Post-synthetically elaborated BODIPY-based porous organic polymers (POPs) for the photochemical detoxification of a sulfur mustard simulant

Article abstract of DOI:10.1021/jacs.0c07784

Designing new materials for the effective detoxification of chemical warfare agents (CWAs) is of current interest given the recent use of CWAs. Although halogenated borondipyrromethene derivatives (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene or BDP or BODIPY) at the 2 and 6 positions have been extensively explored as efficient photosensitizers for generating singlet oxygen (1 O2) in homogeneous media, their utilization in the design of porous organic polymers (POPs) has remained elusive due to the difficulty of controlling polymerization processes through cross-coupling synthesis pathways. Our approach to overcome these difficulties and prepare halogenated BODIPYbased porous organic polymers (X-BDP-POP where X = Br or I) represents an attractive alternative through post-synthesis modification (PSM) of the parent hydrogenated polymer. Upon synthesis of both the parent polymer, H-BDP-POP, and its post-synthetically modified derivatives, Br-BDP-POP and I-BDP-POP, the BET surface areas of all POPs have been measured and found to be 640, 430, and 400 m2 g-1, respectively. In addition, the insertion of heavy halogen atoms at the 2 and 6 positions of the BODIPY unit leads to the quenching of fluorescence (both polymer and solution-phase monomer forms) and the enhancement of phosphorescence (particularly for the iodo versions of the polymers and monomers), as a result of efficient intersystem crossing. The heterogeneous photocatalytic activities of both the parent POP and its derivatives for the detoxification of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), have been examined; the results show a significant enhancement in the generation of singlet oxygen (1 O2). Both the bromination and iodination of H-BDP-POP served to shorten by 5-fold of the time needed for the selective and catalytic photo-oxidation of CEES to 2-chloroethyl ethyl sulfoxide (CEESO).

Full text of DOI:10.1021/jacs.0c07784

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Article
Post-Synthetically Elaborated BODIPY-based Porous Organic Polymers
POPs) for Photochemical Detoxification of a Sulfur Mustard Simulant
(
Ahmet Atilgan, M. Mustafa Cetin, Jierui Yu, Yassine Beldjoudi, Jian Liu, Charlotte L. Stern, Furkan
M Cetin, Timur Islamoglu, Omar K. Farha, Pravas Deria, J. Fraser Stoddart, and Joseph T. Hupp
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c07784 • Publication Date (Web): 26 Sep 2020
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Post-Synthetically Elaborated BODIPY-based Porous Organic
Polymers (POPs) for Photochemical Detoxification of a Sulfur
Mustard Simulant
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†
#
†‡#
†
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∇
Ahmet Atilgan, M. Mustafa Cetin, Jierui Yu, Yassine Beldjoudi, Jian Liu, Charlotte L.
†
†
†
†
*,
∇
Stern, Furkan M. Cetin, Timur Islamoglu, Omar K. Farha, Pravas Deria,
and J. Fraser
Stoddart*
,†,§,^
and Joseph T. Hupp
*,†
†Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois
0208-3113, USA
Department of Bioinformatics and Genetics, Faculty of Engineering and Natural Science, Kadir
Has University, 34083 Cibali Campus Fatih, Istanbul, Turkey
Department of Chemistry and Biochemistry, Southern Illinois University, 1245 Lincoln Drive,
Carbondale, Illinois 62901, USA
Institute of Molecular Design and Synthesis, Tianjin University, 92 Weijin Road, Nankai District,
Tianjin, 300072, P. R. China
School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
6
‡
∇
§
^
*
E-mail: pderia@siu.edu, stoddart@northwestern.edu and j-hupp@northwestern.edu
*
Correspondence
Address
*Correspondence
*Correspondence
Address
Address
Professor Pravas Deria
Department of Chemistry
and Biochemistry
Professor J. Fraser Stoddart
Department of Chemistry
Northwestern University
2145 Sheridan Road
Professor Joseph T. Hupp
Department of Chemistry
Northwestern University
2145 Sheridan Road
Evanston, IL 60208 (USA)
Email:
Southern Illinois University
1245 Lincoln Drive
Carbondale, IL 62901 (USA)
Email:
Evanston, IL 60208 (USA)
Email:
stoddart@northwestern.edu
j-hupp@northwestern.edu
pderia@siu.edu
1
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ABSTRACT: Designing new materials for effective detoxification of chemical warfare agents (CWAs)
is of current interest given the recent use of CWAs. Although halogenated boron-dipyrromethene
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derivatives (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene or BDP or BODIPY) at the 2 and6 positions have
1
been extensively explored as efficient photosensitizers for generating singlet oxygen ( O
2
) in homogenous
media, their utilization in the design of porous organic polymers (POPs) has remained elusive due to the
difficulty of controlling polymerization processes through cross-coupling synthetic pathways. Our
approach to overcome these difficulties and prepare halogenated BODIPY-based porous organic
polymers (X-BDP-POP where X = Br or I) represents an attractive alternative through post-synthetic
modification (PSM) of the parent hydrogenated-polymer. Upon synthesis of both the parent polymer,
H-BDP-POP, and its post-synthetically modified derivatives, Br-BDP-POP and I-BDP-POP, the
2
–1
BET surface areas of all POPs have been measured and found to be 640, 430, and 400 m ·g ,
respectively. In addition, the insertion of heavy halogen atoms at the 2 and 6 positions of the
BODIPY unit leads to quenching of fluorescence (both polymer and solution-phase monomer forms)
and enhancement of phosphorescence (detectable for polymer form only), as a result of efficient
intersystem crossing. The heterogeneous photocatalytic activities of both the parent POP and its
derivative for the detoxification of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES),
have been examined; the results show significant enhancement in the generation of the singlet
1
oxygen ( O
2
). Both bromination and iodination of H-BDP-POP served to shorten by five-fold the
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time needed for selective and catalytic photo-oxidation of CEES to 2-chloroethyl ethyl sulfoxide
(CEESO).
