Kinetic and mechanistic aspects of solid state, nanostructured porphyrin diacid photosensitizers in photooxidation of sulfides

Article abstract of DOI:10.1039/c8cy02433b

In continuation of our studies on the photocatalytic performance of porphyrin diacids, the kinetics and mechanisms of the photooxidation of para-substituted phenyl methyl sulfides (para X = H, CH₃, OCH₃, Cl, and F) catalyzed by a series of meso-tetra(aryl)porphyrins (aryl = phenyl, 2-chlorophenyl, 2-methylphenyl, 4-chlorophenyl, 4-methylphenyl and 4-methoxyphenyl) immobilized on Amberlyst 15 nanostructures (nanoAmb), H₂T(2 or 4-X)PP@nanoAmb, are reported. The immobilization of porphyrins on the polymer was confirmed by diffuse reflectance UV-vis spectroscopy and EDX analysis. While little or no catalyst degradation was observed for a reaction time of ca. 3 h, the electron-deficient porphyrins (pseudo-first-order rate constants, k_obs = 0.0049-0.012 min^-1) showed faster second-order kinetics than the electron-rich ones (k_obs = 2.30 × 10^-5-9.92 × 10^-4 min^-1). The order of photocatalytic activity of the porphyrins approximately correlates with the singlet oxygen quantum yield (φ_Δ) of the photosensitizers. Diffuse reflectance UV-vis spectra of the immobilized porphyrins demonstrated a large red shift of the Soret and Q bands of the porphyrins which was more dominant in the case of H₂T(4-OMe)PP. The weak overlap between the emission spectrum of the light source and the absorption spectrum of the latter was used to explain the low photocatalytic activity of H₂T(4-OMe)PP@nanoAmb. The observation of a slope (ρ) of -2.80 for the oxidation of methyl phenyl sulfide and para-substituted phenyl methyl sulfides is in accord with the involvement of an electrophilic oxidation mechanism mediated by singlet oxygen species. H₂TPP@naoAmb was recovered and reused at least five times without significant loss of the catalytic activity and detectable catalyst degradation, giving a turnover number of 5 × 5000 for five successive reactions. The catalyst was successfully used for large-scale (up to 6.6 mmol of sulfide per batch, in a 1:10000 catalyst-to-sulfide molar ratio) photooxidation of a wide range of sulfides to the corresponding sulfoxide in a water/acetonitrile solvent mixture.

Full text of DOI:10.1039/c8cy02433b

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ISSN 2044-4753
PAPER
Qingzhu Zhang et al.
Catalytic mechanism of C–F bond cleavage: insights from QM/MM
analysis of fluoroacetate dehalogenase
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Catalysis Science & Technology
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DOI: 10.1039/C8CY02433B
Journal Name
ARTICLE
Kinetic and mechanistic aspects of solid state, nanostructured
porphyrin diacid photosensitizers in photooxidation of sulfides
Rahele Nasrollahi, Akram Heydari-turkmani and Saeed Zakavi*
Received 00th January 20xx,
Accepted 00th January 20xx
In continuing our studies on the photocatalytic performance of porphyrin diacids, kinetics and mechanism of the
DOI: 10.1039/x0xx00000x
photooxidation of para-substituted phenyl methyl sulfides (para X = H, CH
tetra(aryl)porphyrins (aryl phenyl, 2-chlorophenyl, 2-methylphenyl, 4-chlorophenyl, 4-methylphenyl and 4-
methoxyphenyl) immobilized on Amberlyst 15 nanostructures (nanoAmb), H T(2 or 4-X)PP@nanoAmb are reported. The
3
, OCH
3
, Cl, F) catalyzed by a series of meso-
www.rsc.org/
=
2
immobilization of porphyrins on the polymer was confirmed by diffuse reflectance UV-vis spectroscopy and EDX analysis.
While little or no catalyst degradation was observed for a reaction time of ca. 3 h, the electron deficient porphyrins
-
1
(
pseudo-first order rate constants, kobs = 0.0049-0.012 min ) showed faster second order kinetics than the electron-rich
-
5
-4
-1
ones (kobs = 2.30 × 10 -9.92 × 10 min ). The order of photocatalytic activity of the porphyrins approximately correlates
with the singlet oxygen quantum yield (φ ) of the photosenisitizers. Diffuse reflectance UV-vis spectra of the immobilized
porphyrins demonstrated large red shift of the Soret and Q bands of the porphyrins which was more dominant in the case
of H T(4-OMe)PP. The weak overlap between the emission spectrum of the light source and the absorption spectrum of
the latter was used to explain the low photocatalytic activity of H T(4-OMe)PP@nanoAmb. The observation of a slope (ρ)
of –2.80 for the oxidation of methyl phenyl sulfide and para-substituted phenyl methyl sulfides is in accord with the
involvement of an electrophilic oxidation mechanism mediated by singlet oxygen species. H TPP@naoAmb was recovered
Δ
2
2
2
and reused at least five times without significant loss of the catalytic activity and detectable catalyst degradation, giving a
turnover number of 5 × 5000 for five successive reactions. The catalyst was successfully used for large scale (up to 6.6
mmol of sulfide per batch, in a 1:10000 catalyst to sulfide molar ratio) photooxidation of a wide range of sulfides to the
corresponding sulfoxide in water/acetonitrile solvent mixture.
remains as
a
challenge for heterogeneous aerobic
photocatalytic systems. Aerobic photooxidation of sulfides is
an efficient strategy for selective oxidation of sulfides to
Introduction
8-10
sulfoxides.
On the other hand, the synthesis of novel
Aerobic oxidation of organic compounds with the aim of porphyrin photosensitizers with increased photo-stability and
conducting the oxidation reactions in the absence of toxic, catalytic activity has been the subject of many studies over the
high cost and usually environmentally harmful terminal past decades.11-16 The introduction of electron-withdrawing
oxidants is an important goal particularly from the green substituents at the periphery of the aromatic macrocycle has
1
-3
chemistry point of view.
Sulfoxides and sulfones are been generally utilized to improve the stability of porphyrins
important intermediates in the synthesis of organic and metalloporphyrins towards oxidative decomposition
4-5
compounds, medicine and industrial applications. The partial under the reaction conditions. However, the formation of
oxidation of sulfides provides sulfoxides as pharmaceutically molecular complexes between porphyrins and different protic
important intermediates. Also, the oxidation of sulfides to and Lewis acids may be used as an efficient alternative to
sulfoxides is an attractive process from mechanistic complicated chemical syntheses. Porphyrin diacids have been
6
-7
17
standpoint.
