Highly Efficient and Selective Photooxidation of Sulfur Mustard Simulant by a Triazolobenzothiadiazole-Moiety-Functionalized Metal-Organic Framework in Air

Article abstract of DOI:10.1021/acs.inorgchem.8b00106

A photoactive triazolobenzothiadiazole (TBTD)-conjugated terphenyldicarboxylate (TPDC) linker was introduced into a porous and robust UiO-68 isoreticular zirconium metal-organic framework (denoted as UiO-68-TBTD) by the de novo synthetic approach of mixed TPDC struts. Under blue-light-emitting-diode irradiation, UiO-68-TBTD can serve as a heterogeneous photocatalyst for the highly efficient and selective oxidation of a sulfur mustard simulant (2-chloroethyl ethyl sulfide) to the corresponding much less toxic sulfoxide product, with a half-life of only 3 min in the open air atmosphere.

Full text of DOI:10.1021/acs.inorgchem.8b00106

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Highly Efficient and Selective Photooxidation of Sulfur Mustard
Simulant by a Triazolobenzothiadiazole-Moiety-Functionalized
Metal−Organic Framework in Air
Wen-Qiang Zhang,†,‡ Ke Cheng,†,‡ He Zhang,† Qiu-Yan Li,*,† Zheng Ma,† Zixuan Wang,† Jialing Sheng,†
Yinwei Li,§ Xinsheng Zhao,§ and Xiao-Jun Wang*,†,∥
†School of Chemistry and Materials Science and §School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou
221116, P. R. China
∥Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong
Province, Shantou University, Shantou, Guangdong 515063, P. R. China
S
* Supporting Information
Among these above materials, MOFs as a versatile platform for
ABSTRACT: A photoactive triazolobenzothiadiazole
(TBTD)-conjugated terphenyldicarboxylate (TPDC) link-
er was introduced into a porous and robust UiO-68
isoreticular zirconium metal−organic framework (denoted
as UiO-68-TBTD) by the de novo synthetic approach of
mixed TPDC struts. Under blue-light-emitting-diode
irradiation, UiO-68-TBTD can serve as a heterogeneous
photocatalyst for the highly efficient and selective
oxidation of a sulfur mustard simulant (2-chloroethyl
ethyl sulfide) to the corresponding much less toxic
sulfoxide product, with a half-life of only 3 min in the
open air atmosphere.
degrading CWAs are more appealing because of their high
porosity and surface area as well as tunable composition,
structure, and functionality.15−20 In particular, Farha, Hupp, and
their co-workers have recently made significant strides in
developing MOF-based photocatalysts for the oxidative
decontamination of sulfur mustard.21−26 Different photosensi-
tizer moieties, such as porphyrin,21 fullerene,24 and boron
dipyrromethene (BODIPY),25 have been incorporated into
MOF scaffolds via a straightforward or postsynthetic method.
These photoactive moieties in MOFs can be effectively excited
under proper irradiation and subsequently transfer the energy to
ground-state oxygen (3O2) with the facile generation of singlet
oxygen (1O2),27 which is responsible for the highly selective
oxidation of sulfide analogues into nontoxic sulfoxide species.
Moreover, the ordered 3D structure of the MOF can greatly
reduce the aggregation and deactivation of the photosensitizer in
the framework and also facilitate diffusion of the substrate toward
the active site, thereby accelerating such a photocatalytically
oxidative degradation process. For instance, it was observed that
the half-life (t1/2) for oxidation of the HD simulant 2-chloroethyl
ethyl sulfide (CEES) into 2-chloroethyl ethyl sulfoxide (CEESO)
by using a BODIPY-functionalized MOF could even be as low as
2 min.25
ulfur mustard [bis(2-chloroethyl) sulfide; Scheme 1], also
S
known as HD or mustard gas, is a vesicant and blistering
Scheme 1. Oxidation of HD into a Less Toxic Sulfoxide
(HDO) and a Highly Toxic Sulfone (HDO2), Meaning That
the Selectivity of Oxidation Is Very Critical for the Safe
Degradation of HD
However, it should be noted that these above-reported
oxidations of CEES to CEESO have to be conducted in pure
molecular O2 in order to ensure such a fast conversion (Table
1).21−26 While the same transformation was performed in an air
atmosphere, the efficacy would be largely depressed (such as that
21
for a porphyrinic MOF, PCN-222/MOF-545;
t
= 13 min in
1/2
O2 and 21 min in air). Obviously, if the selective photooxidation
of CEES could still be accomplished with a high reaction rate by
directly using air instead of pure O2 as the 1O2 source, it would be
much more convenient for a practical operation, especially for
the case of HD detoxification on site. In this regard, the further
development of novel photosensitizer-based organic linkers for
MOFs may offer highly promising potential.
