Photoswitching storage of guest molecules in metal-organic framework for photoswitchable catalysis: Exceptional product, ultrahigh photocontrol, and photomodulated size selectivity

Article abstract of DOI:10.1039/c7ta01388d

MOF materials, as new catalysts, show high catalytic activity and size-, regio-, and stereo-selectivity. However, artificially controlling their catalytic process by convenient external stimulus such as light is still unexploited. Such photocontrol over an organic reaction may enable switchable catalytic activities and/or selectivities, consequently producing desired products from a pool of building blocks according to the order and type of stimuli applied. In this study, we present a novel MOF catalyst, which not only offers ultrahigh photocontrol with the on/off ratio as high as 407, but also displays disparate photomodulation in reaction kinetics towards various aldehyde substrates in light of their sizes, thus creating the first example of MOFs showing photoswitchable catalysis. The origin, as unveiled by photoswitching adsorption experiments and density functional theory calculations, is due to photoswitching storage of guest molecules in the metal-organic framework (MOF).

Full text of DOI:10.1039/c7ta01388d

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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
2
rsc.li/materials-a

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DOI: 10.1039/C7TA01388D
Journal Name
ARTICLE
Photoswitching storage of guest molecules in metal-organic
framework for photoswitchable catalysis: exceptional product,
ultrahigh photocontrol, and photomodulated size selectivity
Received 00th January 20xx,
Accepted 00th January 20xx
ac‡
a‡
c
c
a
Le Le Gong, Wan Ting Yao, Zhi Qiang Liu, An Min Zheng *, Jian Qiang Li , Xue Feng
a
b
a
a
a*
DOI: 10.1039/x0xx00000x
Feng , Lu Fang Ma, * Chang Sheng Yan , Ming Biao Luo , and Feng Luo
www.rsc.org/
MOF materials as new emerged catalyst have been demonstrated to show high catalytic activity and size-, regio-,
and stereo-selectivity. However, how to artifically controlling the catalytic process by convenient external stimulus
such as light is still unexploited. Such photocontrol over organic reaction may enable switchable catalytic activities
and/or selectivities, consequently producing desired products from a pool of building blocks according to the order
and type of stimuli applied. In this work, we present a novel MOF catalyst, which not only offers ultrahigh
photocontrol with the ON/OFF ratio as high as 407, but also displays disparate photomodulation in reaction kinetics
towards various aldehyde substrates in light of their sizes, thus creating the first example in MOFs showing
photoswitchable catalysis. The origin, as unveiled by photoswitching adsorption experiments and density functional
theory calculations, is due to photoswitching storage of guest molecules in metal-organic framework (MOF).
For such purpose, photoactive MOFs13 would be one of the best
candidates since such materials often enable smart photoresponse
Introduction
towards external stimulus; however, the issue of photoswitchable
catalysis based on MOF catalyst is still not addressed untill now.
Previous researches have disclosed that photosensitive MOFs, a
subclass of MOFs, presents a new interesting and important material,
showing unique photomodulated host-guest response and
Metal-organic frameworks (MOFs), constructed by metal ions and
organic ligands through coordination bonds, owning several
outstanding merits such as high specific surface area, regular pore,
adjustable aperture, and functionalized pore wall, are recently
extensively pursued, due to not only their topological aesthetics, but
also broad applications in storage, separation, sensor, catalysis, and so
on. Among these applications MOF materials as catalyst are highly
attractive and have been demonstrated to catalyze a great deal of
chemical reactions involving in, but not limited to, Knoevenagel
condensation, Aza-Michael condensations, cyclohexene oxidation,
1
4
consequently important applications in practice. For example, Hill
1-4
et al proposed low-energy carbon dioxide capture and release by
1
5
means of azobenzene MOFs. Shustova et al used a dithienylethene-
1
6
porphyrin MOF to give turn-on/off fluorescence. The photochromic
switch in MOFs, as shown by Zhou et al, can be even applied for
1
7
controlled generation of singlet oxygen in living cells. Recently, we
also demonstrated the potential of photoactive MOFs for green
removal of VOC (volatile organic compound) and low-cost U(VI)
Suzuki-Miyaura
hydrogenation.
coupling,
CO
oxidation,
cyclooctene
5
-8
Note that once the reaction conditions are chosen, all established
MOF catalysts are inherently limitted to a fixed catalytic rate and/or
selecitivity, which means that such synthesis process could not be
artifically controlled by external stimulus. However, as we know, even
1
8
adsorption/release.