■
INTRODUCTION
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Despite bans by the Chemical Weapons Convention (CWC) endorsed in 1993 by the vast majority of the
members of the United Nations, the stockpiling and use of chemical warfare agents (CWAs) constitute
1,2
ongoing global concerns. Bis(2-chloroethyl)sulfide, also known as sulfur mustard (HD) was one of the
earliest CWAs to be deployed in war-time conflicts. That it is still used by rogue elements is likely a
consequence of its low cost and facile production.1,3,4 Remarkably, and unfortunately, a century after its
invention, devising superior methods, materials, and protective equipment for the detoxification of HD is
of contemporary relevance. Among the known methods for HD degradation are hydrolysis,5,6
7
8-12
dehydrohalogenation, and oxidation. Two of these methods, hydrolysis and dehydrohalogenation,
typically proceed slowly because of the low solubility of HD in water – a problem as well for its less toxic
derivative, the CWA simulant 2-chloroethyl ethyl sulfide (CEES).7,13-17 Stoichiometric and/or catalytic
oxidative degradation of HD (or CEES), has been explored using polyoxometalates (POMs),18,19
20
11
21
peroxides, metal oxides, and enzymes. These oxidants, however, are reportedly non-selective,
yielding, in part, doubly-oxygenated sulfone derivatives of HD or CEES. While not as acutely dangerous
as HD, the sulfone derivative – unlike the sulfoxide – is highly toxic.11,21 In contrast, oxidative degradation
1
of HD or CEES via photo-generated singlet oxygen ( O
2
) has been shown to proceed with generally faster
kinetics and with good to excellent selectivity for the sulfoxide over the sulfone derivative.22
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Effective heterogenous photocatalysis using O
2
is predicated on satisfying two main criteria: (i) efficient
photosensitization, and (ii) presentation of sufficient porosity to attain high catalyst surface area (high
catalyst exposure to reactants), and to enable rapid diffusive transport of reactants and products to and
from catalyst active-sites. In principle, heterogenizing a photocatalyst may allow for ready separation of
the catalyst from a reaction mixture while also facilitating reuse and allowing flexibility in solvent
selection. Several metal-organic frameworks (MOFs)23,24 based on various photosensitizers22,25-29 have
been employed to achieve fast and selective detoxification of HD or its simulant CEES; however, these
microcrystalline powder materials could present processing challenges for some implementations.
Complementary to crystalline MOFs are non-crystalline porous organic polymers (POPs).30-32 Similar to
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MOFs, they offer high surface areas and chemical tunability, as well as high chemical and thermal
stability. POPs have been explored for myriad applications, ranging from gas adsorption32 and
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separation to catalysis.
The versatile designs, high porosity, and chemical stabilities of these
materials are based on the functionalization of their respective building-blocks. In this context, the design
of a suitable POP requires the utilization of a building-block that is an efficient singlet-oxygen
photosensitizer or is a precursor to one.