chemical warfare agent (CWA).1 The partial oxidation of HD to
the much less toxic bis(2-chloroethyl) sulfoxide (HDO) but
without formation of the quite toxic full-oxidation sulfone
derivative (HDO2; Scheme 1) is regarded as a feasible
decontamination route.2−4 Toward this end, a variety of
materials or systems have been developed and evaluated to
achieve the catalytic and selective oxidation of HD or its
simulants into nontoxic sulfoxide analogues in the past few
years,5−17 such as polyoxometalates,9 modified mesoporous
silica,10,11 metal oxides,12 polymer networks,13,14 and metal−
organic frameworks (MOFs).15−17
Herein, we have designed and synthesized a triazolobenzo-
thiadiazole (TBTD)-conjugated terphenyldicarboxylate
Received: January 11, 2018
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b00106
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
a
Table 1. Comparison of t1/2 Values for CEES Oxidation by Using Various MOF-Based Photocatalysts
b
MOF photocatalyst
effective photosensitizer
mol %
atmosphere
LED (mW cm−2
)
t1/2 (min)
ref
PCN-57-S
benzothiadiazole
benzoselenadiazole
pyrene
0.1
0.1
1
pure O2
pure O2
pure O2
pure O2
pure O2
air
UV (865)
purple (865)
UV (450)
UV (450)
blue (325)
blue (325)
green (325)
blue (100)
7.5
3.5
6.2
3.5
13
26
PCN-57-Se
26
NU-1000
23
NU-1000-PCBA
PCN-222
pyrene and C60
porphyrin
1
24
0.5
0.5
0.2
0.2
21
PCN-222
porphyrin
21
21
Br-BDP@NU-1000
UiO-68-TBTD
BODIPY
pure O2
air
2.5
3
25
TBTD
this study
a
All of the reactions were performed in a methanol solvent at room temperature. No overoxidized product CEESO2 was observed in all cases, which
b
1
should be attributed to the high selectivity of the mild O2 oxidant. The molar ratio of the catalyst loading was calculated based on the moles of
effective photosensitizers in MOF photocatalysts.
(TPDC) linker (denoted as H2-TBTD; Scheme 2a), in which the
benzothiadiazole (BTD) part was annelated with a benzotriazole
mixed-strut approach was thus employed to incorporate the
ligand H2-TBTD with a small percentage into the UiO-68
analogue MOF because of the well-known high porosity and
chemical and thermal stability of the UiO series zirconium
MOFs.28,33 Specifically, a mixture of H2-TBTD and H2-mTPDC
linkers (in a 1:3 molar ratio) with matching ligand lengths was
reacted with ZrCl4 in N,N′-dimethylformamide at 100 °C for 2
days to produce the target MOF UiO-68-TBTD (for details, see
the Supporting Information). This mix-and-match synthetic
approach will guarantee formation of the UiO-68 framework as
well as maintain the pore opening. As expected, a powder X-ray
diffraction (PXRD) investigation of UiO-68-TBTD confirmed
that its framework is isostructural with the parental MOF UiO-68
along with a highly crystalline architecture (Figures 1a and S1).
Additionally, N2 sorption at 77 K was performed to reveal its
porosity. As shown in Figure 1b, a typical type I reversible
isotherm with a sharp increase prior to a plateau was observed,
indicative of a microporous feature. Also, the Brunauer−
Emmett−Teller surface area and pore-size distribution by
Scheme 2. (a) Synthetic Route for the MOF UiO-68-TBTD
with Mixed TPDC Linkers of H2-TBTD and H2-mTPDC and
(b) Selective Photooxidation of a HD Simulant, CEES,
Catalyzed by UiO-68-TBTD under Blue-LED Irradiation in
an Air Atmosphere
1
(BTz) moiety to give birth to an efficient O2 photosensitizer.