In this work, as an ongoing work in photoactive MOFs,18-19 we
attempt to develop a new conceptually MOF based photoswitchable
catalysis. To implement such goal, three crucial pre-requisites such as
porosity, photoresponse unit, and catalytic-active site are initially
considered. Accordingly, we make a precise choice in organic ligands
in simple living organisms many essential functions such as
photosynthesis are highly controllable by external factor.9 In this
regard, to meet future catalysis we have to focus on the development
of switchable catalysis, especially photoswitchable catalysis, as light
stimulus is non-invasive and can offers excellent temporal and spatial
and 4,4΄-diazene-1,2-diyldibenzoate acid (H
because, i) the long carboxylate ligand of H
coordinate with metal ions and enables to generate porous
2
AzDC) ligand is selected,
2
AzDC facilitates to
1
0-12
resolution.
2
0
framework; ii) as a typical T-type photochrome, azobenzene system
often provides good stability, good photomechanical properties, fast
and
reversible
photoisomerization,
and
exquisite
E-Z
photoisomerization with a large geometrical change from d4-4΄≈9Å of
the co-planar E (tans) configuration to d4-4΄≈6Å of the non-planar Z
aState Key Laboratory for Nuclear Resources and Environment, and School of
Biology, Chemistry and Material Science, East China University of Technology,
Nanchang, Jiangxi344000, China, *E-mail: ecitluofeng@163.com
(
cis) configuration, suggesting it as a good candidate to play a
b
21
College of Chemistry and Chemical Engineering, Luoyang Normal University,
photoresponse role; iii) the -N=N- group of H
fascinating functional group capable of acting as a base-type catalyst.
As a result, the new prepared MOF, [In(AzDC) ] [H N(CH ],
2
AzDC is also a
Luoyang, 471022, P. R. China. *E-mail: mazhuxp@126.com
c
State Key Laboratory of Magnetic Resonance and Atomic and Molecular
2
2
3 2
)
Physics,Wuhan Institute of Physics and Mathematics, The Chinese Academy of
Sciences, Wuhan 430071, China, *E-mail: zhenganm@wipm.ac.cn
These authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: additional figures. See
DOI: 10.1039/x0xx00000x
namely ECUT-50, shows regular 1D channel of 8.4Å×8.4Å along a
axis, excellent catalysis performance for the Knoevenagel
condensation reactions, and unique photoswitchable catalysis.
‡
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
Catalysis Performance.We note that the KnoevenageVlicewonAdrteicnlesOatniloinne
reaction, typically presenting a base-catalyzeDdOmI: 1o0d.1e0l3r9e/aCc7tiToAn0,13is88aDn
important methodology in organic synthesis for formation of new C-
C bond. It has been demonstrated that both MOFs and COFs (covalent
Results and discussion
3 2
The Structure of ECUT-50. Reacting InCl and H AzDC in
DMF at 110ºC for three days yields large block crystals of
ECUT-50 with high yield (92%) and purity. Its structure is
determined by single crystal X-ray diffraction, giving the
Orthorhombic, Pnna space group. The In(III) site displays a
somewhat distorted square-antiprismatic geometry finished by
2
5
organic frameworks), containing certain base-like catalysis position
in the pore wall, could not only catalyze such reaction but also perform
size-selectivity. To characterize its base properties of ECUT-50a
2
-
stemming from the -N=N- segment of AzDC ligands, we
systematicly studied it as a catalyst for the Knoevenagel condensation
reaction, involving dosage of catalyst (Fig. S4), reaction temperature
2
-
eight oxygen atoms from four AzDC ligands (Fig. 1a). The
2
-
AzDC ligand takes the trans configuration and bi(bidentate)
(Fig. S5), and various aldehyde substrates. Table 1 shows the catalytic
mode. As shown in Fig. 1b, the combination of In(III) ions and
2
-
results of the condensation between aldehyde substrates and
cyanoethylacetate over the MOF catalyst, ECUT-50a. Higher
catalytic performance is observed for these substrates with the size of
less than 6.7 Å, and especially the substrates of more than 7.2 Å even
could not be converted to corresponding product. The results imply
high size-selectivity of ECUT-50a. And as suggested in the
AzDC ligands builds a 3D framework with large open channel,
which further allows to occur four-fold interpenetration in the
2
2
[
2+2] fashion. Thereby the resulted open window with the
consideration of atom radius is estimated to be 8.4Å×8.4Å (Fig.