However, control of product selectivity still the subject of many studies since the late 1960s. However,
no attention was paid to their potential for use in catalytic and
photocatalytic reactions; In 2008, we have reported the first
a.Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS),
Zanjan 45137-66731, Iran. E-mail: zakavi@iasbs.ac.ir; szakavi@gmail.com
use of porphyrin diacids as catalyst for ring opening reaction of
18
epoxide. Recently, we have reported the improvement in the
†
Electronic Supplementary Information (ESI) available: [Spectral data of
photocatalytic performance of porphyrins in the aerobic
photooxidation of olefins through adduct formation with
porphyrins, sulfides and the corresponding sulfoxides; experimental setup and
general procedure of the photooxidation reactions; spectral changes upon the
photooxidation of DPBF ]. See DOI: 10.1039/x0xx00000x
different
heterogeneous conditions
σ and /or π acids under homogeneous and
12-13
The new metal free
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J. Name., 2013, 00, 1-3 | 1
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Page 2 of 16
ARTICLE
Journal Name
photosensitizers are of great interest from the green chemistry It is noteworthy that highly chemoselective VoiexwidAartticiloenOnlionef
19
point of view. The molecular complexes and diacids were sulfides to sulfoxides with turnover num
D
b
O
e
I:
r
1
s
0.
i
1
n
03
t
9
h
/C
e
8
r
C
a
Y
n
0
g
24
e of
33
B
found to show higher oxidative stability, catalytic activity and 4500-9900 and short reaction times is achieved using the
significantly red shifted absorption bands, compared to those immobilized porphyrins which can be scaled up to 0.78 ml of
of the corresponding free base porphyrins. Furthermore, sulfide per batch. Furthermore, little or no photocatalyst
porphyrin diacids were used as efficient photosensitizers with degradation was detected during the oxidation of sulfides. To
improved oxidative stability for chemoselective aerobic our knowledge, this is the first kinetic study of the
photooxidation of sulfides to sulfoxides under homogeneous photocatalytic activity of porphyrin diacids using a series of
20
conditions. However, due to highly conjugated structure of electron-rich and electron-deficient para-substituted phenyl
free base porphyrins and their dications, they are still sensitive methyl sulfides and meso-tetra(aryl)porphyrin diacids with
to extensive degradation by singlet oxygen and other reactive electron-demanding and electron-releasing meso substituents
oxygen species in the homogeneous phase.21 Also, while using under heterogeneous conditions.
water and other polar green solvents fulfils the requirements
22-23
of green chemistry
, most porphyrin dications and
molecular complexes suffer from partial to significant
dissociation into porphyrin and the acid molecules in hydrogen
1
3,20,24-25
bond forming and coordinating solvents.
Interestingly,
these issues may be substantially overcome by immobilization
of photosensitizers on suitable organic and inorganic
26-27
supports.
Furthermore, due to several advantages of
heterogeneous catalysts over the homogeneous counterparts
such as the ease of separation, increased stability and
improved reusability, much attention was paid to the
28-29
heterogenization of homogeneous catalysts.
In continuing
our studies on the photocatalytic activity of porphyrins
supported on Amberlyst 15 nanostructures, in the present
study, a series of electron-rich and electron-deficient meso-
tetra(aryl)porphyrins (Figure 1) were used for the oxidation of
sulfides in water/acetonitrile mixed solvent. Furthermore, the
kinetics and mechanistic aspects of the aerobic photooxidation
of para-substituted methyl phenyl sulfides in the presence of
the porphyrin diacids were studied. It is noteworthy that most
previous kinetic studies on oxidation and photooxidation of
organic compounds have been devoted to those catalyzed by
Figure 1. Photocatalysts used in this study.
30-40
non-porphyrinic photosensitizers or metalloporphyrins
and little attention was paid to the porphyrin Experimental
41-42
photosensitizers.
Instrumental
Previously, according to the correlations between the rate
constants and Hammett substituent constants, it was shown
that aerobic oxidation of sulfides with singlet oxygen is carried
out through an electrophilic mechanism by initial attack of
UV-vis and diffuse reflectance UV-vis (DR UV-vis) spectra were
prepared on a Pharmacia Biotech Ultrospec 4000 UV-vis
spectrophotometer and
a
Varian Cary 5000 UV-Vis-NIR
43-44
singlet oxygen on the sulfur atom.
Albini et al. have
1
absorption spectrometer, respectively. H NMR spectra were
obtained on a Bruker Avance DPX-400 MHz spectrometer. The
reaction mixtures were analyzed by a Varian-3800 gas
studied the quenching of the singlet oxygen by a series of 4-
substituted thioanisoles under homogeneous conditions and
provided evidence for an electrophilic mechanism for the
photooxidation reaction. Moreover, a decreased reaction rate chromatograph equipped with a HP-5 capillary column and a
was observed in aprotic solvents. Also, the formation of flame-ionization detector. FT-IR spectra were prepared using a
persulfoxide intermediates was elucidated in these reactions. Bruker Vector 22 instrument. Nitrogen adsorption/desorption
3
7, 45
isotherms were recorded on a Belsorp Max instrument (BEL-
Japan, Inc.) for porosimetry analysis. The mean diameter and
size distribution of the solid catalyst before and after loading
of porphyrin were measured by with a Malvern Zetasizer
In free base meso-tetra(aryl)porphyrins and metalloporphyrins
with a planar or nearly planar porphyrin conformation, the
meso substituents are almost perpendicular to the porphyrin
plane and therefore there is no efficient resonance interaction
between the π systems of the meso substituents and
porphyrin core. Protonation of meso-tetra(aryl)porphyrins is
accompanied with a decrease in dihedral angle between meso
aryl groups and porphyrin mean plane leading to an increase in
Nano-ZS
instrument
(Malvern
°
Instruments
Ltd.,
Worcestershire, UK) at 25 C with a detection angle of 90°.
Field-emission scanning electron microscopy (FE-SEM; Carl
Zeiss ULTRA PLUS) was utilized for determination of the
the resonance interactions between the aryl group and morphology and size of the nanoparticles. For this purpose,
porphyrin π systems. Accordingly, the difference between the crushed Amberlyst beads obtained after 5 and 24 h were
46
the stereoelectronic properties of the meso substituents is placed on a clean glass slide and then vacuum-coated with
more pronounced in porphyrin diacids. 12
gold. Digital images of the samples were taken with
2
| J. Name., 2012, 00, 1-3
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HitachiS4160 field emission scanning electron microscope general oxidation procedure using H
ARTICLE
2
TPP@nanoAmb (0.00066
View Article Online
DOI: 10.1039/C8CY02433B
operating at 20 kV.
mmol) as photocatalyst. The catalyst was filtered and
separated from the reaction mixture. Crude material was
separated by Thin-layer chromatography (TLC) (1:4 ratio of
Synthesis and immobilization of porphyrins
ethyl acetate, n-hexane) to give methyl phenyl sulfoxide (425
Meso-tetraphenylporphyrin, H
substituted derivatives, H T(4-OMe)PP, H
Cl)PP, T(2-Me)PP and T(2-Cl)PP were synthesized,
characterized and purified according to the literature
methods. The H NMR, C NMR and UV-Vis spectral data of
the porphyrins are presented in ESI,† S1. Amberlyst 15 dry
2
TPP and its para and ortho
1
mg, 92%). H NMR (400 MHz, CDCl
3
): δ= 7.56–7.38 (m, 5H),
2
2
T(4-Me)PP, H T(4-
2
2
.61 (s, 3H).
Singlet oxygen quantum yield determination
The φ values of the photosensitizer were measured through
H
2
H
2
4
7
1
13
Δ
the reaction of the reactive oxygen species with 1,3-
diphenylisobenzofuran (DPBF) as a quencher of singlet oxygen
(Acros) was used as received. A solution of the desired
4
8
and methylene blue (φ
reference photosensitizer. The equation φ
Δ
= 0.52 in water and acetonitrile) as a
porphyrin (0.08 mmol) in 25 ml ethyl acetate was added to 1.5
g Amb. The mixture was stirred for 24 h at room temperature
in air and the initial pale yellow polymer turned into green.