Subsequently, the ligand was readily integrated into the UiO-68
isoreticular zirconium MOF by the mixed TPDC struts28−33
(H2-TBTD and H2-mTPDC; Scheme 2a). In the open air
atmosphere and under blue-light-emitting-diode (LED) irradi-
ation, the photoactive TBTD-functionalized MOF UiO-68-
TBTD can work as a heterogeneous photocatalyst for the highly
efficient and selective oxidation of the HD simulant CEES into
CEESO (Scheme 2b).
The photoactive organic linker H2-TBTD can be conveniently
obtained starting from our recently reported precursor
compound of the diamino-BTD derivative after a three-step
reaction.32 As depicted in Scheme S1, the precursor dimethyl
4,4′-(5,6-diaminobenzo[c][1,2,5]-thiadiazole-4,7-diyl)-
dibenzoate (1) was cyclized with NaNO2 under acidic conditions
to give compound 2 with formation of a BTz moiety, which was
further reacted with 1-bromohexane in the presence of
triethylamine to afford N-alkylated compound 3. Then, the
ester 3 was hydrolyzed to generate the target linker H2-TBTD
with a high overall yield. Here an n-hexyl group was introduced
with the purpose of increasing the linker solubility, whereas such
a long tail fragment would possibly block the pores or channels in
the MOF architecture. To overcome this drawback, a de novo
Figure 1. PXRD patterns (a) and N2 sorption isotherm at 77 K (b) for
UiO-68-TBTD (fresh and after five successive CEES oxidation cycles).
B
DOI: 10.1021/acs.inorgchem.8b00106
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
nonlocal density functional theory were estimated to be ∼2900
m2 g−1 and ∼1.6 nm (Figure S8), respectively. This high porosity
and large open channel of UiO-68-TBTD will aid in the diffusion
of substrate and product in and out of the framework, thus
facilitating an enhanced performance for heterogeneous catalysis.
We first investigated organic linker H2-TBTD for the
photocatalytic oxidation of the HD simulant CEES in a
homogeneous system34 because it has been demonstrated that
the featured structure of a BTD/BTz hybrid can function as an
excellent sensitizer moiety for O2 generation. Because the
linker has an absorption band in the visible-light range of 425−
500 nm (Figure S10), commercially available blue-LEDs with
λmax = 450 nm were employed to excite the TBTD chromophore
in the photocatalytic reaction (power density = 100 mW cm−2).
After 20 min of irradiation in the open air atmosphere at room
temperature, the full conversion of CEES to CEESO was
observed in the presence of 0.2 mol % H2-TBTD as the
(Figure S15), indicating the high photostability of the TBTD
moiety. Additionally, PXRD and N2 sorption after five reaction
cycles confirmed the highly robust framework of UiO-68-TBTD
(Figure 1).
In order to validate the critical role of the featured TBTD
moiety on the highly efficient oxidation of CEES, two control
MOFs, UiO-68-BTD and UiO-68-BTz containing only the half
of the TBTD, were further prepared (for details, see the
Supporting Information). As shown in Figure 2, the conversion
of CEES to CEESO by UiO-68-BTD exhibited a much slower
rate with a long t1/2 of 43 min under the same conditions. As for
the case of UiO-68-BTz, only 12% conversion of CEES was
observed after 60 min of blue-LED irradiation (t1/2 = 6.5 h),
suggesting negligible catalytic activity. These observations
confirmed the need for the TBTD moiety (i.e., the hybrid of
BTD/BTz) functioning as an active photocatalytic center to
highly drive the selective oxidation of CEES.
35
1
photocatalyst (Figures 2 and S12), in which the half-life (t1/2
)
In summary, a photoactive TBTD-conjugated TPDC
derivative linker has been rationally developed and subsequently
integrated into a porous and robust UiO-type isoreticular
zirconium MOF UiO-68-TBTD with mixed dicarboxylate struts.
In the open air atmosphere, the MOF can efficiently and
selectively photocatalyze CEES into CEESO without the
formation of CEESO2 under blue-LED irradiation, along with a
half-life of as low as 3 min. In comparison to the reported MOF-
based analogue photocatalysts, which should utilize pure O2 as a
1O2 source to ensure rapid oxidation, this study may provide a
much more convenient and practical detoxification method for
mustard-related agents.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.8b00106.
■
S
Figure 2. Oxidation of CEES to CEESO over time with different
photocatalysts under blue-LED irradiation (100 mW cm−2; 0.2 mmol of
CEES in 1 mL of methanol) in the open air atmosphere.
