Visible light-driven Suzuki-Miyaura reaction by self-supported Pd nanocatalysts in the formation of Stille coupling-based photoactive microporous organic polymers

Article abstract of DOI:10.1039/d0cy00997k

Stille coupling was applied to synthesize microporous organic polymers (MOPs). Metallic Pd was in situ self-supported during the networking of 1,3,6,8-tetrabromopyrene with 1,4-bis(tributylstannyl)benzene to form Stille coupling-based MOP (St-MOP)?Pd. The size of St-MOP particles and the amount of metallic Pd in St-MOP?Pd depended on the amount of Pd catalyst. As the amount of Pd catalyst increased, the size of St-MOP particles decreased with an increase of metallic Pd, due to the increased St-MOP nuclei in the early growth stage of St-MOP. The St-MOP bearing pyrenes showed absorption and emission of visible light and St-MOP?Pd showed excellent catalytic performance in the visible light-driven Suzuki-Miyaura coupling. The optimal St-MOP?Pd-2 (0.14 mol% Pd) showed a TON of 657 and a TOF of 219 h-1 in the visible light-driven Suzuki-Miyaura coupling of 1-acetyl-4-bromobenzene and phenylboronic acid at 25 °C. The optimal amount of St-MOP and metallic Pd in St-MOP?Pd was critical to achieve excellent catalytic performance. The overall photocatalytic principles of St-MOP?Pd were rationalized by computational simulation. This journal is

Full text of DOI:10.1039/d0cy00997k

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2020, DOI: 10.1039/D0CY00997K.
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Chaoqiu Chen, Yong Qin et al.
Highly dispersed Pt nanoparticles supported on carbon
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Page 1 of 9
CP al et aa lsy es i ds oS c ni eo nt c ae d &j uTs et c mh na or lgo i ng sy
View Article Online
DOI: 10.1039/D0CY00997K
Journal Name
ARTICLE
Visible Light-Driven Suzuki-Miyaura Reactions by Self-Supported
Pd Nanocatalysts in the Formation of Stille Coupling-Based
Photoactive Microporous Organic Polymers
Received 00th January 20xx,
Accepted 00th January 20xx
a,ǂ
a,ǂ
b
c
d
d
DOI: 10.1039/x0xx00000x
Sang Hyun Ryu, Sung Jae Choi, Ji Hui Seon, Bonghyun Jo, Sang Moon Lee, Hae Jin Kim,
e
b
c
a
Yoon-Joo Ko, Kyoung Chul Ko,* Tae Kyu Ahn,* and Seung Uk Son*
www.rsc.org/
Stille coupling was applied to synthesize microporous organic polymers (MOPs). Metallic Pd was in situ self-
supported during the networking of 1,3,6,8-tetrabromopyrene with 1,4-bis(tributylstannyl)benzene to form
Stille coupling-based MOP(St-MOP)@Pd. The size of St-MOP particles and the amount of metallic Pd in the
St-MOP@Pd depended on the amount of a Pd catalyst. As the amount of a Pd catalyst increased, the size of
St-MOP particles decreased with an increase of metallic Pd, due to the increased St-MOP nuclei in the early
growth stage of St-MOP. The St-MOP bearing pyrenes showed absorption and emission of visible light and
the St-MOP@Pd showed excellent catalytic performance in the visible light-driven Suzuki-Miyaura coupling.
-1
The optimal St-MOP@Pd-2 (0.14 mol% Pd) showed a TON of 657 and a TOF of 219 h in the visible light-
o
driven Suzuki-Miyaura coupling of 1-acetyl-4-bromobenzene and phenyl boronic acid at 25 C. The optimal
amount of St-MOP and metallic Pd in the St-MOP@Pd was critical to achieve excellent catalytic performance.
The overall photocatalytic principles of St-MOP@Pd were rationalized by computational simulation.