The solid was separated by centrifuging and washed with ethyl
acetate until the filtrate was colorless. The amount of
porphyrin loaded on the polymer was measured by UV-vis
spectroscopy; Tetra-n-butylammonium hydroxide was added
to the nanoAmb supported porphyrin in ethyl acetate to
release the immobilized porphyrin. The released porphyrin
was measured by the absorbance measurement at the
wavelength of its Soret band using a calibration curve
prepared by plotting the absorbance versus concentration of
the respective porphyrin.
std
Δ
= φ
values; φ
value of the standard photosensitizer
Δ
× (ν
i
×
std
std
std, υ
std,
I
I
(
/υ
i
×I) was used to determine the φ
Δ
Δ
i
, υ
i
std
and I show the φ
Δ
-
4
methylene blue, MB), the rate of DPBF (8 × 10 M) oxidation
in the presence of a given photosensitizer and a 10 W red LED
lamp, the rate of DPBF oxidation in the presence of methylene
blue, the number of photons absorbed by the standard
solution and those absorbed by the respective photosensitizer,
4
9
respectively.
Results and Discussion
Amberlyst beads are readily nanosized using a proper solvent.
As we have reported previously , the vigorous stirring of
General oxidation procedure
11
Unless otherwise mentioned, in all photooxidation reactions, amberlyst and porphyrins in ethyl acetate leads to the
the catalyst (0.025 mol%, 0.00066 mmol) was added to the formation of polymer supported porphyrins with a size in the
solution of sulfide (3.3 mmol) in acetonitrile (5 mL) /water (5 range 200-240 nm. Diffuse reflectance UV-vis spectroscopy
mL) and stirred in a double walled cylindrical glass vessel showed the immobilization of porphyrins on the acidic support
equipped with water circulation to maintain a constant in the form of porphyrin diacid (Figure 2); as seen from Figure
temperature (ESI,† S2). The solution was saturated with 2 and Table 1, the immobilization of porphyrins on the
oxygen by slow purging through a glass needle for 30 min. The polymeric support leads to the red shift of the Soret and Q(0,0)
reactions were conducted under irradiation with a 20 W white bands that is in accord with the formation of porphyrins
50
LED lamp as the light source for the required time. Also, diacids. It is noteworthy that diprotonation of porphyrins is
sunlight with an intensity of 59000 lux was used as a control accompanied with the reduction of the Q bands from 4 to 2 or
51
reaction. The reaction progress was monitored by TLC using one bands. For most meso-tetra(aryl)porphyrins, only one Q
authentic samples. GC analysis was used to determine the band, Q(0,0) is observed and the other band, Q(0,1) appears as
52
yields of sulfoxide and sulfone. No sulfone product was a shoulder on the Q(0,0) band. Furthermore, the wavelength
observed in the oxidation of different sulfides in a 1:1 of the Q(0,0) band of the diacids increases from H T(2-Cl)PP to
2
acetonitrile/water mixture. However, in the case of using neat H2T(4-OMe)PP that correlates with the electron-donor ability
acetonitrile as the solvent, sulfone product was also obtained of the meso-substituents.
in low yields (vide infra). Furthermore, as was described
20
elsewhere, the reaction mixture was worked up to isolate the
sulfoxide product from solvent and unreacted sulfide; the
catalyst was separated from the reaction mixture by centrifuge
and filtration. Thin layer chromatography on a silica gel plates
(with a thickness of ca. 0.25 mm and a length of 20 cm) using
n-hexane and ethyl acetate in 4:1 to 10:1 volume ratios led to
1
the separation of sulfoxide as the sole product. The H NMR
spectra of the sulfoxides summarized in the ESI,† S3) show
high purity of the isolated sulfoxides. Oxidation of 1-
(
methylsulfinyl)benzene and other sulfides (ESI,† S3) was
conducted as follows:
-(methylsulfinyl)benzene (1b): Methyl(phenyl)sulfane (1a)
410 mg, 3.3 mmol) was oxidized according to the above
1
(
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The immobilization of porphyrins on NanoAmb is accompanied
with the formation of diprotonated species of the used
porphyrins. On the other hand, in the micropores, the SO H
3
View Article Online
DOI: 10.1039/C8CY02433B
Figure 2. DR UV-vis spectra of
H
2
T(2-Cl)PP@nanoAmb (black curve),
TPP@nanoAmb
T(4-Cl)PP@nanoAmb (dark
H
2
T(4-
OMe)PP@nanoAmb(red),
pink curve), H T(4-Me)PP@nanoAmb (green curve) and H
blue).
2 2
H T(2-Me)PP@nanoAmb (blue curve), H
(
2
2
groups responsible for protonation of porphyrin are closer to
each other and therefore the formation of a diprotonated
porphyrin is more facilitated under these conditions. It should
be noted that as was shown in several studies, for most
porphyrins the formation of a diprotonated species is more
convenient and preferred over a monoprotonated species due
to thermodynamic and kinetic effects. The formation of
monoprotonated is more difficult than a diprotonated one.
The formation of a monoprotonated species leads to out of
plane deformation of porphyrin core so that the second
pyrrole ring is in a better orientation to make a strong bond
with the second acid molecule. Also, the Vtotal and SBET values
(Table 2) show significant decrease in the BET surface area and
pore volume values after the immobilization of the porphyrins.
Also, DLS of the nanoparticles suspended in water showed an
Table 1. DR UV-vis spectral data of the photosensitizers.
Absorption bands (λ/nm)
Photosensitizer
Soret
441
Q(0,1)
605
Q(0,0)
656
H
2
TPP@nanoAmb
H
H
2
T(2-Me)PP@nanoAmb
T(2-Cl)PP@nanoAmb
436
435
587
583
636
634
2
H
H
H
2
T(4-Me)PP@nanoAmb
2
T(4-OMe)PP@nanoAmb
2
T(4-Cl)PP@nanoAmb
444
456
446
a
a
a
662
697
664
a
The band appeared as a shoulder on the longer wavelength band.
average diameter of 198 and 238 nm for nanoAmb and H
Cl)PP@NanoAmb, respectively (Figure 4). Accordingly, there is
little or no difference between the particles size of H T(2-
Me)PP@NanoAmb and H T(2-Cl)PP@NanoAmb. Furthermore,
2
T(2-
The presence of bulky substituents at the ortho position of the
phenyl groups leads to an increase in the dihedral angle
between the meso aryl groups and porphyrins mean plane.46
This, in turn, prevents efficient π-π resonance interactions
between the porphyrin core and meso substituents π systems
and consequently a blue shift is observed in the position of the
2
2
field-emission scanning electron microscopy (FESEM) images
revealed the formation of nearly spherical nanoparticles with
an average diameter of ca. 50 nm in the case of H
Cl)PP@NanoAmb.
2
T(2-
5
3
Q(0,0) band. In contrast, the presence of strong electron-
donating groups such as –OCH at the phenyl substituents
The observed difference between the particle size obtained
from DLS and FESEM is probably due to the high hydrophilicity
3
shifts the Q(0,0) band of porphyrins to higher wavelength due
to the increased electron-donation from the meso substituents
54
of the used polymer. A Particle size of ca. 50 nm was also
2 2
obtained for H TPP@NanoAmb and H T(2-Me)PP@NanoAmb.