The BODIPY core (Figure 1) and its derivatives, with their tunable chemical structures and remarkable
38
photophysical properties, have been examined for candidate applications such as molecular imaging,
photocatalysis, and photodynamic therapy (PDT).39-41 Application of BODIPY as a fluorescent probe
requires enhancement of the radiative relaxation pathways from the singlet state. In contrast, the
application of BODIPY in photodynamic therapy requires favorable relaxation pathways through
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intersystem crossing (ISC) to enhance yields of the triplet excited state, i.e. verymuch the same as required
for effective photocatalytic oxidative degradation of CWAs. Thus, lessons learned from the design of
BODIPY-based chromophores for PDT can be co-opted. Chromophore functionalization with heavier
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halogens engenders ISC via the enhanced spin-orbit coupling. Given suitable energy-matching, the
triplet excited state of BODIPY can sensitize the otherwise forbidden conversion of ground-state triplet
3
1
.42,43 Although halogenated versions of
oxygen ( O
2
) to electronically excited and chemically reactive O
2
1
BODIPY have been used in homogenous media as photochemical sensitizers for O
2
formation, their
application as heterogenized sensitizers remains relatively unexplored.
The development of versatile chemical structures of BODIPY requires molecular engineering at the
different ring positions to access BODIPY-based polymers. Notably, numerous syntheses of non-porous
2D linear polymers via functionalization of the (2,6), (3,5) or 8 (meso) positions (Figure 1) of BODIPY
have been described.44-58 Among these studies, Chujo et al. showed that highly emissive nonporous
BODIPY-based polymers can be obtained by replacing the boron’s fluorine atoms with phenylethynyl
groups using chemistry elaborated by Ziessel et al.59,60 In contrast, examples of BODIPY-based porous
organic polymers (POPs) are comparatively scarce. Among the examples are BODIPY POPs designed
61
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63-65
for iodine capture, lithium-ion storage, and photocatalysis.
Both polymerization of tridentate aryl
co-monomers and of BODIPY core (Figure 1) functionalized at its 2 and 6 positions are reported to have
been carried out via Sonogashira63,64 or Suziki coupling to generate conjugated porous polymers as
candidate photocatalysts. Studies of the photocatalytic performance of BODIPY-based POPs, in
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particular, showed that full conversion of thioanisole to methylphenyl sulfoxide is comparatively slow,
evidently due to aggregation of the chromophores.
An important consideration from an in-field application perspective is the rate of photocatalytic
degradation of the chemical threat. To enhance photodegradation rates, iodo-BODIPY, in molecular form,
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has previously been noncovalently doped into non-porous polymeric matrices to yield a photosensitizer
1
for oxidative degradation of HD and CEES by O
2
. While the doped material yielded reasonably fast
reaction rates, problems attributable to dopant (sensitizer) aggregation and leaching were evident. A
redesign of BODIPY-based POPs ideally would: a) make use of halogenated-BODIPY chromophores to
enhance intersystem crossing yields oxygen, b) employ a polymerization schemecapable of yielding good
porosity and, therefore, good reactant accessibility, and c) employ a polymerization scheme that disfavors
chromophore aggregation. Unfortunately, the preparation of halogenated-BODIPY POPs from pre-
halogenated-BODIPY monomers, using carbon-carbon coupling reactions, such as Sonogashira,66
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Yamamoto, and Suzuki, may induce uncontrolled polymerization and dehalogenation of the BODIPY
center. We reasoned, however, that post-synthetic modification (PSM) – which has recently drawn
attention with respect to evolving pristine polymers into more functional materials for specific
applications, such as metal removal,69,70 energy conversion,71,72 and gas adsorption73-75 – might be an
excellent tool for the insertion of needed halogen atoms on pre-formed BODIPY-containing POPs.
In the present article, we report a new BODIPY-based monomer (H-BDP-M) featuring multiple
polymerizing groups (two extending from the boron, and one from the meso position of the BODIPY core
(Scheme 1), leaving the 2 and 6 positions of BODIPY accessible for post-synthetic halogenation. The
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polymerization of this new monomer produces the parent POP (H-BDP-POP), which is only
subsequently halogenated to produce desired daughter POPs (Br- and I-BDP-POPs). Gas adsorption
studies have been undertaken to unravel the porosity characteristics of each POP, while the activity and
selectivity of both the parent and daughter materials as heterogeneous photocatalysts for the detoxification
of a sulfur mustard simulant have been investigated. Furthermore, optical absorption and luminescence
studies have been undertaken to establish/confirm the basis for the high activity of the halogenated-
BODIPY POPs.