It has been well documented that conventional Pd-catalyzed
coupling reactions follow Pd 0/+2 cycles. During the catalytic
Introduction
6
Recently, various microporous organic polymers (MOPs) have
been prepared by Pd-catalyzed couplings of organic building
cycles, molecular Pd species can be gradually decomposed to
7
metallic Pd, the so called Pd black. Usually, the formation of
1
blocks. Since conjugated microporous polymers (CMPs) were
metallic Pd is regarded as an unwanted reaction pathway for
Pd-catalyzed couplings because the uncontrolled Pd black has
2
prepared by Cooper research group, based on Sonogashira
coupling of multihaloarenes with multiethynylarenes, there
have been extensive studies on the synthesis and application of
7
poor catalytic activity. However, one can speculate that the
gradual deposition of metallic Pd can be utilized for in situ
loading of Pd nanoparticles (NPs) on solid supports.
1
functional CMP. In addition to Sonogashira coupling, other
Pd-catalyzed coupling reactions have also been applied to
prepare MOP. For example, Suzuki-Miyaura coupling and
Heck reaction have been applied to synthesize MOP.3,4 It is
noteworthy that Stille coupling is a powerful synthetic method
The microporosity and the high surface areas of MOP are
beneficial features in its use as a solid support for the Pd
loading. In this regard, MOP@Pd materials have been prepared
8
and applied to heterogeneous Pd catalysis. However, in the
5
that doesn’t require additional bases. However, as far as we are
conventional synthesis of MOP@Pd materials, metallic Pd was
additionally deposited on pre-synthesized MOP using Pd
precursors.8 Regarding pot economy,9 one pot synthesis of
MOP@Pd will be more attractive. One can expect that the
metallic Pd can be in situ deposited in the synthetic process of
MOP to form MOP@Pd materials in a one pot manner.
Moreover, the amount of metallic Pd in the MOP materials can
be systematically controlled via quantitative control of Pd
catalysts. In addition, the size of MOP materials can be
controlled by kinetic growth control using Pd catalysts. For
example, as the amount of Pd catalysts increases, the number of
MOP nuclei may increase in the early growth stage of MOP,
resulting in a size decrease of the MOP materials.10 Our
aware, surprisingly, Stille coupling reaction has not been
explored in the synthesis of MOP.
a.Department of Chemistry, Sungkyunkwan University, Suwon 16419,
Korea E-mail: sson@skku.edu
b.
Department of Chemistry Education, Chonnam National University,
Gwangju 61186, Korea E-mail: kcko1982@jnu.ac.kr
Department of Energy Science, Sungkyunkwan University, Suwon
c.
1
6419, Korea E-mail: taeahn@skku.edu
d.
e.
Korea Basic Science Institute, Daejeon 34133, Korea
Laboratory of Nuclear Magnetic Resonance, NCIRF, Seoul National
University, Seoul 08826, Korea
†
Electronic Supplementary Information (ESI) available: Additional
characterization
data
of
St-MOP@Pd
materials.
See research group has reported that the size and morphology
DOI: 10.1039/x0xx00000x
These authors contributed equally.
engineering of MOP materials is important in their
application.11
ǂ
This journal is © The Royal Society of Chemistry 20xx
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CP al et aa lsy es i ds oS c ni eo nt c ae d &j uTs et c mh na or lgo i ng sy
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ARTICLE
Journal Name
Recently, visible light has been recognized as a sustainable Experimental procedures for catalytic reaction View Article Online
energy source not only in the generation of electricity12 but also
Aryl bromide (0.500 mmol), aryl boronic acid (0.625 mmol),
DOI: 10.1039/D0CY00997K
in organic synthesis.13 Visible light-induced cross-coupling by St-MOP@Pd-2 (9.0 mg, 0.831wt% Pd, 0.14 mol% Pd), K
CO
3
2
the combination of Pd catalysts with visible light-harvesting (0.104 g. 0.750 mmol), and methanol (3 mL) were added to a
1
4
materials has been an important research subject. For test tube under argon. The reaction temperature was kept at
example, surface plasmonic nanomaterial@Pd systems15 and g- 25 C using a circulated water bath. After white LED (light
o
@Pd16 have been utilized as catalytic systems for the intensity of 0.9 mW/cm measured on the surface of a glass
2
C
3
N
4
visible light-driven Suzuki-Miyaura coupling reactions. In ware) was irradiated, the reaction progress was monitored by
addition, visible light-absorbing MOP@Pd can be applied as 1H NMR studies. As a control system of dark conditions, the
catalysts to the visible light-driven cross coupling reactions.17 test tube was wrapped with an aluminum foil and a black
In this work, we report one pot synthesis of visible light active insulating tape. For the catalytic reactions of other St-MOP@Pd
MOP@Pd materials based on Stille coupling (St-MOP@Pd) catalysts, St-MOP@Pd-1 (35.9 mg, 0.203wt% Pd, 0.14 mol%
and their excellent photocatalytic performance in the visible Pd) and St-MOP@Pd-3 (5.7 mg, 1.34wt% Pd, 0.14 mol% Pd)
light-driven Suzuki-Miyaura coupling reactions.