46
to porphyrins core. The porosimetry experiments confirmed
the porous structure of the nanoparticles (Figure 3).
This observation is in line with the results of BET analysis
confirming the immobilization of porphyrins into the pores of
the porous polymer.
The nitrogen sorption isotherms of the solid catalysts shown in
Figure 3 are in accord with the mesoporous structure of the
catalysts and mean pore size diameters in the range of 32.4-
3
7.8 nm, for different porphyrin@nanoAmb compounds. It is
noteworthy that in NanoAmb both micropores and mesopores
are found with mean pore diameters of 3.2 and 28.2 nm,
respectively. As seen from Figure 3, the number of former is
higher than the latter.
Table 2. BET analysis of nanoAmb and porphyrin@nanoAmb compounds.
α
b
Entry Photosensitizer
S
BET
V
t
Pore
m2g-
(cm g )
3
-1
diameter
(
1)
1
2
4
5
3
5
5
nanoAmb
85.0
33.0
45.0
37.8
44.2
46.1
40.7
0.5183
0.3000
0.3600
0.3532
0.3422
0.3456
0.3458
3.2, 28.2
32.4
H
H
H
H
H
H
2
2
2
2
2
2
TPP@nanoAmb
T(2-Cl)PP@Amb
32.6
T(2-Me)PP@nanoAmb
T(4-OMe)PP@nanoAmb
T(4-Me)PP@nanoAmb
T(4-Cl)PP@nanoAmb
37.8
32.6
32.4
32.6
a
α
b
S
BET and V
t
are the specific surface area and total pore volume, respectively.
4
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Journal Name
ARTICLE
View Article Online
DOI: 10.1039/C8CY02433B
Figure 3. N2 adsorption/desorption isotherms of nanoAmb and porphyrin@nanoAmb compounds.
2
Figure 3. N adsorption/desorption isotherms of nanoAmb and porphyrin@nanoAmb compounds.
2 2
Figure 4. FE-SEM images of nanoAmb and H T(2-Cl)PP@NanoAmb and DLS characterization of H T(2-Cl)PP@NanoAmb.
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
Further evidence on the immobilization of porphyrins on photosensitizers. Indeed, high degrees of catalystVidewegArrtaicdleaOtniolinne
nanoAmb was provided by EDX spectrum and carbon, by ROS usually observed in porphyrin baDsOeId: 10c.a1t0a3l9y/tCic8CsYy0s2t4e3m3Bs
nitrogen, oxygen, sodium and sulfur elemental mapping may be prevented by increasing the substrate concentration. It
captured for H
2
T(2-Cl)PP@nanoAmb (Figure 5).
should be noted that the catalyst degradation may be
considered as an unwanted attack by ROS on the
photosensitizer as an oxidizable organic compound. Oxidation
of methyl phenyl sulfide was conducted using different catalyst
to substrate molar ratios to find the optimized one (Table 3).
To optimize the reaction conditions, the oxidation of methyl
C K
S K
1000
900
800
700
600
500
400
300
200
100
0
2
phenyl sulfide in the presence of H TPP@nanoAmb was
studied under various conditions (Table 3, Figure 6).
The change of solvent from neat acetonitrile to
acetonitrile/water mixture (entries 1 and 2) led to a slight
increase in the conversion value but a significant increase in
the chemoselectivity of the reaction towards the formation of
sulfoxide. Accordingly, the use of acetonitrile/water mixed
solvent led to the formation of sulfoxide as nearly the
exclusive product. Also, the increase in the catalyst to
substrate molar ratio up to 1:5000 has little effect on the
conversion value but remarkable increases in turnover number
N K
S K
O K
NaK
ClK
ClK
keV
6.800
0
(TON) and turnover frequency (TOF) were observed (entries 2,
3
and 4). Further increase in the catalyst to substrate molar
Figure 5. EDX spectrum and element map analysis of H
2
T(2-Cl)PP@nanoAmb. Also, the
ratio increases the reaction time from 3 to 6 h for completion
of the reaction (entries 5 and 6).
results of EDX elemental analysis of H T(2-Cl)PP@nanoAmb are shown in the ESI,† S4.
2
The rate of photooxidation of sulfides and the
chemoselectivity of reaction depend on different parameters
including the catalyst to sulfide molar ratio, polarity of solvent,
temperature, intensity and wavelength of the light source. The
molar ratio of photosensitizer to substrate is among the main
factors influencing the performance of porphyrin
Table 3. The optimized reaction conditions for the oxidation of methyl phenyl sulfide.
Entry
Catalyst:sulfide
solvent
CH CN
Light Source
Time
Conversion (%)a
TON [TOF (h-1)]b,c
Sulfoxide
Sulfone
1
2
3
4
5
6
7
8
1:1000
1:1000
3
White LED (20 W)
White LED (20 W)
White LED (20 W)
White LED (20 W)
White LED (20 W)
White LED (20 W)
White LED (20 W) (air)
Sunlight
3 h
3 h
3 h
3 h
3 h
6 h
8 h
6 h
81
99
93
92
84
99
90
92
12
<1
<1
<1
<1
<1
<1
<1
810 [270]
990 [330]
CH
CH
CH
CH
CH
3
CN/H
3
CN/H
3
CN/H
3
CN/H
3
CN/H
2
2
2
2
2
O
O
O
O
O
1:3000
2790 [930]
4600 [1533]
8400 [2800]
9900 [1650]
9000 [1125]
9200 [1533]
1:5000
1:10000
1:10000
1:10000
1:10000
CH
CH
3
CN / H
2
O
3
CN / H
2
O
a
1
b
All reactions were repeated three times, analyzed by GC and the average values were reported. The products were also characterized by H NMR (ESI,† S1). TON is
c
defined as the number of product moles obtained by one mole of the catalyst. TOF shows the turnover number of the reaction per time unit.
6
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Figure
6.
a)
Photooxidation
of
methyl
phenyl
sulfide
with
H
2
TPP@nanoAmb
using
1:1000
to
1:10000 molar ratios of catalyst:substrate in acetonitrile / water under oxygen and white LED lamp (20 W); b) The optimized conditions for aerobic sulfoxidation of methyl phenyl
sulfide.
Table 4. Effect of light source on the photooxidation of methyl phenyl sulfide catalyzed by H
2
TPP@nanoAmb.a
-
1
Entry
Conversion (%)
Selectivity (%)
Photostability (%)
TON [TOF(h )]
4600 [1533]
2600 [866]
Withe LED (20W)
Blue LED (20W)
Red LED (20W)
Sunlight
92
52
21
86
100
100
100
100
100
100
100
100
1050 [350]
4300 [1433]
a
See Table 3 for more experimental details.
emission spectra of the used LED lamps used in this study are
shown in Figure 7. It is observed that the emission spectrum of the
blue LED lamp overlaps more efficiently with the absorption region
of the latter. In the case of the red LED lamp, the emission band
appears in the range of 600 to 640 nm with maximum intensity at
The increased chemoselectivity of the oxidation reaction in the
presence of water seems to be due to the stabilization of the
persulfoxide intermediate by hydrogen bonds in protic solvents
(
vide infra). In other words, while the formation of hydrogen bonds
stabilizes the persulfoxide intermediate, the presence of extensive
hydrogen bonds around this intermediates decreases it reactivity
towards the oxidation of sulfoxide. On the other hand, the use of
water together with acetonitrile is consistent with the requirements
of green chemistry principles. The oxidation of methyl phenyl
sulfide was also studied by using air as the oxygen source (entry 7).
