Building a shp: A Rare-Earth Metal-Organic Framework and Its Application in a Catalytic Photooxidation Reaction

Application in a Catalytic Photooxidation Reaction

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Building a shp: A Rare-Earth Metal−Organic Framework and Its

Victor Quezada-Novoa, Hatem M. Titi, Amy A. Sarjeant, and Ashlee J. Howarth*

Cite This: Chem. Mater. 2021, 33, 4163 −4169

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sı Supporting Information

ABSTRACT: The design and synthesis of new metal−organic frameworks

MOFs) is important from both a fundamental and application standpoint. In

(

this work, a novel, highly connected rare-earth (RE) MOF with an shp

topology is reported, named RE-CU-10 (RE, rare-earth; CU, Concordia

University), composed of a nonanuclear RE(III)-cluster node (RE = Y(III)

and Tb(III)) and a tetratopic pyrene-based linker. This represents the ﬁrst

time that the 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H TBAPy) linker is

integrated in the shp topology. RE-CU-10 is explored as a heterogeneous

photocatalyst for the selective oxidation and detoxiﬁcation of a sulfur mustard

simulant, 2-chloroethyl ethyl sulﬁde (2-CEES), with Tb-CU-10 showing a half-life for conversion to the less toxic 2-chloroethyl ethyl

sulfoxide (2-CEESO) of 3.5 min under O and 22 min under air.

INTRODUCTION

Metal−organic frameworks (MOFs) are hybrid materials

composed of metal ions or clusters interconnected by organic

linkers, giving rise to open structures with accessible pores.

MOFs have been studied for many potential applications

tetrakis(4-carboxyphenyl)benzene (BTEB) linkers. The same

2-connected nonanuclear RE(III)-cluster was used as a

■

building block in the synthesis of RE-pek-MOF-1 (RE =

Y(III) and Tb(III)), RE-aea-MOF-1 (RE = Y(III)), Eu(III)-

based PCN-905-SO and PCN-906-O, and in the recently

reported RE-htp-MOF-1 (RE = Y(III), Ho(III), and Er-

−4

7,8

including, but not limited to, gas adsorption, catalysis,

,10

11,12

photocatalysis,

remediation.

chemical sensing,

Rare-earth (RE) metals, which include

and wastewater

(III)).

3−16

In this work, we report the synthesis of a new RE-MOF, RE-

CU-10 (RE = Y(III) and Tb(III); CU, Concordia University),

with shp topology, composed of nonanuclear RE(III)-cluster

nodes and a rectangular tetratopic pyrene-based linker, 1,3,6,8-

tetrakis(p-benzoic acid)pyrene (H TBAPy) (Figure 1). The

shp topology has not yet been reported for a MOF composed

of tetratopic H TBAPy linkers since the use of this linker tends

to favor the formation of scu and csq topologies driven by the

formation of eight-connected hexanuclear cluster nodes (NU-

scandium, yttrium, and the 15 lanthanoids, have been used

to synthesize a diverse library of MOFs, including many with

unique structures and properties driven by the high

coordination numbers and geometries of RE-metals.

Like other classes of MOFs, RE-MOFs have been reported

7−19

with several diﬀerent secondary building units (SBUs),

1,22

23−25

including inorganic nodes that are metal ions,

chains,

,26−29

or clusters.

In 2013, Eddaoudi et al. showed that the use

of ﬂuorinated modulators, such as 2-ﬂuorobenzoic acid, favors

the formation of RE-cluster nodes instead of the ion or chain

nodes that tend to preferentially form in the presence of

9,40

01 (scu, Zr -cluster),

Ce-CAU-24 (scu, Ce -cluster), or

1,42

NU-1000 (csq, Zr

-cluster or Ce

-cluster)).