were used.
For the recyclability tests, after reaction, the St-MOP@Pd-2
was recovered by centrifugation, washed with a mixture of
distilled water (15 mL) and methanol (15 mL) three time and a
mixture of methanol (10 mL), acetone (10 mL), and methylene
chloride (10 m) three times, dried under vacuum, and used for
the next run.
Experimental
General Information
Scanning electron microscopy was conducted using a FE-SEM
(
JSM6700F). Transmission electron microscopy was conducted
using a JEOL 2100F. N sorption isotherm curves were
obtained at 77K using a Micromeritics ASAP2020. Pore size Laser photophysics
2
distribution diagrams were analyzed by the density functional
Time-resolved photoluminescence curves were obtained using
theory method. Infrared spectra were obtained using a Bruker a commercial TCSPC system (FluoTime 200, PicoQuant). A
VERTEX 70 FT-IR spectrometer. Solid state 13C nuclear picosecond diode laser of 485 nm (LDH-P-C-485, PicoQuant)
magnetic resonance (NMR) spectra were obtained at CP/TOSS was used to excite St-MOP@Pd materials in methanol (a
o
mode using a 500 MHz Bruker ADVANCE II NMR repetition rate of 4 MHz, an incident angle of 30 ). The
spectrometer. A 4 mm magic angle spinning probe and a photoluminescence signals at 520 nm were accumulated by a
1
spinning rate of 5 kHz were applied. Solution state H NMR fast photomultiplier tube (PMT) detector (PMA 182, PicoQuant)
o
spectra were obtained using a 400 MHz and 500 MHz Varian with an optimized angle (54.7 ). The channels per a curve were
spectrometers. Power X-ray diffraction patterns were obtained set to 6250. The instrumental response function (IRF) was 160
using a Rigaku MAX-2200 (filtered Cu-Kα radiation). X-ray ps in a full width at half maximum. We used convoluting decay
photoelectron spectra were obtained using a Thermo VG curves to calculate decay lifetime using exponential functions;
equipment. Diffuse reflectance spectra were obtained using a
Shimadzu UV-3600. UV/vis absorption spectra of St-MOP@Pd
materials were obtained through the conversion of the The fitted values of the goodness-of-fit parameter (χ ) were all
τ
A
avg(amplitude weighted average lifetime) = A
1 1
exp(−t/τ ) +
2
exp(−t/τ ), A and A : amplitude, τ and τ : life time, t: time.
2
1
2
1
2
2
corresponding diffuse reflectance spectra. Emission spectra close to 1.0.
were obtained using a JASCO FP-6200. Inductively coupled
Computational Simulation
plasma-atomic emission spectroscopy was conducted using an
The density functional theory (DFT) calculations were carried
OPTIMA 8300. Thermogravimetric analysis was conducted
out using FHI-aims code.18 We designed four model systems of
2
under N using a Seiko Exstar 7300 analyzer.
St-MOP-I, II, III, and ꝏ (Refer to Fig. 6a) to simulate the
valence band (VB) and conduction band (CB) energy levels.