Interestingly, a conversion value of ca. 90 % was achieved in a
reaction time of 8 h that is comparable with that obtained in the
presence of oxygen gas with the same pressure. It is noteworthy
that little or no oxidation of methyl phenyl sulfide was observed
under nitrogen gas atmosphere.
6
15 nm.
The oxidation was performed by irradiation of the reaction mixture
with different light sources (Table 4) and a 20 W white LED was
found to be more efficient than the corresponding blue and red LED
lamps. The significantly increased conversion value in the presence
of the blue lamp compared to that in the presence of the red lamp
shows that the excitation at the Soret band region is mainly
Figure 7. The emission spectra of the LED lamps.
2
involved in the photocatalytic activity of H TPP@nanoAmb. The
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Journal Name
For the blue LED lamp (λmax = 463 nm), a band is observed between considered in this comparison. Interestingly, no signiVfiiecwanAtrticclaetOanlylinset
40-500 nm. For the white LED lamp, a narrow intense emission degradation was observed under sunlight iDrrOaId: 1ia0t.1io0n39a/Cn8dCtYh0e24L3E3DB
4
band (λmax = 447 nm) is observed at ca. 418 to 475 nm. Also, two lamps.
broad bands are observed in the range of 498 to 640 nm (λmax = 547 It is noteworthy that the bands around ca. 440 nm (Table 1) are
and 594 nm). The higher efficiency of the white LED lamp than the appropriate for the excitation of the photosensitizers in the Soret
blue and red LED lamps seems to be due to the overlap of the latter band region. Also, the emission bands of the red LED lamp and the
with both the Soret and Q bands of the photosensitizer. higher wavelength region of the white LED lamp are appropriate for
Furthermore, a conversion value comparable with that achieved the excitation at the Q band region.
under sunlight conditions was observed. Accordingly, sunlight may In order to study the substituent effects on the reactivity of sulfides,
be successfully used as the light source instead of the LED lamps. It the oxidation of various sulfides was conducted under optimized
is noteworthy that the oxidative degradation of porphyrin reaction conditions (Table 5). The reactions were also performed in
photosensitizers is a serious problem associated with the use of acetonitrile.
these compounds under oxidative conditions should be also
Table 5. Photooxidation of different para-substituted phenyl methyl sulfides by H
2
TPP@nanoAmb.a
b
TON [TOF(h-1)]c,d
Para-substituent
Major product
Conversion [Sulfoxide selectivity](%)
CH
3
CN:H
2
O (1:1)c
CH
CNd
3
c
d
c
d
H
F
92 [100]
49 [92]
4600 [1533]; 490 [280]
c
d
c
d
99 [100]
43 [95]
4950 [1650]; 430 [246]
c
d
c
d
Cl
99 [100]
17 [94]
4950 [1650]; 170 [97]
c
3d [75]
c
d
CN
93 [100]
4650 [1550]; 30 [17]
c
d
c
d
CH
3
99 [100]
76 [90]
4950 [1650]; 760 [434]
c
d
c
d
OCH
3
95 [100]
90 [91]
4750 [1583]; 900 [514]
a
The catalyst and substrate were used in a 1:5000 molar ratio. A 20 W white LED lamp was used as the light source. b See the footnotes of Table 3. c For a reaction time
of 3 h in 1:1 acetonitrile (5 mL)/ water (5 mL) solvent mixture. d For a 1:1000 molar ratio of catalyst to substrate, using a 10 W white LED lamp as the light source and a
reaction time of 105 min in neat acetonitrile. The results for the oxidation of some other sulfides are summarized in ESI,† S6.
8
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Scheme 1. Proposed mechanism for the photooxidation reaction; acid catalysis with the involvement of water molecules and porphyrin dication (path A). Path B shows
the formation of sulfone in the absence of acid catalysis. Ps, E.T and KISC show photosensitizer, energy transfer and intersystem crossing rate constant, respectively.
1
As seen from Table 5, there is little or no difference between the the increased diffusion coefficient of the O
reactivity of para-substituted phenyl methyl sulfides for the in this observation.55
reactions conducted in acetonitrile/water mixed solvent. Also, the
2
may be also involved
sulfides were generally much more reactive in acetonitrile/water Kinetics of oxidation of para-substituted methyl phenyl
compared to neat acetonitrile (see also Table 3). Apparently, the sulfides
hydrogen bond formation between the persulfoxide intermediate The kinetics of the photooxidation of sulfides with the singlet
and water molecules in the former which facilitates the formation
2
O sensitizers was studied under pseudo-first order conditions
of the persulfoxide intermediates leads to a comparable reactivity by fitting the concentration change of sulfides against the
for these sulfides.
irradiation time. The plot of ln(A
The slope (kobs) and the initial consumption rate of sulfides (ν
are determined by equations and , respectively. Herein, A
, kobs, t, and ν stand for the concentration of sulfide at
t 0
/A ) vs. time (t) was linear.
i
)
Table 6.Temperature effect on the oxidation of methyl phenyl sulfide.a
1
2
t
,
Methyl phenyl sulfide
Temperature
A
0
different time intervals (t), the initial concentration of sulfide,
pseudo-first-order rate constant, irradiation time (t) and the
consumption rate of sulfides, respectively.
-
22 °C (2 h)
25°C (3 h)
6.50
Sulfide
Sulfoxide
Sulfone
0.48
93.80
5.72
ln(A
t
/A
0
) = kobs.t
(1)
80.80
ν
i
= kobs[Sulfide]
(2)
The oxidation of phenyl methyl sulfides with different
electron-demanding and electron-donating groups at the para
position of the phenyl group was conducted in acetonitrile
(Figure 8a)
The concentration vs. time curves for the sulfides are shown in
Figure 8b. An induction period of ca. 25 observed for the
oxidation reactions may be due to the time required for
swelling of polymer support which makes the porphyrin sites
more accessible for the photooxidation reactions.
12.56
a
Due to the relatively high freezing point of water, the reactions were conducted
in acetronitrile. A white LED lamp (20 W) was used as the light source. Catalyst
and substrate were used in 1:1000 molar ratio.
b
The oxidation of methyl phenyl sulfide was also studied at different
temperatures (Table 6) and a significant decrease in the reaction
time was observed at 251 K. This observation seems to be due to
the increased solubility of molecular oxygen in acetonitrile at lower
temperature. Also, thermal deactivation of the triplet state of the
photosensitizer by singlet oxygen at lower temperatures caused by
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Figure 8. a) Kinetic curves for the photooxidation of para-substituted methyl phenyl sulfides (0.066 M) in the presence of H
2
TPP@nanoAmb in acetonitrile and a 10 W white LED
lamp. b) The change in the concentration of para-substituted methyl phenyl sulfides vs. time with an induction period of ca. 25 min.
