n, R, E0, and β are
the equilibrium pressure, the saturation vapor pressure of the gas
at the analysis temperature (T), the volume adsorbed at equilibrium
pressure, the monolayer capacity, the Astakhov exponent, the gas
constant, characteristic energy, and the affinity coefficient of the
analysis gas, respectively.
2-x
more stable Cu(CN)x species.18 This type of AIE-active POSS-based
HOF materials could be used as a promising chemosensor for
potential applications in the detection of Cu2+ ion as well as for gas
storage and separation provided POSS structures are appropriately
tailored with desired substituents.
Synthesis of compounds.
Generally procedures. As shown in Scheme 1, POSS-T8A was
synthesized from a 4-(1,2,2-triphenylvinyl)benzoic acid (2), which
was synthesized by two steps with 91% yield staring from 1-
bromotriphenylethylene. After that, compound 2 reacts with octa-
ammonium POSS in the present of 1-hydroxybenzotriazole and
N,N′-dicyclohexylcarbodiimide to generate POSS-T8A with
reasonable yield of 70%. POSS-T8A was structurally characterized by
various spectroscopic methods and elemental analysis. The 1H NMR
spectrum of POSS-T8A is illustrated in Fig. S6. The presence of
signals at δ 7.54 and 7.09-6.90 with an integration ratio of 2 : 17,
which were assigned to protons of tetraphenylethene (TPE).
Furthermore, the integration ratio for signals at δ 7.54, 3.11, 1.51
Experimental
General.
All synthetic manipulations were carried out under an
atmosphere of dry argon gas using standard vacuum-line
Schlenk techniques. 1-Bromotriphenylethylene was purchased
from Tokyo Chemical Industry Co., Ltd. All solvents were
degassed and purified before use according to standard
literature methods. Diethyl ether, hexanes, tetrahydrofuran,
and toluene were purchased from Aldrich Chemical Co. Inc.
and distilled from sodium/benzophenone ketyl before use.
Other commercially available reagents and solvents were used
as received.
1
and 0.58 is 1 : 1 : 1 : 1. Those H NMR data together with results of
MALDI-TOF indicate that eight TPE moieties are introduced into
octa-ammonium POSS successfully. Similarly, POSS-T8B can be
prepared through the same route by 3 steps with overall yield as
53%. All of those POSS materials are structurally characterized by
various spectroscopic methods and elemental analysis.
Instrumentation.
1H and 13C nuclear magnetic resonance (NMR) spectra were
recorded on a Bruker DRX 400-MHz NMR spectrometer in CDCl3 at
room temperature using tetramethylsilane (TMS) as an internal
standard. Operating frequencies of the NMR spectrometer were
400.13 MHz (1H), 100.61 MHz (13C) and 79.49 MHz (29Si). Electron
impact mass spectra (EIMS) and high resolution MS (HRMS) were
recorded using a Micromass 7034E mass spectrometer. Elemental
analysis was conducted on a Perkin-Elmer 240C elemental analyzer
for C, H, and N determination. UV-vis and fluorescence spectra
Ethyl
4-(1,2,2-triphenylvinyl)benzoate
(670.5 mg, 2.00
(1).
Bromotriphenylethylene
mmol),
4-
(ethoxycarbonyl)phenylboronic acid (456.2 mg, 2.40 mmol), Na2CO3
(2.76 g, 20.00 mol) and Pd(PPh3)4 (115.6 mg, 0.10 mmol) were
placed in a Schlenk flask and the flask was evacuated and recharged
with Ar gas. Toluene (40.0 mL), ethanol (10.0 mL) and water (10.0
mL) was added, then the resulting mixture was degassed for 30 min
and the mixture was stirred for 12 h at 110 oC under Ar gas. After
cooling to room temperature, the mixture was poured into
saturated aqueous NaHCO3, extracted with dichloromethane (3 ×
40.0 mL), dried over Na2SO4, filtered, and evaporated. The resulting
residue was purified by chromatography over silica gel eluting with
were obtained using
spectrophotometer and
a
Shimadzu UV3101PC UV-vis-NIR
Perkin-Elmer LS 50B luminescence
a
spectrometer with a Xenon lamp as light source, respectively.