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■
RESULTS AND DISCUSSION
Molecular Design, Synthesis, and Structural Characterization. The novel and stable conjugated
porous organic polymers (H-, Br-, and I-BDP-POPs) and their respective monomers (H-, Br-, and
I-BDP-Ms) were synthesized via a multistep synthetic pathway. See Supporting Information,
Section B and Scheme S1. The general synthetic routes and chemical structures of monomers and
polymers are shown in Schemes 1 and 2, respectively. To access the porous organic polymers
(POPs), we employed a BODIPY-based monomer (H-BDP-M) elaborated with three brominated
phenyl units, one connected to the meso-carbon, and the other two to the boron atom through ethynyl
units. Once Br-Ph-BODIPY was available, the parent monomer H-BDP-M was prepared according
7
6
to a previous literature procedure with slight modifications (84% isolated yield). See Supporting
Information. The other two monomers, Br- and I-BDP-M, were synthesized77-79 (Scheme 2) by
bromination and iodination of H-BDP-M with N-bromosuccinimide (NBS) and N-iodosuccinimide
(NIS), respectively. The molecular structural characterization of all three monomers was confirmed
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(
Figures S1–S8) by H and C (decoupled mode) nuclear magnetic resonance (NMR) spectroscopy.
The structures of H-, Br-, and I-BDP-Ms were determined (Table S1, Figures S9-11) by single-
crystal X-ray analysis. According to the crystal structures of the monomers, the BODIPY moieties
are distant from each other, indicating that the three substituents connected to the chromophore
through the boron atom and the meso position of BODIPY are sufficiently bulky to prevent
chromophore [π...π] stacking.
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Sonagoshira coupling was used to convert the monomer, H-BDP-M, to the parent BODIPY-based
POP, H-BDP-POP. Optimization of the reaction temperature (~90 ºC) and the solvent
(dimethylformamide (DMF)) led to an isolated yield of 90%. The polymer was then modified by
either bromination or iodination creating the daughter polymers, Br- and I-BDP-POPs.
Polymer formation was confirmed, in part, by diffuse reflectance infrared Fourier transform
spectroscopy (DRIFTS). The stacked spectra (Figure 2) demonstrate the emergence of a carbon-
carbon triple bond (C–C≡C–C) between H-BDP-M and 1,4-bis(ethynyl)benzene, with a stretching
–1
frequency (Figure S20) of ~2211 cm . This value is in good agreement with reported stretching
frequencies62,64 for C≡C bonds in similar chemical environments. Polymer structures were further
1
3
confirmed by solid-state C NMR (Figure S21). The signals at 81.5 and 85.9 ppm arising from the
carbons (H–C≡ and ≡C–C, respectively) of 1,4-diehynylbenzene were shifted downfield from their
original places after the carbon-coupling reaction with H-BDP-M monomer.
With the aims of further corroborating (or not) the formation of polymers and of confirming their
indicated that H-, Br-, and I-BDP-POPs are stable toward mass loss up to 300, 245, 215 ºC,
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respectively. Powder X-ray diffraction (PXRD) measurements (Figure S22) confirmed that the
polymers are amorphous. The post-synthetic halogenations of H-BDP-POP to form Br- and I-BDP-
POPs were confirmed by X-ray photoelectron spectroscopy (XPS), percentages of bromine and
iodine atoms in Br-BDP-POP and I-BDP-POPs, respectively, were approximately equal to
atomic % of nitrogen (Table S3) in each polymer. This indicates two halogen atoms were inserted
on a BODIPY core. Scanning electron microscopy (SEM) images (Figure 3) showed that the parent
polymer forms aggregates of micron and sub-micron size particles, and neither bromination nor
iodination changes the polymer particle/aggregate morphology. According to energy dispersive
spectroscopy (EDS), the post-modification of the pristine polymer led to homogeneous distributions
of bromine and iodine atoms over the desired polymers (Figure S24). Dynamic light scattering
studies showed the average colloidal particle diameters of polymers to be approximately 600, 1000,
and 2000 nm (Figure S28) for H, Br, and I-BDP-POPs, respectively. Zeta-potential distributions of
polymers (Figure S27) show that the pristine polymer particles have nearly neutral zeta-potential,
while zeta-potentials of Br- and I-BDP-POPs are +38 and +43 mV, respectively. These results
imply that post-synthetic halogenation of H-BDP-POP improves the dispersity of resultant
polymers, which provides better sedimentation stability and solid loading capacity for halogenated
POPs compared to H-BDP-POP.
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Gas Sorption and Surface Area Measurements. The obtained nitrogen sorption measurements at
77 K (Figure 4A) yield Type I isotherms with hysteresis, as defined by the International Union of
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micropores while the subsequent more gradual increase points to the presence of larger pores in all
polymers. The hysteresis in the isotherms is tentatively ascribed to the swelling of polymer with
increasing pressure as commonly observed in POPs, and to slow kinetics for N
2
uptake at 90 K.81
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The Brunauer-Emmett-Teller (BET) surface areas of H-, Br-, and I-BDP-POPs are 640, 430, and
2
–1
400 m ·g , respectively. The decreases with halogenation are consequences of the mass contributed
by the halogen atoms, and perhaps also blocking of small apertures by these larger atoms. Non-local
density functional theory (NLDFT)-based pore size distributions (Figure 4B) indicate that post-
synthetic halogenation diminishes the pore widths of the resulting polymers.