Table 7. Oxidation of p-substituted-phenyl methyl sulfides in the presence of H
2
TPP@nanoAmb in acetonitrile.a
b
2
b
(×102)
0
p-X-phenyl methyl sulfide
k
obs (×10 )
(
ν
i
-
1
(M.min-1)
min )
= kobs[Sulfide]
4
-Methoxyphenyl methyl sulfide
14.48
95.57
Methyl p-tolyl sulfide
6.68
1.30
0.90
0.34
0.03
44.09
8.58
5.94
2.24
0.22
Methyl phenyl sulfide
4
4
4
-Fluorophenyl methyl sulfide
-Chlorophenyl methyl sulfide
-Cyanophenyl methyl sulfide
a
The catalyst and substrate (0.066 M) were used in 1:1000 molar ratio. A 10 W white LED lamp was the light source. b
kobs and v show the pseudo-first order rate
i
constants and initial consumption rate of sulfides, respectively.
The kobs values, summarized in Table 7 are consistent with or a superoxide radical anion mediated charge transfer
higher reactivity of the electron-rich sulfides so that nearly no mechanism (Scheme 1). According to the previous studies,
reaction was observed in the case of methyl para-cyanophenyl small ρ values (> 1) and large ones (< 1) were observed for the
sulfide. However, methyl para-methoxyphenyl sulfide and former and latter, respectively.37 Furthermore, weak
+
methyl para-tolyl sulfide are much more reactive than the correlation between the rate constants and σ constants (R
2
=
other sulfides. The Hammett treatment of data for the 0.93) indicates that a single electron transfer (ET) mechanism
oxidation of methyl phenyl sulfide and para-substituted phenyl is not considerably involved in this reaction (Figure 9) It is
methyl sulfides (Figure 9) gave a slope (ρ) of –2.80, which is noteworthy that in the case of ET, referred to as the type II
consistent with an electrophilic mechanism35. The observation mechanism, the sulfide radical cation intermediate could be
of a ρ value of -2.8 (R
was comparable with that observed for the myoglobin- donor substituents such as such as –OCH
catalyzed sulfoxidation of the same sulfides was attributed to reactions conducted in the presence of singlet oxygen and
2
= 0.99) for the oxidation of sulfides that stabilized by resonance interactions with π interactions with π
3
. Also, the control
3
4, 36-
the involvement of an electrophilic oxidation mechanism.
superoxide anion radical quenchers confirmed the presence of
37
It is noteworthy that the aerobic photooxidation of organic singlet oxygen as the main reactive oxygen species (ROS) in
compounds may proceed through a singlet oxygen mechanism this catalytic system.
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+
Figure 9. Linear free energy relationships for the oxidation of para-substituted methyl phenyl sulfides using σ and σ parameters.
Figure 10. (a) The change in the DR UV-vis spectrum of H
2
TPP@nanoAmb separated from the reaction mixture after 5 successive runs. (b) Reusability of
2
H TPP@nanoAmb in the oxidation of methyl phenyl sulfide in water/acetonitrile solvent mixture using a 20 W white LED lamp for a reaction time of 3 h. Catalyst and
substrate were used in a 1:5000 molar ratio.
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The oxidation of methyl phenyl sulfide was conducted in the
presence of H
2
2
TPP@nanoAmb to study the reusability of the Table 8. Oxidation of methyl phenyl sulfide in the presence of H T(2 or 4-
catalyst (Figure 10b). As seen from Figure 10b, the catalysts X)PP@nanoAmb.a
may be recovered and reused at least five times without a Photosensitizer
significant decrease in its catalytic activity and selectivity
3
(×102)
= kobs[Sulfide]
(Mmin-1)
k
obs (×10 )
ν
i
-
1
(min )
12.00
10.63
9.09
4.91
0.99
0
H
H
H
H
H
H
2
2
2
2
2
2
T(4-Cl)PP@nanoAmb
T(2-Cl)PP@nanoAmb
T(2-Me)PP@nanoAmb
TPP@nanoAmb
T(4-Me)PP@nanoAmb
T(4-OMe)PP@nanoAmb
79.20
70.16
59.99
32.40
6.53
towards the formation of sulfoxide. This observation is
probably due to the significant oxidative stability of the
catalyst after the 5th run.
The photocatalytic activity of different porphyrins immobilized
on nanoAmb for the oxidation of methyl phenyl sulfide was
studied to investigate the influence of meso substituents on
the efficiency of the photosensitizers (Figure 11, Table 8).
0.02
0.13
aSee the footnotes of Table 7, for more experimental details.
As seen from Table 8,
H
2
T(4-Cl)PP@nanoAmb,
H
2
T(2-
and
The extent of overlap between the emission spectrum of the
light source (Figure 7) and the absorption spectrum of the
Cl)PP@nanoAmb,
H
2
T(2-Me)PP@nanoAmb
2
H TPP@nanoAmb were much more efficient photosensitizers
porphyrinic photosensitizers (Figure 2) is
a key factor
than H T(4-Me)PP@nanoAmb and H T(4-OMe)PP@nanoAmb.
2
2
determining the photocatalytic performance of the
photosensitizers. The position of the absorption bands of the
immobilized porphyrins (Figure 2) are summarized in Table 1.
As seen from Table 1, the emission maxima of the white LED
lamp less efficiently overlap with the absorption bands of
H T(4-OMe)PP@nanoAmb, due to the red shifted Soret and Q
2
bands of this porphyrin with respect to those of the other
porphyrins.
In other words, the electron deficient porphyrins showed
higher catalytic activities compared to the electron-rich ones.
With respect to the negligible oxidative degradation of the
porphyrins used in this study, the relative catalytic activity of
the porphyrins can not be attributed to their relative oxidative
stability. The higher efficiency of H
T(2-Cl)PP@nanoAmb is probably due to the heavy atom
effect that facilitates the singlet to triplet intersystem crossing
of the S state of the photosensitizer; the latter is necessary for
the formation of the T state of photosensitizer responsible for
the formation of singlet oxygen species.
2
T(4-Cl)PP@nanoAmb and
H
2
In order to elucidate the nature of reactive oxygen species
1
(ROS) in this catalytic system, 1,3-diphenylisobenzofuran
1
56-57
(DPBF) and 1,4-benzoquinone were used as the quencher of
singlet oxygen and superoxide radical anion, respectively.5
8-59
Figure 11. Kinetic curves for the oxidation of methyl phenyl sulfide in the presence of
different porphyrinic photocatalysts (see the footnotes of Figure 8a for more details).
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Figure 12. (a) The change in the UV-vis spectrum of DPBF (λmax = 415 nm) in acetonitrile in the presence of H
80 s); (b) Kinetic curves for the oxidation of DPBF in the presence of various photocatalysts.
2
T(2-Cl)PP@nanoAmb after irradiation with a 10 W red LED lamp (0 to
5
As was shown in some recent studies,60-61 the addition of DPBF Table 9. Kinetics data for the oxidation of DPBF and the singlet oxygen quantum
led to nearly complete disappearance of the absorption band yields of the photosenistizers in acetonitrile.