Synthesis of St-MOP@Pd materials
For the preparation of St-MOP@Pd-1, (PPh
3
)
4
Pd (2.3 mg, 2.0 For St-MOP-I, II, and III, the B3LYP/light-tier-1 level of
µmol) and distilled DMF (60 mL) were added to a 150 mL theory was employed for the DFT calculation. For ꝏ, the
flame-dried Schlenk flask under argon. The reaction mixture PBE/light-tier-1 level of theory was used for the optimization
was sonicated for 30 min. After 1,3,6,8-tetrabromopyrene (62 of atomic position as well as unit cell parameters. A k-point
mg, 0.12 mmol) and 1,4-bis(tributylstannyl)benzene (0.14 mL, grid was chosen as 7 × 7 × 7. The unit cell parameters of St-
0
1
.24 mmol) were added, the reaction mixture was stirred at MOP-ꝏ were optimized as a = 14.56 Å , b = 17.95 Å , and c =
10 C for 24 h. After being cooled to room temperature, the 45.51 Å. The slab was separated by a vacuum spacing of 40ꢀÅ
o
resultant powder was separated by centrifugation, washed with along with c axis to avoid the interaction between slabs within
methanol (40 mL) three times, methylene chloride (40 mL) periodic boundary condition. After the geometrical
three times, and dried under vacuum. For the preparation of St- optimization of St-MOP-ꝏ with a PBE function, single point
MOP@Pd-2, the same synthetic procedures of St-MOP@Pd-1 calculation with B3LYP/light-tier-1 was performed to obtain
were applied except using (PPh ) Pd (4.6 mg, 4.0 µmol). For the VB and CB energy levels. Considering computational costs,
3 4
the preparation of St-MOP@Pd-3, the same synthetic the convergence criteria for structure optimizations were set to
procedures of St-MOP@Pd-1 were applied except using 0.01 eV/Å for St-MOP-I and St-MOP-II, and as 0.02 eV/Å for
(
PPh
3
)
4
Pd (9.2 mg, 8.0 µmol).
St-MOP-III and St-MOP-ꝏ, respectively.
2
| J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
Result and Discussion
Fig. 1 shows a synthetic scheme for the St-MOP@Pd. Using
View Article Online
DO(Ic: )10.1039/D0CY00997K
(
(
a)
d)
(b)
(e)
1
eq.
1,3,6,8-tetrabromopyrene
and
2
eq.
1,4-
bis(tributylstannyl)benzene as building blocks, Stille coupling
o
was conducted at 110 C in DMF for 24 h in the presence of
tetrakis(triphenylphosphine)palladium(0). We systematically
increased the amount of Pd catalysts from 1.7 mol% to 3.3 and
5
00 nm
500 nm
200 nm
20 nm
500 nm
6
.6 mol% of 1,3,6,8-tetrabromopyrene and the resultant
(f)
materials were denoted as St-MOP@Pd-1, St-MOP@Pd-2, and
St-MOP@Pd-3, respectively. When we used 1.7 mol% Pd
catalyst of 1,3,6,8-tetrabromopyrene, greenish yellow powder
was obtained. As the amount of Pd catalysts increased to 3.3
and 6.6 mol% of 1,3,6,8-tetrabromopyrene, the color of
powders became darker and darker.
200 nm
200 nm
(
g)
(h)
(
i)
2
0 nm
20 nm
Fig. 2 SEM images of (a) St-MOP@Pd-1, (b) St-MOP@Pd-2, and (c)
St-MOP@Pd-3. TEM images of (d, g) St-MOP@Pd-1, (e, h) St-
MOP@Pd-2, and (f, i) St-MOP@Pd-3. Also, refer to Fig. S1 in the ESI.
The surface areas of St-MOP@Pd materials were
characterized by the analysis of N
isotherm curves, based on the Brunauer-Emmett-Teller theory.