Finally, RE-

carboxylic acid linkers. This includes RE-cluster nodes with

high nuclearity and connectivity, giving rise to MOFs with

complex and intricate topologies, some of which are likely to

CU-10, with a high density of pyrene chromophores, ∼11 Å

channels, and high porosity, is applied for the photocatalytic

oxidation and detoxiﬁcation of a sulfur mustard simulant, 2-

chloroethyl ethyl sulﬁde (2-CEES), demonstrating perform-

29−32

be inaccessible with other metals.

with an shp topology, named RE-shp-MOF-1 (RE = Y(III)

and Tb(III)), was reported, representing one of the four

edge transitive (4,12)-c nets where a double six-membered ring

d6R) building block acts as a 12-connected (12-c) node.

RE-shp-MOF-1 is composed of square, tetratopic porphyrin-

based linkers (5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin;

H TCPP) and 12-connected nonanuclear Y(III)-cluster nodes,

In one example, a MOF

ance under O and air that is comparable to the best MOF

catalysts reported for this application.

(

Received: March 15, 2021

Revised: May 11, 2021

Published: May 27, 2021

giving a structure with 1D triangular channels. In another

example, RE-shp-MOF-5 was reported, composed of 12-c

nonanuclear RE(III)-cluster nodes and rectangular 1,2,4,5-

2021 American Chemical Society

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Article

Figure 2. Scanning electron microscopy (SEM) images of micro-

crystalline samples of Y-CU-10 (mean size, 89 μm) (a) and Tb-CU-

0 (mean size, 90 μm) (c). Optical microscopy images of single

crystals of Y-CU-10 (mean size, 152 μm) (b) and Tb-CU-10 (mean

size, 226 μm) (d).

Figure 1. Structure of RE-CU-10 showing the RE -cluster node and

,3,6,8-tetrakis(p-benzoic acid)pyrene linker.

connectivity and spatial arrangement of RE-metals as the

nonanuclear cluster reported in Y-shp-MOF-1 and pek-

MOF-1. Each individual nonanuclear RE(III)-cluster is

RESULTS AND DISCUSSION

The combination of the tetratopic linker H TBAPy with

Y(III), or Tb(III) in the presence of 2-ﬂuorobenzoic acid (2-

HFBA), under solvothermal conditions in DMF, yields the

MOF RE-CU-10. Single-crystal X-ray diﬀraction (SCXRD)

shows that RE-CU-10 crystallizes in the trigonal space group

4−

■

coordinated by 12 crystallographically independent TBAPy

linkers, giving a 12-connected (12-c) node. All carboxylates

coordinated to the cluster bridge adjacent RE atoms and

arrange to form a d6R hexagonal prism (Figure 1). Structural

and topological analysis of the resulting structure show the

formation of a (4,12)-c MOF, building a net with the shp

topology (Figure 1 and Figures S6 −S10 ). The carboxylphenyl

groups in RE-CU-10 are rotated from the plane of the pyrene

core, showing a dihedral angle of ∼58°. This angle is similar or

inferior in magnitude compared to other shp MOFs made with

diﬀerent tetratopic linkers and nonanuclear RE(III)-clusters

m1 and is composed of a nonanuclear RE-cluster, which

appears as a RE -cluster due to disorder (Figures S1 and S2).

Analogous disorder of the nonanuclear RE-cluster has been

observed in other RE-MOFs, including Y-shp-MOF-1, Y-

shp-MOF-5, Y-kce-MOF-1, and Y-ken-MOF-1. A similar

phenomenon was also observed in the metal cluster of PCN-

(∼59° Y-shp-MOF-5 and ∼68° for RE-shp-MOF-1) and

23, a Zr -based MOF composed of H TCPP linkers with shp

also similar to a dihedral angle of ∼60° found for the same

topology, where the hexanuclear Zr(IV)-cluster is disordered

over three positions, appearing as a Zr -cluster. In a diﬀerent

linker in NU-1000 (csq topology). This highlights the

diversity of topologies that can be made with RE(III)-cluster

nodes owing, in part, to the existence and stability of high

nuclearity clusters with somewhat ﬂexible coordination geo-

metries. The crystalline structure features one-dimensional

triangular channels along the c axis of 10 Å in diameter and 9 Å

hexagonal-prismatic cages enclosed by six linkers and two

metal clusters (Figures S6 and S7).