-
1
-1
104ν
(min-1)
of DPBF at 415 nm in the UV-vis spectrum (Figure 12a) which Porphyrin@nanoAmb
kobs (M min )
i
φ
∆
was in accord with the presence of singlet oxygen species as
the ROS (see the ESI,† S5, for the reaction conducted in the
presence of the other Porphyrin@nanoAmb compounds). The
kinetic curves for the oxidation of DPBF in the presence of the
immobilized porphyrins (Figure 12b, Table 9) demonstrate
significant influence of the peripheral substituents on the
photocatalytic activity of the immobilized porphyrins. On the
other hand, running the oxidation of methyl phenyl sulfide in
the in the presence of 1,4-benzoquinone led to no detectable
change in the conversion value. The latter gives evidence for
the absence of superoxide radical anion in the catalytic cycle of
the oxidation reaction.
H
H
H
H
H
H
H
4
2
2
2
2
2
2
TPP(HSO
4
)
2
0.0107
7.00
1.34
1.18
0.71
0.63
0.54
0.12
-
0.203
0.028
0.030
0.016
0.019
0.019
0.004
0.52
T(2-Cl)PP@nanoAmb
T(4-Cl)PP@nanoAmb
T(2-Me)PP@nanoAmb
TPP@nanoAmb
T(4-Me)PP@nanoAmb
T(4-OMe)PP@nanoAmb
0.00204
0.00179
0.00109
0.000952
0.000828
0.00019
-
MB
Conclusion
A series of electron-rich and electron-deficient ortho- or para-
substituted meso-tetra(phenyl)porphyrins immobilized on
Amberlyst 15 nanostructures, H T(2 or 4-X)PP@nanoAmb
2
The singlet oxygen quantum yield (φ
Δ
) of the photosensitizers
62-63
measured DPBF
as a quencher of singlet oxygen and
methylene blue as a standard are summarized in Table 9. This
factor shows the efficiency of the photosensitizer in utilizing
the absorbed light for the conversion of triplet oxygen to
singlet oxygen species. As seen from Table 9, the exception of
were used as photosensitizers in the aerobic photooxidation of
sulfides and found that: (i) the acid modified porphyrin
photosensitizers showed the Soret and Q(0,0) bands in the
range of 435-456 and 634-697 nm, respectively. In other
words, the absorption bands of the novel photosensitizers
shifted towards the therapeutic window; (ii) little or no
catalyst degradation was observed for the immobilized
porphyrins after a reaction time of 3 h; (iii) the electron
deficient porphyrins showed much faster second order kinetics
4
-Me, the order of photocatalytic activity of the other
porphyrins correlates with the
photosensitizers.
φ
Δ
values of the
-
1
(
pseudo-first order rate constants, kobs = 0.0049-0.012 min )
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than the electron-rich ones (kobs = 2.30 × 10-5 -9.92 × 10-4 min-
Journal Name
17 S. Aronoff, J. Phys. Chem., 1958, 62, 428–431.
View Article Online
1
18 S. Zakavi, G.R. Karimipour and N. Gholami-gharab, Catal.
)
; (iv) the order of photocatalytic activity of the immobilized
porphyrins approximately correlated with the singlet oxygen
quantum yield (φ ) of the photosensitizers. The decreased
DOI: 10.1039/C8CY02433B
Commun. 2009, 10, 388-390.
1
9 D. S. Su, J. Zhang, B. Frank, A. Thomas, X. Wang, J.
Δ
Paraknowitsch and R. Schlögl, ChemSusChem, 2010,
69-180.
0 A. G. Mojarrad and S. Zakavi, Catal. Sci. Technol., 2018, 8,
68-781.
1 M. Klaper, W. Fudickarand T. Linker, J. Am. Chem. Soc.,
016, 138, 7024-7029.
3
dihedral angle between the meso substituents and porphyrin
mean plane in porphyrin dications compared to that in the
corresponding free base porphyrins leads to more efficient
resonance interactions between the two π systems. This, in
turn, probably leads to large difference between the
photosensitizing properties of porphyrins with various aryl
groups at the porphyrin periphery; (v) control reactions
performed in the presence of DPBF and 1,4-benzoquinone
revealed the involvement of singlet oxygen as the sole ROS;
1
2
2
7
2
22 S. Y. Tang, R. A. Bourne, R. L. Smith and M. Poliakoff,
Green Chem., 2008, 10, 268-269.
23 C. Xing, J. Deng, R. Tan, M. Gao, P. Hao, D. Yin and D. Yin,
Catal. Sci. Technol., 2017, 7, 5944-5952.
2
4 a) S. Zakavi, M. N. Ragheb and M. Rafiee, Inorg. Chem.
Commun., 2012, 22, 48-53; (b) S. Zakavi, M. N. Ragheb,
Inorg. Chem. Commun., 2013, 36, 113-116.
(vi) the oxidation of sulfides was scaled up to ca. 3.3 to 6.6
mmol of sulfoxide per batch, using 1:5000 and 1:10000 molar
ratios of catalyst to sulfide; (vii) the catalyst was reused five
times without significant loss of catalytic activity.
2
5 S. Zakavi and N. Gholami-gharab, Polyhedron, 2007, 26
425-2432.
6 N. E. Leadbeater and M. Marco, Chem. Soc. Rev., 2002,
02, 3217-3274.
27 A. Heydari-turkmani and S. Zakavi, J. Catal., 2018, 364,
94-405.
,
2
2
1
Acknowledgements
3
Financial support of this work by the Institute for Advanced
Studies in Basic Sciences (IASBS) is acknowledged. Also, the
authors thank to Dr. Ehsan Ahadi Akhlaghi and Mr. Pooria
Omidi from the Optics Laboratory at the Department of
Physics for recording the emission spectra of the LED lamps.
2
8 Y. Zhi, K. Li, H. Xia, M. Xue, Y. Mu and X. Liu, J. Mater.
Chem. A, 2017, 5, 8697-8704.
29 A. G. Griesbeck, T. T. El‐Idreesy and A. Bartoschek, Adv.
Synth. Catal., 2004, 346, 245-251.
3
0 R. Nasrollahi and S. Zakavi, Eur. J. Inorg. Chem., 2017,
2
017, 2002-2010.
3
3
3
1 W. Nam, Acc. Chem. Res., 2007, 40, 522-531.
2 D. P. Goldberg, Acc. Chem. Res., 2007, 40, 626-634.
3 J. Rosenthal, B. J. Pistorio, L. L. Chng, and D. G. Nocera, J.
Org. Chem. 2005, 70, 5, 1885-1888.
References
3
4 N. Xie, R. A. Binstead, E. Block, W. D. Chandler, D. G. Lee,
T. J. Meyer and M. Thiruvazhi, J. Org. Chem., 2000, 65,
1
Z. Amara, J. F. Bellamy, R. Horvath, S. J. Miller, A. Beeby,
A. Burgard, K. Rossen, M. Poliakoff and M. W. George,
1
008-1015.
3
3
3
3
5 N. S. Venkataramanan, S. Premsingh, S. Rajagopal and K.
Pitchumani, J. Org. Chem., 2003, 68 ,7460-7470.
6 J. H. Acquaye, J. G. Muller and K. J. Takeuchi, Inorg.
Chem., 1993, 32, 160-165.
Nat. Chem., 2015,
Y. Zhang, Z. Wang and X. Lang, Catal. Sci. Technol., 2017,
, 4955-4963.
J.-L. Shi, H. Hao, X. Li and X. Lang, Catal. Sci. Technol.,
018, , 3910-3917.
Y. Xu, Z.-C. Fu, S. Cao, Y. Chen and W.-F. Fu, Catal. Sci.
Technol., 2017, , 587-595.