Fig. 3a-b) The St-MOP@Pd-1 showed a surface area of 32
2
adsorption-desorption
(
2
m /g and poor porosity, which is attributable to the incomplete
networking. (Also, refer to the analysis of 13C NMR spectrum
of St-MOP@Pd-1 in Fig. 3e) In comparison, the surface area of
2
St-MOP@Pd-2 increased to 341 m /g with enhanced
microporosity. Because of the increased amount of Pd NPs, the
2
surface area of St-MOP@Pd-3 decreased to 285 m /g,
compared to that of St-MOP@Pd-2. (Fig. 3a-b)
The chemical structures of St-MOP@Pd materials were
characterized by X-ray photoelectron spectroscopy (XPS),
infrared (IR) absorption, and solid state 13C nuclear magnetic
resonance (NMR) spectroscopy. (Fig. 3c-e) The XPS spectra of
all St-MOP@Pd materials showed Pd 3d orbital peaks at 335.4
and 340.8 eV, corresponding to zerovalent Pd species.19 (Fig.
Fig. 1 One pot synthesis of St-MOP@Pd based on Stille coupling.
Scanning electron microscopy (SEM) showed that all St-
MOP@Pd materials have spherical shapes. (Fig. 2a-c) Their
average diameters decreased from 556 nm (St-MOP@Pd-1) to
3
3
c) Additional Pd 3d orbital peaks were observed at 337.0 and
42.4 eV in the XPS spectrum of St-MOP@Pd-3, indicating the
formation of PdO species on the surface of Pd NPs through
partial surface oxidation.19 (Fig. 3c) The IR absorption spectra
of St-MOP@Pd materials showed the vibration peaks of
1
92 nm (St-MOP@Pd-2) and 117 nm (St-MOP@Pd-3).
Transmission electron microscopy (TEM) showed that the St-
MOP particles were decorated with metallic Pd NPs with sizes
of 1 ~ 3 nm. (Fig. 2d-i) Whilst Pd NPs were hardly detected in
the St-MOP@Pd-1, a significant amount of Pd NPs was
observed on the St-MOP of the St-MOP@Pd-2. (Fig. 2g-h) In
the case of St-MOP@Pd-3, the St-MOP particles were coated
with excess Pd NPs. (Fig. 2i and S1 in the ESI) The amounts of
Pd were analyzed to be 0.203, 0.831, and 1.34wt% in the St-
MOP@Pd-1, St-MOP@Pd-2, and St-MOP@Pd-3, respectively,
by the inductively coupled plasma-atomic emission
spectroscopy (ICP-AES).
-
1
aromatic C-H and oop C-H at 3035 and 833 cm , respectively.
(
1
Fig. 3d) The aromatic C=C stretching peaks were observed at
-
1
593, 1481, and 1460 cm . In addition, aliphatic C-H
-
1
stretching peaks were observed at 2952, 2922, and 2859 cm ,
corresponding to tributylstannyl groups in the materials. The IR
intensities of the tributylstannyl groups gradually decreased
from St-MOP@Pd-1 to St-MOP@Pd-2 and St-MOP@Pd-3,
indicating the enhanced progress of networking due to the
increased Pd catalysts. (Fig. 3d)
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ARTICLE
The solid state 13C NMR spectra of all St-MOP@Pd materials
Journal Name
The optical properties of St-MOP@Pd were invesVtieigwaAtretidcle. O(Fnliinge.
showed the aromatic 13C peaks at 139, 136, and 127 ppm. (Fig. 4) As shown in Fig. 4a, St-MOP@Pd-D1OaI:n1d0.1S03t-9M/DO0CPY@00P9d97-K2
e) In addition, the aliphatic 13C peaks of tributylstannyl groups showed three ultraviolet absorption bands at 247, 290, and 360
were observed at 26 and 12 ppm. The intensity of the aliphatic nm. In the visible light region, the St-MOP@Pd-1 and St-
13C peaks gradually decreased from St-MOP@Pd-1 to St-
MOP@Pd-2 showed absorption bands at 450 and 454 nm,
MOP@Pd-2 and St-MOP@Pd-3, matching well with the results respectively. In the case of St-MOP@Pd-3, the intensities of
3
of IR spectroscopy. (Fig. 3e)
absorption at 247, 290, and 360 nm were significantly reduced,
due to the reduced amount of St-MOP in the materials, and the
absorption at ~450 nm was not clearly observed. Instead,
absorption was observed over the whole visible light region,
due to the black Pd NPs in the St-MOP@Pd-3.