interpretation by Farha et al., the disordered Zr -cluster in

NU-904 (scu topology) was found to be caused by merohedral

twinning in the structure where three scu nets overlap, giving

sixfold symmetry and the appearance of an shp net. It should

be noted that the scanning electron microscopy (SEM) images

taken from NU-904 show prolate spheroid-shaped particles,

indicative of the scu topology and diﬀerent from the

hexagonal-shaped particles expected to be observed for

Bulk microcrystalline samples of RE-CU-10 (Figure 2) were

synthesized, and the phase purity of the product was conﬁrmed

by powder X-ray diﬀraction (PXRD) (Figure 3a). N₂

adsorption analysis shows a reversible type I isotherm with

6,47

MOFs with the shp topology.

(

Based on SEM images

Figure 2a,c), H-NMR spectroscopy (Figures S3 and S4 ), and

−1

thermogravimetric analysis (TGA) (Figure S5 ), we conclude

that RE-CU-10 possesses the shp topology with an

experimental chemical formula for Y-CU-10 of DMA [Y (μ -

calculated BET surface areas (pore diameter) of 1800 m g

−1

(11 Å) and 1780 m g (11 Å) for Y- and Tb-CU-10,

respectively (Figure 3b and Figure S11), after activation under

vacuum at 120 °C. Although we would expect Tb-CU-10 to

have a lower gravimetric surface area than Y-CU-10, factors

such as activation and the presence of structural defects (i.e.,

missing linkers or missing nodes) can contribute to the

gravimetric surface areas being more similar. SEM shows the

OH) (μ -O) (TBAPy) (2-FBA) ]·2DMF and for Tb-CU-10

of DMA [Tb (μ -OH) (μ -O) (TBAPy) (2-FBA) ]·(DMF)-

(

2-HFBA). Although not all of the bridging hydroxyl and/or

oxo ligands could be assigned by SCXRD due to the level of

disorder in the structure, the cluster possesses similar

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Article

Figure 4. (a) Conversion of 2-CEES to 2-CEESO using RE-CU-10 as

a catalyst under UV-LED irradiation and (b) conversion vs time for

Figure 3. (a) Calculated PXRD pattern of RE-CU-10 obtained from

the Y-CU-10 SCXRD data and experimental PXRD patterns of bulk

Y- and Tb-CU-10. (b) Nitrogen adsorption−desorption isotherms of

RE-CU-10 (inset: pore size distribution plots).

the selective oxidation of 2-CEES by Tb-CU-10 under O saturation,

as determined by GC-FID analysis.

characteristic hexagonal-prismatic microcrystals derived from

the trigonal space group and as expected for a MOF with the

shp topology (Figure 2a,c). Diﬀuse reﬂectance infrared Fourier

transform spectroscopy (DRIFTS) shows the expected

absorption bands from the symmetric and asymmetric

carboxylate stretching (Figure S12) as well as O−H stretching

ratiﬁcations of the Chemical Weapons Convention treaty

(CWC). Sulfur mustard is a very reactive alkylating agent

that causes failure of cellular functions, presenting as a strong

blistering agent that causes acute and chronic injuries to the

1,52

skin, eyes, and respiratory system.