Optical Studies. UV-Vis absorption and fluorescence spectroscopies of all monomers were carried
out to investigate the effect of the halogen substituents at the 2 and 6 positions of the BODIPY unit,
and all obtained data are summarized in Table 1. The solutions of H-, Br-, and I-BDP-Ms, all at 2.5
–
6
x 10 M in CH
2
Cl , were prepared. The UV-Vis absorption spectrum for H-BDP-M (Figure 5)
2
displays a maximum at 502 nm, which is slightly red-shifted for Br-BDP-M (526 nm) and I-BDP-
M (532 nm). These data imply that substituents at the 2 and 6 positions directly influence the
energies of the frontier orbitals of the BODIPY moiety. The parent monomer, H-BDP-M, fluoresces
strongly (40% quantum yield (QY) in glassy MeTHF under Ar atmosphere) with a spectral
maximum at 513 nm in CH
2
Cl . As illustrated in Figure 5 (right) and Table 1, the halogenated-
2
monomers, Br- and I-BDP-Ms, are much less efficient fluorophores. See Supporting Information,
Figure S15 for emission/excitation spectra of BODIPY monomers in glassy MeTHF at 77 and 298
K. The decreased fluorescence QYs are consequences of halogen-induced enhancement (spin-orbit
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coupling induced enhancement) of intersystem crossing from the initially formed singlet
photoexcited state to the lowest triplet excited state. (Recall that the strength of spin-orbit coupling
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within a given atom scales as the fourth power of the effective nuclear charge. )
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Figure 6 (left) shows the combined UV-Vis diffuse reflectance spectra. The reflectance spectrum
maxima for H- (489 nm), Br- (507 nm), and I-BDP-POPs (520 nm) are reasonably similar to the
absorption maxima of the corresponding monomers. The room-temperature fluorescence behaviors
(i.e., emission maximum, QY, and singlet excited-state lifetime) of the series of polymers (Table 1)
are parallel to those of the monomeric model chromophores and match expectations based on
changes in intersystem crossing yield. Furthermore, no excimer formation was observed in the
fluorescence spectra of polymers. This implies the absence of aggregation among the BODIPY units
of the polymers. The excitation spectra (Figure S16) establish that energy can be transferred from
photoexcited phenyl-alkyne units to the emissive singlet excited state of the BODIPY unit.
Lowering the temperature to 77 K unveils detectable phosphorescence from Br- and I-BDP-POPs
(and the corresponding monomers in glassy MeTHF) with phosphorescence being more prominent
for the iodo versions. Figure 7 shows the excitation and emission spectra of I-BDP-M and I-BDP-
POPs at 77 K. See Supporting Information for further details. Both the monomer and polymer
emission spectra show far-red peaks attributable to phosphorescence. The phosphorescence intensity
–1
maximum is at λ = 759 nm (Eem(phos) = 13,120 cm ). This, within the experimental uncertainty, is
nearly an exact match for the energy of the forbidden 3Ʃ–
ground-state to 1Ʃ+
excited-state transition
g
g
in the absorption spectrum of ground-state triplet oxygen, i.e. the transition that imparts to liquid O
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its characteristic pale blue color. Taken into consideration together with the evidence for high
intersystem crossing yield, the energy match by I-BDP-POP points to the likelihood of unusually
efficient sensitized singlet oxygen formation.
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Density Functional Theory (DFT) Calculations. The DFT calculations (Figure 8 and Table 2) on
geometry-optimized molecular structures of all monomers qualitatively reproduced experimental
variations in HOMO–LUMO energy gaps (ΔE). The structures of H-, Br-, and I-BDP-Ms were
*+
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geometry-optimized at the B3LYP/3–21G energy level using Jaguar software. The gas-phase
DFT calculations (Figure 8 and Table 2) on these geometry-optimized molecular structures showed
that both the HOMO and the LUMO are localized on BODIPY unit with no significant participation
of the alkyne substituent, whereas the HOMO–1 and LUMO+1 are exclusively based on the alkyne
substituents (Figure S26) at the meso and 4 positions of BODIPY core. Therefore, the HOMO–
LUMO energy gap should be comparatively insensitive to chromophore polymerization via Scheme
2
. Although halogenation at the 2 and 6 positions leads to stabilization of the HOMO and LUMO
orbitals, the HOMO–LUMO energy gap (ΔE) differs only very slightly as a function of
derivatization. For all compounds the energy gap between the HOMO–1 and LUMO+1 is
substantially greater (> 4.5 eV) than the HOMO–LUMO gap between (≤3.0 eV), implying that the
visible-region photosensitization entails electronic excitation exclusively for the BODIPY units,
with no significant participation by the alkyne substituents.