c), giving a solvent-accessible volume of 66.3%.23 Topology
analysis suggests dia net with four-fold interpenetration (Fig.
1
1
1
2
2
literature, such size-selectivity should be mainly dependent on the
open window of MOFs. For ECUT-50a, although it provides about
0.84 nm open window, however the location of charge-balance ions
1
d).
a)
b)
2 3 2
of [H N(CH ) ] inside the channel would reduce the size of open
window, consequently leading to that the large substrates with the size
of more than 7.2 Å is excluded from the channel of ECUT-50a.
To attest its heterogeneity, a hot filtration experiment was
carried out for 5h, however no further conversion of substrate
was observed (Fig. S6). Moreover, ECUT-50a
,
as
heterogeneous catalyst, can be readily isolated from the reaction
system via filtration and further reused at least three times just
with a little drop in activity (Fig. S7).
Table 1. Knoevenagel condensation reactions catalyzed by
ECUT-50a.
c)
d)
Substratea
Molecular Sizeb
Conversionc
Fig. 1 The structure of ECUT-50. a) the coordination
surrounding of In(III) site; b) the 3D open framework
2
-
constructed by In(III) and AzDC ligands; c) four-fold
interpenetrating framework with the open window of 8.4Å×8.4Å;
d) topological view of the dia net with four-fold interpenetration
in the [2+2] fashion. All hydrogen atoms are omitted for clarity.
Color code: In/purple, O/red, C/gray, N/blue. The
interpenetration is respectively distinguished by color of black,
green, blue, and red.
6
4
2.4%
3.5%
Porosity of ECUT-50. Thermal gravimetric analysis (TG, Fig.
S1) plus powder X-ray diffraction (PXRD, Fig. S2) is employed
to confirm the thermostability and robust framework of ECUT-
92.6%
86.1%
50. The first major weight loss of 37% before 200ºC belongs to
the loss of free DMF molecules. The PXRD patterns of activated
samples, ECUT-50a, match with that of as-synthesized samples,
indicative of maintenance of its framework integrality after
degassing. The permanent porosity of ECUT-50a is evaluated
by N
2
adsorption at 77K. The results are presented in Fig. S3,
9
7
2.4%
2.6%
giving a Brunauer-Emmett-Teller (BET) surface area of 175
2
2
m /g and Langmuir surface area of 223 m /g. The pore size
distribution (PSDs) is calculated using the well-known method
of nonlocal density functional theory (NLDFT),24 and a narrow
pore width of ca. 0.98 nm is observed, comparable with the
predicted value of 0.84 nm from crystal data.
2
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for not only photoswitching catalytic activity but also pVhieowtoAsrtwiclietcOhnilninge
catalytic selectivity.