Sulfur mustard

accumulated in facilities or present at inadequate disposal

sites must be destroyed in an eﬃcient and controlled manner,

and one method to safely detoxify the compound involves

selective oxidation to its less toxic sulfoxide derivative.

bands corresponding to μ -OH ligands in the nonanuclear

RE(III)-cluster node. Thermogravimetric analysis (TGA) of

activated samples of RE-CU-10 under air (Figure S5) shows

that decomposition occurs at 450 °C, comparable to other RE-

In 2015, Farh et al. demonstrated that the sulfur mustard

simulant, 2-CEES, could be selectively oxidized and detoxiﬁed

to the less toxic 2-chloroethyl ethyl sulfoxide (2-CEESO) by

using the MOF PCN-222/MOF-545 as a photosensitizer to

33,35

cluster-based MOFs.

Variable temperature PXRD (VT-

PXRD) analysis performed up to 305 °C (the limit of the

instrumentation used) shows that RE-CU-10 remains stable to

05 °C (Figure S13 ) without any indication of amorphization

generate singlet oxygen under LED irradiation. The group

or phase transformations occurring in this temperature range.

has since studied several diﬀerent pyrene-containing MOFs for

H-NMR spectroscopy of digested samples of RE-CU-10

the degradation of 2-CEES and sulfur mustard, including NU-

shows the presence of the TBAPy⁴linker, DMF, and 2-FBA

−

1000 (csq),

(csq),

54,55

postsynthetically modiﬁed NU-1000

6,57

modulator (Figures S3 and S4).

and NU-400 (fcu). These materials are composed

Given that RE-CU-10 has a high density of pyrene

of hexanuclear Zr(IV)-cluster nodes and tetratopic or ditopic

pyrene-based linkers in NU-1000 and NU-400, respectively. In

all cases, the linker behaves as a photosensitizer for the

generation of singlet oxygen, under LED irradiation, which

subsequently selectively oxidizes 2-CEES.

Activated samples of Y- and Tb-CU-10 were suspended in

methanol and purged with oxygen for 20 min. 2-CEES and the

internal standard, mesitylene, were added, and the mixture was

excited using a UV LED photoreactor (λ_m_a_x= 400−410 nm;

Figure S14, see details in the Supporting Information). Under

chromophores (three pyrene linkers per RE -node, see Table

S1 for more details) coupled with 11 Å channels that can aid in

diﬀusion of reactants and products, we expected the MOF to

perform well in the selective photooxidation of the sulfur

mustard simulant 2-CEES to 2-CEESO (Figure 4a). Sulfur

mustard is a chemical warfare agent that was used for the ﬁrst

time during WWI. Unfortunately, it is still a potential threat to

public health today due to its stockpiling and potential

production from nations that have not signed or followed

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Chem. Mater. 2021, 33, 4163−4169

Chemistry of Materials

reactions, where in between each run, the MOF was isolated

Article

optimized conditions, using 3.6 mg (0.99 μmol, 0.5 mol %) or

and washed with fresh methanol before being reused (see the

Supporting Information for details). The increase in time from

12.5 to 30 min that is required to achieve 100% conversion in

subsequent cycles can be attributed to the unavoidable loss of

the catalyst after isolation and washing since negligible

degradation of the MOFs is observed, as conﬁrmed by

.1 mg (0.95 μmol, 0.5 mol %) of Y- and Tb-CU-10 as a

catalyst, respectively, 2-CEES can be completely and selectively

oxidized to 2-CEESO within 15.0 min (half-life 5.0 min) and

2.5 min (half-life 3.5 min) for Y- and Tb-CU-10, respectively

(

Figure 4b). Gas chromatography−ﬂame ionization detector

PXRD (Figure 5b and Figure S23b), N sorption isotherms

(

GC-FID) analysis, H-NMR spectroscopy, C-NMR spec-

(

Figure S24 ), and inductively coupled plasma−mass spec-

troscopy, and high-resolution−mass spectrometry (HR-MS) of

the supernatant indicate that no sulfone product was formed

during the process (Figures S15 −S22 and Tables S2 −S6). The

half-life for the selective oxidation of 2-CEES by Y- and Tb-

CU-10 is shorter than those reported for NU-1000 (6.2 min

trometry (ICP-MS) (Figure S25 and Table S7 ).