The absorption spectra (Figure S14a) of the H-, Br- and I-BDP-Ms revealed major bands at ~500
nm and ~250 nm associated with →* transitions in the BODIPY and alkyne moieties,
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respectively. Therefore, the optical band gaps are estimated to be approximately 2.36, 2.23, and 2.21
eV for the BODIPY moieties of the H-, Br-, and I-BDP-Ms, while the alkyne substituents for three
monomers have approximately 4.2 eV of the optical bandgap. These results are consistent with the
gas phase DFT calculations which have shown that the HOMO→LUMO gap is associated with the
BODIPY moiety and is ~3 eV, while the HOMO–1 →LUMO+1 gap of > 4 eV is associated to the
alkyne moieties. Therefore, for excitation approximately at 2.36 eV (525 nm), the photosensitizing
properties arise exclusively from the BDP moiety while the alkyne substituents have a structural
role.
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Photosensitized Catalysis. Figure 9A presents reaction rate data (in the form of plots of conversion
1
vs. time) for photosensitized degradation of CEES by O
2
, where the degradation yields exclusively
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CEESO (confirmed by H and C NMR data, see Supporting Information, Figures S31 and S32). A
schematic representation of a plausible mechanism29,84 for the formation of CEESO (the desired
sulfoxide product) in preference to CEESO (the much less desirable sulfone product) is presented
2
in Figure 9B. Br-BDP-POP and I-BDP-POP behave essentially performed identical, yielding
conversion half-lives of about 3 min. In contrast, the conversion half-life with H-BDP-POP as the
photocatalyst is 17 min. Similar, but slightly faster catalysis, was observed with the model monomer
catalysts, i.e. reaction half-lives of 2 min with Br- or I-BDP-Ms as the photocatalyst and ~9 min
with H-BDP-M.
Catalyst reusability (Figure 9C) was examined over four reaction cycles. During each cycle, samples
were irradiated for 11 min, and then the same amount of fresh CEES was added to each reaction
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vessel (without removal of the product from the previous cycle(s)). For neither halogenated polymer
was a significant decrease in catalytic efficacy detected. When the reaction time was extended to 55
min, the photooxidation of CEES showed an accumulation of monooxygenated-sulfoxide (CEESO)
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product; no detectable over-oxidation to the toxic sulfone (CEESO
2
) was observed (Figure S34) in
the NMR spectra.
The halogenated-POPs were further investigated by solution screening (using UV-Vis absorption
spectroscopy) for chromophore leaching (Figure S37); none was detected. The combined results are
consistent with efficient excited-state intersystem crossing for the halogenated-photocatalysts, and
efficient sensitization of singlet oxygen formation by these catalysts in their lowest-lying triplet
excited states.
Thioanisole is one of the most common model compounds used to gauge and compare the
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photoactivity of catalysts. Results for photooxidation of thioanisole under various conditions are
shown in Table S4. Little conversion of thioanisole was observed in the absence of irradiation or
catalyst (I-BDP-POP). The addition of candidate scavengers for reactive oxygen species (ROS)
1
such as NaN
3
(as O
2
scavenger) and benzoquinone (as superoxide scavenger) led to significant
decreases in the conversion yield of thioanisole under irradiation. However, no benzoquinone
conversion was observed, implying that superoxide is not generated. Furthermore, direct quenching
of photo-excited I-BDP-POP by azide can’t be ruled out. The addition of NaI (as a hole scavenger)
diminishes conversion, but by less than other scavengers. These results suggest that the candidate
ROS scavengers used here primarily function not by scavenging, but instead by quenching photo-
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excited I-BDP-POP and thereby suppressing ROS generation. We turned, therefore, to the well-
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known singlet oxygen probe 1,3-diphenylisobenzofuran (DPBF), which decomposes to its peroxo
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derivative upon reaction with singlet oxygen. Monitoring the electronic absorption of the probe
molecule (Figure S29), revealed that irradiation of the catalysts Br- and I-BDP-POPs generates
singlet oxygen. See Supporting Information for further details and discussion.
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Full conversion of thioanisole to methyl phenyl sulfoxide (under 1 bar of air) by four representative
BODIPY-containing porous photocatalysts from the extant literature (Table 3, Entries 2–5)
reportedly requires 15 h or more. In contrast with I-BDP-POP as the photocatalyst under identical
conditions to those for the conversion of CEES to CEESO, the half-life was found to be about 9 min.