Experimental procedure and additional synthesis and
characterization data (PDF)
was calculated to 6.5 min. No overoxidized product of 2-
chloroethyl ethyl sulfone (CEESO2) was detected, which should
be attributed to the highly selective nature of 1O2 working as an
oxidant.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: qyli@jsnu.edu.cn (Q.-Y.L.).
*E-mail: xjwang@jsnu.edu.cn (X.-J.W.).
■
With the desired success of CEES selective oxidation by our
synthesized organic linker in a homogeneous system, the
photocatalytic performance of a TBTD-functionalized MOF in
a heterogeneous system was next studied to estimate its potential
application in the oxidative decontamination of sulfur mustard.
To our delight, it was observed that CEES can be completely
transformed into CEESO without the formation of CEESO2
within 10 min under the same conditions when 0.2 mol % UiO-
68-TBTD (mol % based on the TBTD moiety in the MOF) was
ORCID
Xiao-Jun Wang: 0000-0002-1461-4922
Author Contributions
‡These authors contributed equally.
Notes
The authors declare no competing financial interest.
1
used as a heterogeneous photosensitizer for O2 production
ACKNOWLEDGMENTS
■
(Figures 2 and S13), revealing an improved catalytic activity in
comparison to that of its homogeneous counterpart. The
corresponding t1/2 value was further calculated to be 3 min,
which was lower than that of most reported MOFs in 1 atm of O2
atmosphere, such as PCN-57-Se (or S)26 and PCN-22221 (Table
1). Also, it is even comparable to the reported lowest one (2.5
min) by the BODIPY-functionalized MOF Br-BDP@NU-
1000.25 In contrast, our system can be efficiently performed in
open air instead of pure O2, offering a more convenient practical
operation. Besides, the MOF UiO-68-TBTD can be easily
recycled and reused at least in five successive cycles without any
obvious loss of the original catalytic activity and selectivity
This work was financially supported by the NSFC (Grants
21302072, 11722433, and 21776119), PAPD, and TAPP of
Jiangsu Higher Education Institutions.
REFERENCES
■
(1) Szinicz, L. History of Chemical and Biological Warfare Agents.
Toxicology 2005, 214, 167−181.
(2) Yang, Y. C.; Baker, J. A.; Ward, J. R. Decontamination of Chemical
Warfare Agents. Chem. Rev. 1992, 92, 1729−1743.
(3) Kim, K.; Tsay, O. G.; Atwood, D. A.; Churchill, D. G. Destruction
and Detection of Chemical Warfare Agents. Chem. Rev. 2011, 111,
5345−5403.
C
DOI: 10.1021/acs.inorgchem.8b00106
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
(4) Smith, B. M. Catalytic Methods for the Destruction of Chemical
Warfare Agents Under Ambient Conditions. Chem. Soc. Rev. 2008, 37,
470−478.
Oxidation of Sulfur Mustard Using Singlet Oxygen Generated by a
Pyrene-based Metal−Organic Framework. J. Mater. Chem. A 2016, 4,
13809−13813.
(24) Howarth, A. J.; Buru, C. T.; Liu, Y.; Ploskonka, A. M.; Hartlieb, K.
J.; McEntee, M.; Mahle, J. J.; Buchanan, J. H.; Durke, E. M.; Al-Juaid, S.
S.; Stoddart, J. F.; DeCoste, J. B.; Hupp, J. T.; Farha, O. K. Postsynthetic
Incorporation of a Singlet Oxygen Photosensitizer in a Metal−Organic
Framework for Fast and Selective Oxidative Detoxification of Sulfur
Mustard. Chem. - Eur. J. 2017, 23, 214−218.
(25) Atilgan, A.; Islamoglu, T.; Howarth, A. J.; Hupp, J. T.; Farha, O. K.
Detoxification of a Sulfur Mustard Simulant Using a BODIPY-
Functionalized Zirconium-based Metal−Organic Framework. ACS
Appl. Mater. Interfaces 2017, 9, 24555−24560.
(26) Goswami, S.; Miller, C. E.; Logsdon, J. L.; Buru, C. T.; Wu, Y.-L.;
Bowman, D. N.; Islamoglu, T.; Asiri, A. M.; Cramer, C. J.; Wasielewski,
M. R.; Hupp, J. T.; Farha, O. K. Atomistic Approach Toward Selective
Photocatalytic Oxidation of a Mustard-Gas Simulant: A Case Study with
Heavy-Chalcogen-Containing PCN-57 Analogues. ACS Appl. Mater.