(
a)
(b)
When the St-MOP@Pd-1 was excited with an excitation
wavelength of 450 nm, it showed strong emission at 522 nm.
(
Fig. 4b) In comparison, the emission was significantly reduced
in the excitation of St-MOP@Pd-2 and St-MOP@Pd-3,
indicating the photo-induced electron transfer from St-MOP to
Pd NPs. When the Pd NPs in St-MOP@Pd-2 was etched by the
treament with HCl solution, the resulatnt St-MOP showed
strong emission at 533 nm. The emission quantum yield of St-
MOP of St-MOP@Pd-2 was measured to be 53.1% using
(
f)
(g)
(
c)
(d)
3 6 2
Ru(bpy) ](PF )
as a standard compound.20 The emission
[
decay kinetics of the St-MOP@Pd materials were investigated
by laser photophysics. (Fig. 4c) As the amount of Pd increased
from St-MOP@Pd-1 to St-MOP@Pd-2 and St-MOP@Pd-3, the
average lifetimes of emission gradually decreased from 0.94 ns
to 0.37 and 0.34 ns, respectively, indicating the photo-induced
electron transfer from the excited St-MOP to Pd NPs. As shown
in Fig. 4d, whilst the St-MOP@Pd-1 in methanol showed bright
emission, the emission of St-MOP@Pd-2 and the St-MOP@Pd-
3
was gradually quenched by the Pd NPs in the materials.
(
a) St-MOP@Pd-1
(b)
St-MOP@Pd-1
(
e)
St-MOP
Pd-2
St-MOP
Pd-2
@
@
St-MOP@Pd-3
St-MOP
Pd-3
@
(
b)
c)
(
d)
(
St-MOP St-MOP St-MOP
Pd-1 @Pd-2 @Pd-3
@
St-MOP
@Pd-1
Fig. 3 (a) N
b) pore size distribution diagrams based on the DFT method, (c)
XPS spectra of Pd 3d orbitals, (d) IR absorption spectra, and (e) solid
state C NMR spectra of St-MOP@Pd-1, St-MOP@Pd-2, and St-
MOP@Pd-3.
2
adsorption-desorption isotherm curves obtained at 77K,
(
St-MOP
@Pd-2
13
St-MOP
Pd-3
@
Powder X-ray diffraction (PXRD) studies showed that the St-
MOP@Pd-1 is amorphous, matching with the conventional
features of MOP materials prepared by the Pd-catalyzed cross-
coupling reactions in the literature.1-2 (Fig. S2 in the ESI) In the
IRF
Fig. 4 (a) Absorption spectra (inset: photographs) of St-MOP@Pd-1,
PXRD patterns of the St-MOP@Pd-2 and St-MOP@Pd-3, St-MOP@Pd-2, and St-MOP@Pd-3 powder. (b) Emission spectra (λex
:
o
450 nm), (c) emission decay curves, and (d) photographs of St-
MOP@Pd-1, St-MOP@Pd-2, and St-MOP@Pd-3 in methanol.
broad XRD peaks appeared at 2θ of 40.0 , corresponding to the
(
111) crystal plane of metallic Pd. (Fig. S2 in the ESI)
4
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Journal Name
ARTICLE
Considering the possible visible light-induced electron respectively, after 5 h under dark conditionsV.iewTAhrtiecle Opnolioner
transfer from St-MOP to Pd NPs, we studied the photocatalytic conversions are attributable to the inefDfOicIi:e1n0t.10p3h9/oDto0C-iYn0d0u9c9e7dK
performance of St-MOP@Pds in the visible light-driven electron transfer from the St-MOP to bromobenzene and 1-
Suzuki-Miyaura coupling. We maintained reaction temperature bromo-4-methoxybenzene.