Complete conversion to methyl phenyl sulfoxide (Figure S36) was observed to occur in ~20 min.
When the same reaction was examined under air, the half-life for thioanisole oxidation (Table 3)
was approximately 16 min; full conversion was achieved in ca. 30 min. 89
■
CONCLUSION
A BODIPY-based porous organic polymer (H-BDP-POP), having a substantial BET surface area
2
–1
(
640 m ·g ), can be obtained in ca. 90% yield via Sonogashira coupling, and bromine loss from a
derivative of BODIPY (H-BDP-M) featuring a pair of bromophenyl ethynyl substituents on boron
and a single bromophenyl substituent at the meso-carbon of H-BDP-M. Notably, coupling at these
sites is remote enough from the HOMO and LUMO to leave both orbitals largely unchanged by
polymerization while the linkage scheme serves to prevent stacking/aggregating of the POPs’
component chromophores. Post-synthetic bromination or iodination at the 2 and 6 positions of the
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BODIPY core of H-BDP-POP yields polymers that display the signatures of efficient photo-excited-
state singlet to excited-state triplet intersystem crossing, including greatly attenuated fluorescence
quantum yields, abbreviated singlet excited-state lifetimes, and low-temperature phosphorescence
based on indirect photo-excitation, i.e., initial excitation to singlet states. From measurements at 77
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K, we find the energy for phosphorescence by I-BDP-POP (13,120 cm ) is essentially a perfect
match for the energy gap between ground-state triplet O
2
and the higher of two singlet O excited-
2
states.
When illuminated under an O
2
atmosphere, the POPs catalyze the oxidation of CEES to CEESO in
MeOH. Consistent with enhanced intersystem crossing and photochemical sensitization of the
3
1
otherwise forbidden conversion of O
2
to O , the bromine- and iodine-elaborated derivatives of
2
BODIPY-based POPs (Br- and I-BDP-POPs) accomplish the conversion ca. 5x faster than does the
unelaborated polymer. The three new BODIPY-based POPs are quantitatively selective for the
conversion of the sulfur mustard simulant to the sulfoxide, and not to the toxic sulfone. Given the
ease and synthetic simplicity with which these promising photocatalytic polymers can be
synthetically accessed, we suggest that they merit further investigation at higher technology
readiness levels (TRLs).
■
EXPERIMENTAL
All materials, methods, and instrumentation as well as experimental details, including synthesis,
NMR data, and supportive figures have been described in the Supporting Information.
■
ASSOCIATED CONTENT
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Supporting Information
Materials / General Methods / Instrumentation, Synthetic Protocols, NMR Spectroscopy,
Crystallographic Characterization, N Adsorption, and Desorption Isotherms, Photophysical
2
Characterization, Diffuse Reflectance for Infrared Fourier Transform Spectroscopy (DRIFTS),
Powder X-Ray Diffraction (PXRD), Thermogravimetric Analysis (TGA), X-Ray Photoelectron
Spectroscopy (XPS), Density Functional Theory (DFT) Calculations, Photocatalytic Studies. This
material is available free of charge through the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Authors
E-mails: stoddart@northwestern.edu and j-hupp@northwestern.edu
*
ORCID
Ahmet Atilgan: 0000-0002-1531-3996
M. Mustafa Cetin: 0000-0002-6443-0232
Jierui Yu: 0000-0001-8422-3583
Yassine Beldjoudi: 0000-0002-9500-4308
Jian Liu: 0000-0002-9500-4308
Timur Islamoglu: 0000-0003-3688-9158
Omar K. Farha: 0000-0002-9904-9845
Pravas Deria: 0000-0001-7998-4492
J. Fraser Stoddart: 0000-0003-3161-3697
Joseph T. Hupp: 0000-0003-3982-9812
Author Contributions
#These authors contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGEMENTS
This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King
Abdulaziz City of Science and Technology (KACST) and Northwestern University (NU). The
authors would like to thank both KACST and NU for their continued support of this research. This
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project was also supported by the Defense Threat Reduction Agency under grant number HDTRA1-
1
9-1-0010 (O.K.F and J.T.H.). We thank the personnel in the Integrated Molecular Structure
Education and Research Center (IMSERC) at Northwestern University (NU) for their assistance in
the collection of the data. P.D. thanks to SIUC for the start-up support.
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(
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Mustards: Stability and Reactivity. Org. Biomol. Chem. 2012, 10, 8786–8793.
(7) Wagner, G. W.; Koper, O. B.; Lucas, E.; Decker, S.; Klabunde, K. J. Reactions of VX, GD,
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82) Blundell, S. Magnetism in Condensed Matter; Oxford University Press: Oxford, UK, 2001.