7, 489-495.
2
3
4
5
7
7 S. M. Bonesi, M. Fagnoni and A. Albini, J. Org. Chem.,
2
8
2
004, 69, 928-935.
8 A. L. Zanocco, G. Günther S., E. Lemp M., J. R. de la
7
Fuente and N. Pizarro U., Photochem. Photobiol., 1998
F. Bigi, A. Corradini, Ca. Quarantelli and G. Sartori, J.
Catal. 2007, 250, 222-230.
6
8, 487-493.
3
4
4
9 M. Luiz, A. T. Soltermann, A. Biasutti and N. A. Garcia,
Can. J. Chem., 1996, 74, 49-54.
0 R. Nasrollahi and S. Zakavi, New J. Chem., 2018, 42, 1806-
6
7
M. C. Carreño, Chem. Rev., 1995, 95, 1717-1760.
T. Neveselý, E. Svobodová, J. Chudoba, M. Sikorski and R.
Cibulka, Adv. Synth. Catal., 2016, 358, 1654-1663.
J. M. Zen, S. L. Liou, A. S. Kumar and M. S. Hsia, Angew.
Chem., Int. Ed., 2003, 42, 597 599.
Y. Xu, Z.-C. Fu, S. Cao, Y. Chen and W.-F. Fu, Catal. Sci.
Technol., 2017, 7, 587-595.
1
815.
8
9
1
1
1
1
1
1
1 M. B. Spesia, D. Lazzeri, L. Pascual, M. Rovera and E. N.
Durantini, FEMS Immunol. Med. Microbiol., 2005, 44,
2
89-295.
4
2 E. Silva, M. M. Pereira, H. D. Burrows, M. Azenha, M.
0 Y. Li, M. Wang and X. Jiang, Catal. Sci. Technol., 2018,
Accepted manuscript; DOI: 10.1039/C8CY01139G.
1 A. Heydari-turkmani, S. Zakavi and N. Nikfarjam, New J.
Chem., 2017, 41, 5012-5020.
Sarakha and M. Bolte, Photochem. Photobiol. Sci.,2004,
3, 200-204.
4
4
3 M. L. Kacher and C. S. Foote, J. Photochem. Photobiol.,
979, 29, 765-769.
4 B. M. Monroe, J. Photochem. Photobiol., 1979, 29, 761-
1
2 S. Zakavi, S. Hoseini and A. G. Mojarrad, New J. Chem.,
2
017, 41, 11053-11059.
7
64.
3 A. G. Mojarrad and S. Zakavi, RSC Adv., 2016, 6, 100931-
00938.
4
4
5 E. L. Clennan, Acc. Chem. Res., 2001, 34, 875-884.
6 S. Zakavi and S. Hoseini, RSC Adv., 2015, 5, 106774-
1
4 S. M. Ribeiro, A. C. Serra and A. d. A. R. Gonsalves, J.
Catal., 2008, 256 331-337.
1
06786.
4
7 A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, J.
5 L.-J. Chen, S. Chen, Y. Qin, L. Xu, G.-Q. Yin, J.-L. Zhu, F.-F.
Zhu, W. Zheng, X. Li and H.-B. Yang, J. Am. Chem. Soc.,
Assour and L. A. Korsakoff, J. Org. Chem., 1967, 32, 476-
4
76.
2
018, 140, 5049-5052.
6 G. Mele, R. Del Sole, G. Vasapollo, E. Garcıa
Palmisano and M. Schiavello, J. Catal., 2003, 217, 334-
42.
4
8 F. Wilkinson, W. P. Helman and A. B. Ross, J. Phys. Chem.
Ref. Data, 1993, 22, 113-262.
1
́
-López, L.
3
1
4 | J. Name., 2012, 00, 1-3
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Catalysis Science & Technology
Journal Name
ARTICLE
4
5
5
9 S.-Y. Takizawa, R. Aboshi and S. Murata, Photochem.
View Article Online
DOI: 10.1039/C8CY02433B
Photobiol. Sci., 2011, 10, 895-903.
0 M. Meot-Ner and A. D. Adler, J. Am. Chem. Soc., 1975,
9
7, 5107-5111.
1 R. E. Haddad, S. Gazeau, J. Pécaut, J.-C. Marchon, C. J.
Medforth and J. A. Shelnutt, J. Am. Chem. Soc., 2003,
1
25, 1253-1268.
5
5
5
5
5
2 C. J. Medforth, M. O. Senge, K. M. Smith, L. D. Sparks and
J. A. Shelnutt, J. Am. Chem. Soc., 1992, 114, 9859-9869.
3 A. Rosa, G. Ricciardi and E. J. Baerends, J. Phys. Chem. A.,
2
006, 110, 5180-5190.
4 Z. Wang, H. Liu, H. Cui, M. Zhang and Z. Zhang, Ind. Eng.
Chem. Res., 2015, 54, 7219-7225.
5 J. Suchánek, P. Henke, J. I. Mosinger, Z. K. Zelinger and P.
Kubát, J. Phys. Chem. B, 2014, 118, 6167-6174.
6 M. Bregnhøj, M. V. Krægpøth, R. J. Sørensen, M.
Westberg and P. R. Ogilby, J. Phys. Chem. A, 2016, 120,
8
285-8296.
5
5
7 W. Yang, J. Zhao, C. Sonn, D. Escudero, A. Karatay, H. G.
Yaglioglu, B. l. Kꢀꢁꢀkꢂz, M. Hayvali, C. Li and D.
Jacquemin, J. Phys. Chem. C, 2016, 120, 10162-10175.
8 A. Casado-Sánchez, R. Gómez-Ballesteros, F. Tato, F. J.
Soriano, G. Pascual-Coca, S. Cabrera and J. Alemán,
Chem. Com., 2016, 52, 9137-9140.
5
6
6
6
9 E. A. Mayeda and A. J. Bard, J. Am. Chem. Soc., 1973, 95,
6
223-6226.
0 J. Park, D. Feng, S. Yuan and H. C. Zhou, Angew. Chem.,
Int. Ed., 2015, 127, 440-445.
1 Z. Li, C. Liu, H. Abroshan, D. R. Kauffman and G. Li, ACS
Catal., 2017, 7, 3368-3374.
2 P. Majumdar, X. Yuan, S. Li, , B. Le Guennic J. Ma, C.
Zhang, D. Jacquemin and J. Zhao, J. Mater. Chem. B,
2
014, 2, 2838-2854.
6
3 K. K. Chin, C. C. Trevithick-Sutton, J. McCallum, S.
Jockusch, N. J. Turro, J. Scaiano, C. S. Foote and M. A.
Garcia-Garibay, J. Am. Chem. Soc., 2008, 130, 6912-
6
913.
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Catalysis Science & Technology
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DOI: 10.1039/C8CY02433B
Kinetic and mechanistic aspects of solid state, nanostructured porphyrin diacid photosensitizers in
photooxidation of sulfides
Rahele Nasrollahi, Akram Heydari-turkmani, Saeed Zakavi*
Kinetics and mechanism of aerobic photooxidation of sulfides in the presence of a series of electron-rich
and electron-deficient porphyrins immobilized on Amberlyst 15 nanoparticles in the form of porphyrin
diacids are reported.