o
to 25 C using a circulated water bath. Also, as a control system
(
a)
for dark conditions, reactors were wrapped with an aluminum
foil and an insulating tape. Fig. 5 summarizes the results. When
we used 1-acetyl-4-bromobenzene and phenyl boronic acid as
substrates of Suzuki-Miyaura coupling, the SMOP@Pd-2
showed sharp difference in the yields of products with/without
white LED irradiation. (Fig. 5a) After 3 h, whilst the St-
MOP@Pd-2 (0.14 mol%) showed a 92% yield of a coupled
product under white LED irradiation, a 40% yield was obtained
under dark conditions. When the Pd NPs of St-MOP@Pd-2
were etched through acid treatment, the system lost the original
photocatalytic activities under white LED irradiation. (Fig. S3
in the ESI) When the St-MOP@Pd-2 was removed from a
reaction mixture through filtration, the photocatalytic reaction
was nearly terminated. (Fig. S4 in the ESI)
In comparison, the St-MOP@Pd-3 (0.14 mol% Pd) showed
moderate conversions both under white LED irradiation (42%
after 5 h) and under dark conditions (31% after 5 h), due to the
blocking of visible light absorption by the excess Pd NPs on the
surface of St-MOP. (Fig. 5a) The St-MOP@Pd-1 (0.14 mol%
Pd) also showed poor conversions both under white LED
irradiation (13% after 5 h) and under dark conditions (10% after
(
b)
5
h), due to the diluted and entrapped Pd NPs in the materials
and poor porosity. (Fig. 5a) These results indicate that the
optimal amount between light absorbing materials (St-MOP)
and Pd NPs is critical to be an efficient photocatalytic system
for visible light-driven Suzuki-Miyaura coupling.
Next, we studied the substrate effect of arylbromides and
arylboronic acids. (Fig. 5b-c) To be successful visible light-
driven Suzuki-Miyaura coupling, the energy level of the
conduction band (CB) of visible light-harvesting St-MOP
should be higher than that of the LUMO of arylbromide
substrates.14-17 In addition, the energy level of the valence band
(c)
(
VB) of St-MOP should be lower than that of the HOMO of
arylboronic acid or arylborate substrates. Thus, the electron
deficient arylbromides and electron rich arylboronic acids can
be good substrates for the visible light-driven coupling. Thus,
we tested various aryl bromides with phenyl boronic acid for
the visible light-driven coupling.
Among aryl bromides, 1-acetyl-4-bromobenzene and 1-
bromo-4-formylbenzene showed successful conversions (92%
and 81% yields, respectively, after 3 h) in the visible light-
driven Suzuki-Miyaura coupling by St-MOP@Pd-2 (0.14 mol%
Pd), compared to the poor results (40% and 26% yields,
respectively, after 3 h) under dark conditions. Whilst the 1-
bromo-4-nitrobenzene showed fast conversion (100% after 0.5
h) under white LED irradiation, the reaction under dark
condition also became relatively slow (24% after 0.5 h). As the
electronic surrounding of aromatic rings of arylbromides
became more electron-rich, the yields of products gradually
Fig. 5 Visible light-driven Suzuki-Miyaura coupling reactions (solid
circle), compared to those under dark conditions (blank circle)
depending on (a) catalysts (St-MOP@Pd), (b) aryl bromides, and (c)
aryl boronic acids. Reaction condition: 0.14 mol% Pd, aryl bromide
(
2 3
0.500 mmol), aryl boronic acid (0.625 mmol), K CO (0.750 mmol),
o
2
decreased. Whilst the bromobenzene and 1-bromo-4- 25 C, MeOH, white LED irradiation (0.9 mW/cm ).