DOI: 10.1039/C7TA01388D
8
2.1%
Table 2. The experimental results in the dark and UV (365
nm) for these selected aldehyde substrates.
a
Reaction rate(mmol-1s-
)
Substrates
Conversion
1
b
-4
dark : 92.6%
kon: 6.1×10
3
7
1.8%
8.4%
UV
c
: 6%
Δ : 86.6%
koff: 1.5×10-6
d
e
k
on/koff: 407
Salicylaldehyde
-4
dark: 86.1%
UV:51.4%
Δ: 34.7%
k
k
k
on: 2.97×10
-
5
off: 4.97×10
f
on/koff:
6
2
2
-chlorobenzaldehyde
-nitrobenzaldehyde
6
4
8.6%
7.4%
4
dark: 92.4%
UV:39.6%
Δ: 52.8%
k
k
k
on: 5.73×10-
-
5
off: 2.88×10
on/koff: 19.9f
on: 4.17×10-
4
dark: 78.4%
UV:18.5%
Δ: 59.9%
k
k
k
-
6
off: 9.67×10
on/koff: 43f
6
1
.4%d
4-fluorobenzaldehyde
a
Reactions were performed with 1mmol substrates and 1mmol cyanoethylacetate in
0 mL C OH with 15 mg catalyst of ECUT-50a for 6 h at 60ºC.
1
2 5
H
b
c
d
Reactions are performed in the dark.
Reactions are performed under UV (365nm).
The difference for conversion of substrates in the dark and UV after reaction for
0.4%d
6
h.
e
f
Third-order rate constants, see Figure S8
Second-order rate constants, see Figure S9-11.
5
.0%d
a
Reactions were performed with 1mmol substrates and 1mmol cyanoethylacetate in
0 mL C OH with 15 mg catalyst of ECUT-50a for 6 h at 60ºC.
The size of substrate was calculated as the longest distance of these molecules.
Pure isolated product from recrystallization is obtained and characterized by GC.
No product from recrystallization is obtained.
1
2 5
H
b
c
d
a)
b)
Photoswitchable Catalysis. As we know, azobenzene derivates are
an excellent photochromic candidate, due to its large geometrical
change of E-Z photoisomerization and some unique merits, which is
1
0-12
well realized in photoswitching catalysis of organic synthesis
or
1
4
photomodulating host-guest behavior in MOFs. In this regard, we
carried out photoswichting catalytic experiments and the results are
shown in Fig. 2 and Table 2. For these selected aldehyde substrates,
the conversion of salicylaldehyde under UV (365 nm) is completely
rejected with only negligible conversion to product (<6% by GC,
commonly referred as the OFF state), giving a significant decrease of
more than 86.6%, relative to its high conversion (92.6%, commonly
referred as the ON state) in the dark. The reaction with a third-order
c)
d)
e)
-
4
rate constant in the dark (kon) or UV (koff) is estimated to be 6.1×10
-
1
-1
-6
-1 -1
mmol s and 1.5×10 mmol s , respectively. Such observed 407-
fold (kon/koff) decrease in activity upon UV irradiation presents the
8
highest value in the field of photoswitching catalysis and suggested
us that for salicylaldehyde substrate ECUT-50a catalyst is almost
inactive under UV irradiation to execute the Knoevenagel
condensation reaction. Significant decrease in activity under UV
irradiation for other aldehyde substrates are also observed (2-
chlorobenzaldehyde, kon/koff=6.0; 2-nitrobenzaldehyde, kon/koff= 19.9;
4
-fluorobenzaldehyde, kon/koff=43), however, where we also notice
Fig. 2 The photoswitching catalysis for these selected aldehyde
substrates. a), b), c), d) presents the conversion of these selected
aldehyde substrates in the dark or UV (365 nm). e) the difference in
disparate photomodulation of the reaction kinetics that directly relates
to the size of aldehyde substrates, suggesting photoswitching catalytic
selectivity. Thus, the results suggest ECUT-50a as a superior catalyst
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Journal Name
conversion in the dark or UV after 6 h for these selected aldehyde
substrates.
View Article Online
DOI: 10.1039/C7TA01388D
trans
cis
The Mechanism of Catalysis and Size-Selectivity. To disclose the
catalysis mechanism several appropriate control experiments were
conducted.
condensation
A
homogeneous catalysis of the Knoevenagel
reaction between 2-nitrobenzaldehyde and
cyanoethylacetate was carried out without catalyst or with the reagent
of InCl or H AzDC, giving the conversion of 0%, 29.7%, and 73.8%,
respectively (Fig. S12). These results demonstrate that such reaction
is not spontaneous, but could be accelerated by both InCl and
AzDC, however, with their catalytic ability far less than the
3
2
3
H
2
heterogeneous catalyst of ECUT-50a that shows the value of 92.4%.