Thermal analysis was performed on Perkin-Elmer
a
thermogravimetric analyzer (TGA 7) in nitrogen or in air at a heating
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DOI: 10.1039/C5TC02790J
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Journal Name
hexane-dichloromethane (1 : 4), affording compound as an off mg, 0.50 mmol) is added. After stirring at room temperature for 5
white solid 862.2 mg (92.0%). 1H NMR (CDCl3): δ 7.77 (d, 2H, J = 8.6 days, ethyl acetate (50.0 mL) is added and the mixture is filtered.
Hz), 7.10 (m, 11H), 7.01 (m, 6H), 4.32 (q, 2H, J = 7.1 Hz), 1.35 (t, 3H, The solution is washed with saturated NaCl solution (2 × 100.0 mL).
J = 7.3 Hz). 13C NMR (CDCl3): δ 166.7, 148.9, 143.4, 143.3, 142.6, The organic solution is dried over anhydrous MgSO4, then the
142.5, 140.1, 131.5, 131.4, 129.1, 128.0, 127.8, 127.0, 126.9, 126.8, solvent is removed in vacuo and resulting crude product is purified
60.9, 14.4. IR (thin film): ν = 3420, 3052, 3020, 2979, 1950, 1810, by flash chromatography with ethyl acetate-hexane (1:4), affording
1714, 1603, 1492, 1443, 1274, 1176, 1102, 1020, 762, 749, 699 cm- product POSS-T8B as a light yellow semi solid (126.0 mg, 58%). 1H
1. HRMS (ESI): [M + H+] calcd for C29H25O2, m/z 405.1855; found, m/z NMR (400.13 MHz, CDCl3): δ 7.77 (d, 2H, J = 8.3 Hz), 7.10 (m, 11H),
405.1855.
7.00 (m, 6H), 4.21 (t, 2H, J = 6.9 Hz), 1.73 (m, 2H), 0.58 (m, 2H), 0.07
4-(1,2,2-triphenylvinyl)benzoic acid (2). To the solution of methyl (s, 6H). 13C NMR (100.61 MHz, CDCl3): δ 166.7, 148.8, 143.4, 143.2,
4-(1,2,2-triphenylvinyl)benzoate (1) (808.4 mg, 2.00 mmol) in 142.5, 140.2, 131.4, 131.3, 129.1, 128.4, 128.0, 127.9, 127.0, 126.9,
mixture of THF (10 mL) and H2O (10 mL) was added NaOH (240 mg, 126.8, 67.5, 22.9, 14.4, 0.4. 29Si NMR (79.49 MHz, CDCl3): δ 22.0, -
o
6 mmol). The resulting solution was stirred for 12 h at 90 C under 100.3. IR (thin film): ν = 3421, 3075, 3055, 3022, 2924, 2852, 1717,
Ar gas. After cooling to room temperature, pH value of the mixture 1606, 1492, 1444, 1405, 1384, 1273, 1177, 1102, 1051, 841, 761,
was adjusted to 4.0 by 1 M HCl solution, then extracted with 749, 699, 627 cm-1. MALDI-TOF: [M] calcd for C256H248O36Si16, m/z
dichloromethane (3 × 40.0 mL), dried over Na2SO4, filtered, and 4350.05; found, m/z 4350.60. Anal. Calcd for C256H248O36Si16: C,
evaporated. The resulting residue was purified by chromatography 70.68; H, 5.75; Si, 10.33. Found: C, 70.59; H, 5.81; Si, 10.31.
over silica gel eluting with Ethyl acetate-dichloromethane (1 : 10),
affording compound 2 as an off white solid 744.7 mg (99.0%). 1H
Acknowledgement
NMR (CDCl3): δ 7.80 (d, 2H, J = 8.3 Hz), 7.11 (m, 11H), 7.02 (m, 6H).