Interfaces 2017, 9, 19535−19540.
(27) DeRosa, M. C.; Crutchley, R. J. Photosensitized Singlet Oxygen
and its Applications. Coord. Chem. Rev. 2002, 233−234, 351−371.
(28) Bai, Y.; Dou, Y.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-C. Zr-
based Metal−Organic Frameworks: Design, Synthesis, Structure, and
Applications. Chem. Soc. Rev. 2016, 45, 2327−2367.
(29) Wang, C.; Xie, Z.; deKrafft, K. E.; Lin, W. Doping Metal−Organic
Frameworks for Water Oxidation, Carbon Dioxide Reduction, and
Organic Photocatalysis. J. Am. Chem. Soc. 2011, 133, 13445−13454.
(30) Zhang, W.-Q.; Li, Q.-Y.; Zhang, Q.; Lu, Y.; Lu, H.; Wang, W.;
Zhao, X.; Wang, X.-J. Robust Metal−Organic Framework Containing
Benzoselenadiazole for Highly Efficient Aerobic Cross-Dehydrogen-
ative Coupling Reactions under Visible Light. Inorg. Chem. 2016, 55,
1005−1007.
(31) Li, Q.-Y.; Ma, Z.; Zhang, W.-Q.; Xu, J.-L.; Wei, W.; Lu, H.; Zhao,
X.; Wang, X.-J. AIE-active Tetraphenylethene Functionalized Metal−
Organic Framework for Selective Detection of Nitroaromatic Explosives
and Organic Photocatalysis. Chem. Commun. 2016, 52, 11284−11287.
(32) Zhang, W.-Q.; Li, Q.-Y.; Cheng, J.-Y.; Cheng, K.; Yang, X.; Li, Y.;
Zhao, X.; Wang, X.-J. Ratiometric Luminescent Detection of Organic
Amines due to the Induced Lactam−lactim Tautomerization of Organic
Linker in a Metal−Organic Framework. ACS Appl. Mater. Interfaces
2017, 9, 31352−31356.
(5) Jang, Y. J.; Kim, K.; Tsay, O. G.; Atwood, D. A.; Churchill, D. G.
Update 1 of: Destruction and Detection of Chemical Warfare Agents.
Chem. Rev. 2015, 115, PR1−PR76.
(6) Picard, B.; Gouilleux, B.; Lebleu, T.; Maddaluno, J.; Chataigner, I.;
Penhoat, M.; Felpin, F.-X.; Giraudeau, P.; Legros, J. Oxidative
Neutralization of Mustard-Gas Simulants in an On-Board Flow Device
With In-line NMR Monitoring. Angew. Chem., Int. Ed. 2017, 56, 7568−
7572.
(7) Fallis, I. A.; Griffiths, P. C.; Cosgrove, T.; Dreiss, C. A.; Govan, N.;
Heenan, R. K.; Holden, I.; Jenkins, R. L.; Mitchell, S. J.; Notman, S.;
Platts, J. A.; Riches, J.; Tatchell, T. Locus-Specific Microemulsion
Catalysts for Sulfur Mustard (HD) Chemical Warfare Agent
Decontamination. J. Am. Chem. Soc. 2009, 131, 9746−9755.
(8) Carniato, F.; Bisio, C.; Psaro, R.; Marchese, L.; Guidotti, M.
Niobium(V) Saponite Clay for the Catalytic Oxidative Abatement of
Chemical Warfare Agents. Angew. Chem., Int. Ed. 2014, 53, 10095−
10098.
(9) Dong, J.; Hu, J.; Chi, Y.; Lin, Z.; Zou, B.; Yang, S.; Hill, C. L.; Hu, C.
A Polyoxoniobate-Polyoxovanadate Double-Anion Catalyst for Simul-
taneous Oxidative and Hydrolytic Decontamination of Chemical
Warfare Agent Simulants. Angew. Chem., Int. Ed. 2017, 56, 4473−4477.
(10) Ringenbach, C. R.; Livingston, S. R.; Kumar, D.; Landry, C. C.
Vanadium-Doped Acid-Prepared Mesoporous Silica: Synthesis, Char-
acterization, and Catalytic Studies on the Oxidation of a Mustard Gas
Analogue. Chem. Mater. 2005, 17, 5580−5586.