83) Jaguar, version 8.7; Schrodinger Inc.; New York, 2015.
(
Bochevarov, A. D.; Harder, E.; Hughes, T. F.; Greenwood, J. R.; Braden, D. A.; Philipp, D.
M.; Rinaldo, D.; Halls, M. D.; Zhang, J.; Friesner, R. A. Jaguar: A High-Performance
Quantum Chemistry Software Program with Strengths in Life and Materials Sciences. Int. J.
Quantum Chem. 2013, 113, 2110–2142.
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(84) Jensen F.; Greer A.; Clennan E. L. Reaction of Organic Sulfides with Singlet Oxygen. A
Revised Mechanism. J. Am. Chem. Soc. 1998, 18, 4439–4449.
(
85) Dad'ová, J.; Svobodová, E.; Sikorski, M.; König, B.; Cibulka, R. Photooxidation of Sulfides
to Sulfoxides Mediated by Tetra-O-Acetylriboflavin and Visible Light. ChemCatChem 2012,
4, 620–623.
(86) Nosaka, Y.; Nosaka, A. Y. Generation and Detection of Reactive Oxygen Species in
Photocatalysis, Chem. Rev. 2017, 17, 11302-11336.
(87) Ding, X.; Han, B. H. Metallophtalocyanine – Based Conjugated Microporous Polymers as
Highly Efficient Photosensitizers for Singlet Oxygen Generation, Angew. Chem. Int. Ed.
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88) Poß, M.; Gröger, H.; Feldmann, C. Saline Hybrid Nanoparticles with Phthalocyanine and
Tetraphenylporphine Anions Showing Efficient Singlet Oxygen Production and
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89) While investigations of reaction mechanisms and kinetic rate laws are beyond the scope of
this study, the half-life and completion-time data, together with the linear rate plots in Figures
9 and S28 for catalysis by halogenated chromophores, suggest zeroth-order kinetics for CEES
and thioanisole degradation. In turn, this conclusion suggests that the rate of delivery of
oxygen atoms to sulfur sites via singlet oxygen, and the rates of transport of reactants to
photocatalysts, are rapid in comparison to the rate of production of singlet oxygen. Further
experiments as a function of light flux may help to clarify the kinetics.
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Captions to Schemes and Figures
Scheme 1. Structure and design of H-BDP-POP using tritopic BODIPY monomer (H-BDP-M),
and its halogenation through post-synthetic modification (PSM).
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Scheme 2. Synthetic routes for the halogenation of H-BDP-M to Br- and I-BDP-Ms,
polymerization of H-BDP-M to H-BDP-POP, and post-synthetic halogenation of H-BDP-POP to
Br- and I-BDP-POPs.
Figure 1. Reported polymerization of BODIPY core at different positions for the synthesis of
BODIPY-based polymers
Figure 2. Diffuse reflectance for infrared Fourier transform spectroscopy (DRIFTS) absorption
spectra of the parent monomer and all the POPs.
Figure 3. Scanning electron microscopy (SEM) images of all the POPs.
Figure 4. Nitrogen sorption isotherms (a) of BDP-POPs at 77 K (filled shapes for adsorption, and
hollow shapes for desorption). Estimated pore-size distribution profiles (b) using the 2D–NLDFT
N2–carbon finite pores, As = 6) method.
Figure 5. UV-Vis absorbance and fluorescence emission spectra of H-, Br-, and I-BDP-Ms (2.5
µM) in CH Cl at RT under air.
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Figure 6. UV-Vis diffuse-reflectance (left) and emission spectra (right) for H-, Br-, and I-BDP-
POPs at 298 K.
Figure 7. Excitation and emission spectra of I-BDP-M (left) and I-BDP-POP (right) at 77 K.
Figure 8. Frontier molecular orbital distribution and energy levels of H- (in white), Br- (in red),
and I- (in pink) BDP-POPs from density functional theory (DFT) calculations.
Figure 9. (a) Comparison of CEES oxidation over time with equimolar BODIPY-based monomers
and porous organic polymers. (b) A plausible schematic representation of sulfur mustard simulant
oxidation by singlet oxygen. (c) Reusability of the Br- and I-BDP-POP catalysts for four cycles,
11 min each. All experiments above were performed in 1mL of anhydrous MeOH under 1 atm O
by using 1mol% catalyst irradiated with two green LEDs (total power of 450 mW·cm–2).
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Scheme 1
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I-BDP-POP
Br-BDP-POP
H-BDP-POP
H-BDP-M
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Wavenumber / cm-1
Figure 2
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