13C NMR (CDCl3): δ 171.4, 149.9, 143.3, 143.2, 143.1, 142.8, 140.0,
The authors would like to acknowledge the financial support
131.6, 131.4, 129.8, 128.0, 127.9, 127.1, 127.0, 126.9. IR (thin film):
(Grant No.: 1321760011) from the Institute of Materials
ν = 3422, 3049, 2947, 1720, 1604, 1491, 1443, 1404, 1368, 1283,
Research and Engineering (IMRE), Agency for Science,
1177, 1104, 1075, 1020, 749, 700 cm-1.HRMS (ESI): [M - H+] calcd for
Technology and Research (A*STAR).
C27H19O2, m/z 375.1391; found, m/z 375.1385.
POSS-T8A. 1-Hydroxybenzotriazole (HOBT, 67.5 mg, 0.50 mmol),
4-(1,2,2-triphenylvinyl)benzoic acid (188.0 mg, 0.50 mmol), and
Notes and References
OctaAmmonium POSS (58.7 mg, 0.05 mmol) are dissolved in dry
1
2
3
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DMF (2.0 mL). After addition of triethylamine (69.5 µL, 0.50 mmol),
the stirred solution is cooled in an ice-water bath and N,N′-
dicyclohexylcarbodiimide (103.0 mg, 0.50 mmol) is added. The
resulting mixture is stirred at room temperature for 5 days, then
ethyl acetate (50.0 mL) is added and the mixture is washed with
Mill-Q water (4 × 100.0 mL). After dried of the collected organic
phase, the crude product was first purified by precipitating POSS-
T8A’s diluted solution in a large amount of CHCl3 by methanol. Then
resulting material was isolated by centrifugation, and then collected
solid residue was washed with hexane and methanol followed by
Soxhlet extraction with Et2O, affording product POSS-T8A as a white
powder (142.4 mg, 77%). 1H NMR (400.13 MHz, DMSO-d6): δ 8.33
(m, 1H), 7.54 (d, 2H, J = 8.4 Hz), 7.09-6.90 (m, 17H), 3.11 (m, 2H),
1.51 (m, 2H), 0.58 (m, 2H). 1H NMR (400.13 MHz, pyridine-d5): δ
9.10 (m, 1H), 8.12 (d, 2H, J = 8.8 Hz), 7.28 (d, 2H, J = 8.47 Hz), 7.21-
7.15 (m, 15H), 3.68 (m, 2H), 1.99 (m, 2H), 0.93 (m, 2H). 13C NMR
(100.61 MHz, pyridine-d5): δ 168.0, 147.6, 144.4, 144.3, 144.2,
142.8, 141.2, 134.4, 132.2, 132.1, 128.8, 128.7, 128.0, 127.7, 127.6,
127.5, 43.3, 24.0, 10.1. 29Si NMR (79.49 MHz, pyridine-d5): δ -59.2.
IR (thin film): ν = 3432, 3340, 3054, 2930, 2868, 1639, 1607, 1538,
1493, 1444, 1303, 1195, 1111, 1030, 861, 760, 749, 698, 628 cm-1.
MALDI-TOF: [M + H+] calcd for C240H209N8O20Si8, m/z 3750.03; found,
m/z 3750.20. Anal. Calcd for C240H208N8O20Si8: C, 76.89; H, 5.59; N,
2.99; Si, 5.99. Found: C, 76.81; H, 5.71; N, 2.95; Si, 5.93.
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4
5
POSS-T8B. 1-Hydroxybenzotriazole (HOBT, 67.5 mg, 0.50 mmol),
4-(1,2,2-triphenylvinyl)benzoic acid (188.0 mg, 0.50 mmol) and Pss-
octa[C3-hydoxypropyl)dimethyl-siloxy]subsitituted (74.3 mg, 0.05
mmol) are dissolved in dry DMF (2.0 mL). After the stirred solution
is cooled in an ice-water bath, N,N′-dicyclohexylcarbodiimide (103.0
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6 | J. Name., 2012, 00, 1-3
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Journal of Materials Chemistry C
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DOI: 10.1039/C5TC02790J
Journal Name
ARTICLE
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Journal of Materials Chemistry C
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DOI: 10.1039/C5TC02790J
Graphic Abstract
A hydrogen-bonded organic framework derived from a polyhedral oligomeric silsesquioxane
and an aggregation-induced emission luminogen tetraphenylethene derivative was reported.