(11) Livingston, S. R.; Landry, C. C. Oxidation of a Mustard Gas
Analogue Using an Aldehyde/O2 System Catalyzed by V-doped
Mesoporous Silica. J. Am. Chem. Soc. 2008, 130, 13214−13215.
(12) Bisio, C.; Carniato, F.; Palumbo, C.; Safronyuk, S. L.; Starodub,
M. F.; Katsev, A. M.; Marchese, L.; Guidotti, M. Nanosized Inorganic
Metal Oxides as Heterogeneous Catalysts for the Degradation of
Chemical Warfare Agents. Catal. Today 2016, 277, 192−199.
(13) Bromberg, L.; Pomerantz, N.; Schreuder-Gibson, H.; Hatton, T.
A. Degradation of Chemical Threats by Brominated Polymer Networks.
Ind. Eng. Chem. Res. 2014, 53, 18761−18774.
(14) Chen, L.; Yang, Y.; Jiang, D. CMPs as Scaffolds for Constructing
Porous Catalytic Frameworks: A Built-in Heterogeneous Catalyst With
High Activity and Selectivity Based on Nanoporous Metalloporphyrin
Polymers. J. Am. Chem. Soc. 2010, 132, 9138−9143.
(15) Bobbitt, N. S.; Mendonca, M. L.; Howarth, A. J.; Islamoglu, T.;
Hupp, J. T.; Farha, O. K.; Snurr, R. Q. Metal-Organic Frameworks for
the Removal of Toxic Industrial Chemicals and Chemical Warfare
Agents. Chem. Soc. Rev. 2017, 46, 3357−3385.
(16) Liu, Y.; Howarth, A. J.; Vermeulen, N. A.; Moon, S.-Y.; Hupp, J.
T.; Farha, O. K. Catalytic Degradation of Chemical Warfare Agents and
Their Simulants by Metal-Organic Frameworks. Coord. Chem. Rev.
2017, 346, 101−111.
(17) DeCoste, J. B.; Peterson, G. W. Metal−Organic Frameworks for
Air Purification of Toxic Chemicals. Chem. Rev. 2014, 114, 5695−5727.
(18) Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Introduction to Metal−
Organic Frameworks. Chem. Rev. 2012, 112, 673−674.
(19) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The
Chemistry and Applications of Metal−Organic Frameworks. Science
2013, 341, 1230444.
(33) Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.;
Bordiga, S.; Lillerud, K. P. A New Zirconium Inorganic Building Brick
Forming Metal Organic Frameworks with Exceptional Stability. J. Am.
Chem. Soc. 2008, 130, 13850−13851.
(34) For safety reasons, less toxic CEES rather than highly toxic HD
was used to mimic the detoxification study because CEES also contains
the same reactive −SCH2CH2Cl group.
(35) Patel, D. G.; Feng, F.; Ohnishi, Y.-y.; Abboud, K. A.; Hirata, S.;
Schanze, K. S.; Reynolds, J. R. It Takes More Than an Imine: The Role
of the Central Atom on the Electron-Accepting Ability of Benzotriazole
and Benzothiadiazole Oligomers. J. Am. Chem. Soc. 2012, 134, 2599−
2612.
(20) Li, B.; Wen, H.-M.; Cui, Y.; Zhou, W.; Qian, G.; Chen, B.
Emerging Multifunctional Metal−Organic Framework Materials. Adv.
Mater. 2016, 28, 8819−8860.
(21) Liu, Y.; Howarth, A. J.; Hupp, J. T.; Farha, O. K. Selective
Photooxidation of a Mustard-Gas Simulant Catalyzed by a Porphyrinic
Metal−Organic Framework. Angew. Chem., Int. Ed. 2015, 54, 9001−
9005.
(22) Liu, Y.; Moon, S.-Y.; Hupp, J. T.; Farha, O. K. Dual-Function
Metal−Organic Framework as a Versatile Catalyst for Detoxifying
Chemical Warfare Agent Simulants. ACS Nano 2015, 9, 12358−12364.
(23) Liu, Y.; Buru, C. T.; Howarth, A. J.; Mahle, J. J.; Buchanan, J. H.;
DeCoste, J. B.; Hupp, J. T.; Farha, O. K. Efficient and Selective
D
DOI: 10.1021/acs.inorgchem.8b00106
Inorg. Chem. XXXX, XXX, XXX−XXX