To assess the activity of RE-CU-10 under conditions that

may be more amenable to real-world applications, the

photooxidation of 2-CEES was also evaluated under air.

Using the same catalyst loading of 0.5 mol %, 2-CEES was

converted to 2-CEESO under air with half-lives of 21 and 22

min for Y- and Tb-CU-10, respectively (Figure S26a,b and

Tables S8 and S9 ), with full conversions occurring at 70 and

half-life, 0.5 mol %) and NU-400 (10.2 min half-life, 1 mol

under O saturation. The outstanding photocatalytic

performance of RE-CU-10 is attributed to the balance between

the porosity, high pyrene density, and pore aperture size

20 min, respectively. PXRD patterns of the recovered catalyst

(Table S1), a balance oﬀered by the shp topology. It should be

(

Figure S26c,d) show that the overall structure of RE-CU-10 is

noted that the heavier atomic mass of Tb (158.93 u) compared

to Y (88.91 u) and Zr (91.22 u) may also play a role in the

eﬃciency of singlet oxygen production via stabilization of the

spin-forbidden pyrene triplet state through the heavy atom

maintained, but Tb-CU-10 undergoes an observable loss of

crystallinity. ICP-MS was used to conﬁrm that 12 mol % Y-

CU-10 and Tb-CU-10 was degraded over the 120 min

reaction, compared to only 2−3 mol % degradation observed

eﬀect. Alternatively, there is the potential for energy transfer

under O (Table S7). It is important to note that this loss of

in Tb-CU-10 since Tb(III) has sharp emission bands (491,

crystallinity and degradation is not observed for either MOF

47, 588, and 624 nm), some of which overlap with the

over three subsequent reaction cycles under O (75 min total)

absorption bands of pyrene and could thus enhance light

harvesting and singlet oxygen production (Figure S14).

The recyclability of Y-CU-10 (Figure S23a) and Tb-CU-10

and is also not observed when the MOF is suspended in

MeOH and purged with air for 120 min (Figure S27),

suggesting that the washing steps in between catalytic cycles

(Figure 5a) was demonstrated by completing three successive

and availability of O may contribute to mitigating degradation

of RE-CU-10.

CONCLUSIONS

■

The ability of rare-earth metals to form high nuclearity clusters,

coupled with their versatile coordination numbers and

geometries, allows for the synthesis of structures that are not

as easily accessible with d-block metals. In this report, the

nonanuclear RE(III)-cluster, which acts as a d6R node, enables

the synthesis of RE-CU-10, a MOF with the shp topology

−

composed of TBAPy linkers, a linker that has not yet been

61,62

observed in the shp topology.

permanent porosity, with surface areas of 1780−1800 m g

RE-CU-10 demonstrates

−1

and thermal stability in air up to 450 °C. In addition, the high

density of pyrene chromophores along with the microporosity

of RE-CU-10 allows for the fast and selective photocatalytic

oxidation and detoxiﬁcation of a sulfur mustard simulant, 2-

CEES, at low catalytic loadings (0.5 mol %), with a conversion

half-life of only 3.5 min under O (Tb-CU-10) and 21 min

under air (Y-CU-10). These promising reaction kinetics,

coupled with the wide range of topologies that can be accessed

using RE-metals, demonstrate the potential of RE-MOFs as

photocatalysts for the selective oxidation and detoxiﬁcation of

2-CEES.

EXPERIMENTAL SECTION

Synthesis of Y-CU-10. Single crystals of Y-CU-10 were obtained

solvothermally in a 4 dram vial containing H TBAPy (13.8 mg, 0.02

■

mmol), Y(NO ) ·xH O (31.6 mg, 0.08 mmol of assuming

hexahydrate), and 2-ﬂuorobenzoic acid (1261.0 mg, 9.0 mmol),

suspended in 7.0 mL of DMF, 0.576 mL (0.032 mol) of distilled

water, and 1.6 mL (0.028 mol) of glacial acetic acid. The vial was

sealed, and the suspension was sonicated for 10 min and placed into a

preheated oven at 120 °C for 72 h. Yellow single crystals were

separated by centrifugation, washed three times with fresh DMF over

Figure 5. (a) Reusability of the catalyst Tb-CU-10 over three

successive photocatalytic oxidations of 2-CEES under O₂₍_g₎saturation.