In this regard, the catalytic performance of ECUT-50a is mainly
2
-
derived from AzDC ligands located on its pore wall.
To better understand size-selectivity, both TG and IR
characterizations were employed to trace the inclusion of
aldehyde substrates inside MOFs. Fig. S13 clearly suggests that Fig. 3. DFT calculation of the potential of H
2
AzDC2- ligands in the
the large substrate of 4-biphenylcarboxaldehyde could not be trans or cis-conformation surrounded by benzaldehyde molecule.
accommodated inside ECUT-50a, whereas on the contrary,
ECUT-50a affords considerable adsorption capacity towards the
smaller reactants like that of 2-nitrobenzaldehyde (ca. 3 photoisomerization of AzDC ligands with photoswitching storage of
molecules per ECUT-50a) and salicylaldehyde (ca. 5 molecules guest molecules (Fig. 3). We found that each trans- H AzDC holds
per ECUT-50a). Infrared spectroscopy of the catalyst also the potential surrounded by four benzaldehyde molecules, whereas
presents the fail in infusing large substrate of 4- due to steric hindrance each cis-H AzDC only accommodate three
Furthermore, we also carried out DFT calculation to correlate E-Z
2
-
2
2
biphenylcarboxaldehyde inside ECUT-50a, but the success in benzaldehyde molecules around it; this suggests that the storage
loading of small substrate of salicylaldehyde (Fig. S14). All the capacity of guest molecules in ECUT-50a would be largely decreased
above evidences agree that the size of the open window is the if triggered by UV, consistent with the experimental results.
key factor for ECUT-50a to recognize and distinguish these
We also note that although the substrates of salicylaldehyde
aldehyde substrates with various sizes, consequently leading to and 2-chlorobenzaldehyde own comparable size, however, their
the high size selectivity when it is used to catalyze the outcome in photoswitchable catalysis is very different. Thereby,
Knoevenagel condensation reaction.
the finally products were recrystallized and determination by
single crystal X-ray diffraction (Fig. S18). All the aldehyde
The Mechanism of Photoswitchable Catalysis. The photoactivity of substrates, except for salicylaldehyde, undergo the Knoevenagel
ECUT-50a was initially evaluated by UV-Vis spectrum (Fig. S15), condensation reation with the formation of new carbon-carbon
2
-
where a characteristic E-Z photoisomerization of AzDC ligands bonds of ~1.32Å, comparable with C=C double bond, and a E-
under UV (365nm) irradiation is detected.14 The photoresponse configuration. Surprisedly, the salicylaldehyde substrate
2
towards guest molecule was tested by CO adsorption at 293K, where generates an exceptional product, where both the Knoevenagel
3
an adsorption capacity of 8.4 cm /g is observed for ECUT-50a at 1 condensation and Michael addition reaction are observed,
atm in the dark, whereas under UV (365 nm) its adsorption capacity leading to the formation of two new carbon-carbon bonds (C2-
decreases by 17% (Fig. S16). Similarly, its photoresponse towards C3/1.506(3)Å from the Knoevenagel condensation and C3-
salicylaldehyde is shown in Figure S13, where under UV(365 nm) C10/1.558(3)Å from Michael addition), agreeing with the value
ECUT-50a only adsorbs ca. 2.5 molecules per ECUT-50a, relative of C-C single bond. The results indicate that to conversion of
to the adsorption ability of ECUT-50a in the dark, suggesting a 50% salicylaldehyde, relative to other aldehyde substrates, two-fold
decrease in adsorption of salicylaldehyde. The decrease in adsorption amount of salicylaldehyde are needed. In this regard, in
of guest molecule was obtained in the dark because of the near- conjunction with the TG results, the 50% decrease in loading
complete conversion of the cis form to the trans form, consequently salicylaldehyde within ECUT-50a under UV irradiation could
leading to the unique photoswitchable catalysis observed above.