(

b) PXRD analysis of Tb-CU-10 after three photocatalytic reactions.

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Complete contact information is available at:

Article

the course of 24 h, and later three times with fresh acetone over the

course of 24 h. The material was air-dried and then activated at 120

Authors

Victor Quezada-Novoa − Department of Chemistry and

Biochemistry, Concordia University, Montreal, Quebec H4B

R6, Canada

C for 24 h under ultralow vacuum. Yield (activated material): 70%.

Synthesis of Tb-CU-10. Single crystals were obtained solvother-

mally in a 4 dram vial containing H TBAPy (6.1 mg, 0.0089 mmol),

Hatem M. Titi − Department of Chemistry, McGill University,

Montreal, Quebec H3A 0B8, Canada; orcid.org/0000-

Tb(NO )·xH O (15.5 mg, 0.036 mmol of assuming pentahydrate),

and 2-ﬂuorobenzoic acid (561.1 mg, 4.0 mmol), suspended in 3.1 mL

of DMF and 0.713 mL of glacial acetic acid (0.012 mol). The vial was

sealed, and the suspension was sonicated for 10 min and placed into a

preheated oven at 120 °C for 72 h. Yellow single crystals were

separated by centrifugation, washed three times with fresh DMF over

the course of 24 h, and later three times with fresh acetone over the

course of 24 h. The material was air-dried and then activated at 120

0002-0654-1292

Amy A. Sarjeant − Bristol Myers Squibb, New Brunswick, New

Jersey 08903, United States

https://pubs.acs.org/10.1021/acs.chemmater.1c00917

C for 24 h under ultralow vacuum. Yield (activated material): 35%.

^P^h^o^t^o^o^xⁱ^d^a^tⁱ^oⁿ^uⁿ^d^e^r^O2 Saturation. Activated RE-CU-10

RE = Y (3.6 mg, 0.99 μmol, 0.5 mol %) or Tb (4.1 mg, 0.95 μmol,

Author Contributions

All authors have given approval to the ﬁnal version of the

manuscript.

Notes

The authors declare no competing ﬁnancial interest.

Crystal structures of Y-CU-10 and Tb-CU-10 were deposited

at the Cambridge Crystallographic Data Centre (CCDC)

(

.5 mol %)) was suspended in 1 mL of methanol in a 17 × 83 mm

microwave vial and gently ground using a glass rod. The vial was

capped and purged with O for 20 min, and then 2-CEES (23 μL, 0.2

mmol) and mesitylene (internal standard, 10 μL) were added. The

vial was placed in the center of the LED reactor described in the

instrumentation section. Conversion of 2-CEES was calculated

relative to the internal standard by gas chromatography (GC-FID).

Photooxidation under Air Saturation. Activated RE-CU-10

(

deposition numbers 1998090-1998091).

ACKNOWLEDGMENTS

■

(

RE = Y (3.3 mg, 0.91 μmol, 0.5 mol %) or Tb (4.3 mg, 0.99 μmol,

.5 mol %)) was suspended in 1 mL of methanol in a 17 × 83 mm

V.Q.-N. thanks Concordia University for the Anne Harper

Pallen Entrance Scholarship, the Concordia International

Tuition Award of Excellence, and the Howarth and Majewski

research group members for oﬀering a friendly and supportive

research environment. V.Q.-N. also thanks Prof. Majewski for

helpful discussion regarding organic synthesis, and photo-

chemical characterization techniques. V.Q.-N. and A.J.H. thank

microwave vial and gently ground using a glass rod. The vial was

capped and purged with air for 20 min, and then 2-CEES (23 μL, 0.2

mmol) and mesitylene (internal standard, 10 μL) were added. The

vial was placed in the center of the LED reactor described in the

instrumentation section. Conversion of 2-CEES was calculated

relative to the internal standard by gas chromatography (GC-FID).

Photocatalyst (MOF) Recyclability. The ability to recycle and

reuse the MOF photocatalysts was studied by suspending activated

RE-CU-10 (RE = Y (3.4 mg, 0.94 μmol, 0.5 mol %) or Tb (4.3 mg,

Prof. Tomislav Friscic for access to PXRD and SCXRD

̌ ̌ ́

facilities, Petr Fiurasek (Centre Québécois sur les Matériaux

Fonctionnels) for help with TGA, Prof. Yves Gélinas for access

to and help with GC-FID measurements, and Dr. David

Polcari (Systems for Research) for access to the Phenom

benchtop SEM instrument. We thank Dr. Heng Jiang from

Concordia’s Centre for Biological Applications of Mass

Spectrometry for ICP-MS and HR-MS analysis. We acknowl-

edge the support of the Natural Sciences and Engineering

Research Council of Canada (NSERC) [funding reference

number: DGECR-2018-00344] and Cette recherche a été

ﬁnancée par le Conseil de recherches en sciences naturelles et

en génie du Canada (CRSNG) [numéro de reference:

DGECR-2018-00344]. All structural ﬁgures were made using

.99 μmol, 0.5 mol %)) in 1 mL of methanol in a 17 × 83 mm

microwave vial, and the catalyst was ground using a glass rod. The vial

was capped and purged with O for 20 min, and then 2-CEES (23 μL,

The vial was placed in the center of the LED reactor described in the

instrumentation section. Conversion of 2-CEES was calculated

relative to the internal standard by gas chromatography (GC-FID).

Once the reaction reached a conversion of 100%, the catalyst was

isolated by centrifugation (7500 rpm × 5 min), washed three times

with fresh methanol (2 mL, 7500 rpm × 5 min), and suspended in 1

.2 mmol) and mesitylene (internal standard, 10 μL) were added.

mL of methanol. The suspension was purged with O for 20 min, and

then 2-CEES (23 μL, 0.2 mmol) and mesitylene (internal standard,

VESTA 3.

0 μL) were added to repeat the photocatalytic reaction.

ABBREVIATIONS

MOFs, metal−organic frameworks; RE, rare-earth; 2-CEES, 2-

chloroethyl ethyl sulﬁde; 2-CEESO, 2-chloroethyl ethyl

■

ASSOCIATED CONTENT

■

sı Supporting Information

The Supporting Information is available free of charge at

https://pubs.acs.org/doi/10.1021/acs.chemmater.1c00917.

sulfoxide; H TBAPy, 1,3,6,8-tetrakis(p-benzoic acid)pyrene;

SCXRD, single-crystal X-ray diﬀraction; PXRD, powder X-ray

diﬀraction; VTPXRD, variable temperature powder X-ray

diﬀraction; BET, Brunauer−Emmett−Teller

Instrumentation details, experimental procedures, calcu-

lations, gas chromatograms, additional structural ﬁgures,

and single-crystal X-ray diﬀraction (PDF)

REFERENCES

■

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AUTHOR INFORMATION

■

(

Corresponding Author

Ashlee J. Howarth − Department of Chemistry and

Biochemistry, Concordia University, Montreal, Quebec H4B

09, 2040−2042.

R6, Canada; orcid.org/0000-0002-9180-4084;

(3) Kondo, M.; Yoshitomi, T.; Matsuzaka, H.; Kitagawa, S.; Seki, K.

Three-Dimensional Framework with Channeling Cavities for Small

Email: ashlee.howarth@concordia.ca

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