not meet its conversion criterion, thus leading to the ultrahigh
AzDC ligands as photoswitching catalyst was also measured photocontrol in catalysis activity. To the best of our knowledge,
Fig. S17), and significant decrease in conversion and catalysis the case of showing the coincidence of the Knoevenagel
activity of the condensation reaction between 2-nitrobenzaldehyde condensation and Michael addition reaction in a single system
2
-
H
2
(
-
4
-1 -1
and cyanoethylacetate from 73.8% and kon= 1.3×10 mmol s to catalyzed by MOFs or COFs is never documented.
-
5
-1 -1
2
5.1% and koff=1.2×10 mmol s is observed, giving a 48.7%
decrease in conversion and 8.3-fold (kon/koff) decrease in catalysis
activity. By contrast, ECUT-50a affords a 19.9-fold (kon/koff
decrease in catalysis activity, almost 2.4 times bigger than that
)
Conclusions
2
-
In summary, we have conveyed the concept upon MOF
platform, for the first time, to control organic reaction by
photoswiching catalysis in both catalysis activity and selectivity.
observed for only
H
2
AzDC
ligands, implying that the
photoswitchable catalysis performed by ECUT-50a origins from E-Z
2
-
photoisomerization of AzDC ligands, but incorporation of
2
-
2
The photosensitive H AzDC ligand is the key factor to execute
photoactivated AzDC ligands into MOF platform will largely
enhance its photocontrol ability.
both catalysis and photoresponse performance, while MOF
environment is also critical to enhance the catalysis,
photoswitchable catalysis, and especially unique catalysis
selectivity via confined space within the pores of MOF. The
results present an excellent example of photoswitchable catalysis
and may be transferred to other organic reactions, if with a
4
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precise molecule design in the pores of MOFs or selecting proper
MOFs.
Fukushima, M. Tsujimoto, S. Isoda, S. Kitagawa, J. Am. Chem. Soc. 2012, 134,
View Article Online
4
501.
DOI: 10.1039/C7TA01388D
1
5 (a) R. Lyndon, K. Konstas, B. P. Ladewig, P. D. Southon, C. J. Kepert, M. R.
Hill, Angew. Chem. Int. Ed. 2013, 52, 3695; (b) R. Lyndon , K. Konstas , R. A.
Evans , D. J. Keddie , M.R. Hill , B. P. Ladewig, Adv. Funct. Mater. 2015, 25,
4
405.
Acknowledgements
This work was supported by the NSF of China (21661001,
1
1
6 D. E. Williams, J. A. Rietman, J. M. Maier, R. Tan, A. B. Greytak, M. D. Smith,
J. A. Krause, N. B. Shustova, J. Am. Chem. Soc. 2014, 136, 11886.
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21661002), the Natural Science Foundation of Jiangxi Province
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188.
of China (20143ACB20002, 20151BAB203001), and the Young 18 (a) L. L. Gong, X. F. Feng, F. Luo, X. F. Yi, A. M. Zheng, Green Chem., 2016,
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1
scientist training program of Jiangxi Province of China
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Journal of Materials Chemistry A
Page 6 of 6
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DOI: 10.1039/C7TA01388D
Photoswitching storage of guest molecules in metal-organic framework for
photoswitchable catalysis: exceptional product, ultrahigh photocontrol, and
photomodulated size selectivity
ac‡
a‡
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c
a
a
Le Le Gong, Wan Ting Yao, Zhi Qiang Liu, An Min Zheng *, Jian Qiang Li , Xue Feng Feng , Lu Fang
b
a
a
a*
Ma, * Chang Sheng Yan , Ming Biao Luo , and Feng Luo
We present a novel MOF catalyst, which not only offers ultrahigh photocontrol, but also displays
disparate photomodulation in reaction kinetics towards various aldehyde substrates, thus creating
the first example in MOFs showing photoswitchable catalysis.