methoxybenzene showed 51% and 12% yields after 5 h under
white LED irradiation, they showed 25% and 0% yields,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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Journal Name
Next, we tested the effect of aryl boronic acids with 1-acetyl-
As denoted by I, II, III, and ꝏ in Fig. 6a, the mVoiedweAlrtsicylesOtenmlinse
4
-bromobenzene in the visible light-driven Suzuki-Miyaura of St-MOP were simulated through a syDsOteI:m10a.t1i0c39e/xDt0eCndY0in0g99o7Kf
coupling. (Fig. 5c) As the electronic surroundings of aryl conjugation lengths. According to the density functional theory
boronic acids became more electron-rich, the visible light- (DFT) calculation, the CB and VB energy levels of St-MOP
driven Suzuki-Miyaura coupling was enhanced. Whilst 4- were simulated at -2.05 ~ -2.70 and -5.41 ~ -5.60 eV,
methoxyphenylboronic acid showed a 100% yield by St- respectively. (Fig. 6a and Table S1 in the ESI) The LUMO
MOP@Pd-2 (0.14 mol% Pd) after 1 h under white LED energy levels of 1-bromo-4-methoxybenzene, bromobenzene,
irradiation, it showed a 42% yield after 1 h under dark 1-acetyl-4-bromobenzene, 1-bromo-4-formylbenzene, and 1-
conditions. Whilst phenylboronic acid showed 92% yield after bromo-4-nitrobenzene were simulated at -0.80, -0.83, -2.19, -
3
h under white LED irradiation, it showed a 40% yield after 3 2.44, and -3.13 eV, respectively, indicating that the 1-acetyl-4-
h under dark conditions. 4-Bromophenylbronic acids showed a bromobenzene, 1-bromo-4-formylbenzene, and 1-bromo-4-
moderate yield of 52% after 5 h under white LED irradiation (a nitrobenzene with the LUMO energy levels similar to or lower
3
2% yield after
5
h
under dark conditions). 4- than the CB energy level of St-MOP can act as electron
Nitrophenylbronic acid showed a poor yield of 9% after 5 h acceptors of the photo-excited St-MOP, matching well with the
under white LED irradiation (a 4% yield after 5 h under dark experimental results.
conditions).
The HOMO energy levels of 4-methoxyphenylboronic acid,
The substrate dependency of visible light-driven Suzuki- phenylboronic acid, 4-bromophenylboronic acid, and 4-
Miyaura coupling by St-MOP@Pd was rationalized by nitrophenylboronic acid were simulated at -6.22, -6.96, -6.82,
computational simulation. (Fig. 6a and S5-6 in the ESI)
and -7.78 eV, respectively. (Fig. 6a and Table S1 in the ESI) It
is noteworthy that that aryl boronic acids can be converted to
aryl borates in the presence of bases.21 The HOMO energy
(
a)
levels
methoxyphenylboronic
of
the
trihydroxyborate
forms
of
acid,
4-
4-
acid, phenylboronic
bromophenylboronic acid, and 4-nitrophenylboronic acid were
simulated at -2.08, -2.22, -2.49, and -2.91 eV, respectively.
Those
methoxyphenylboronic
of
dihydroxymethoxyborate
forms
of
acid,
4-
4-
acid, phenylboronic
bromophenylboronic acid, and 4-nitrophenylboronic acid were
simulated at -2.07, -2.15, -2.42, and -2.82 eV, respectively. In
addition, those of dihydroxycarbonatoborate forms of 4-
methoxyphenylboronic
acid,
phenylboronic
acid,
4-
bromophenylboronic acid, and 4-nitrophenylboronic acid were
simulated at 2.32, 2.35, 2.11, and 1.79 eV, respectively. The
HOMO energy levels of aryl borates are higher than the VB
energy levels of St-MOP, indicating that these species can act
as electron donors to the holes of the VB band of excited St-
MOP. As the chemical surrounding of arylborates became more
electron-rich, their HOMO energy levels are located higher,
resulting in the enhanced electron donor ability.
The photocatalytic mechanism of the visible light-driven
Suzuki-Miyaura coupling by St-MOP@Pd-2 was displayed as
Fig. 6b. The St-MOP absorbs the visible light and then, the
excited electron is transferred to arylbromide through Pd NP to
generate an aryl moiety on the Pd NP and a free bromide anion.
The arylborate donates electron to quench the hole of the VB of
the St-MOP. The aryls on the Pd NP are coupled to form the
Suzuki-Miyaura cross-coupled product. The substrate
selectivity originates from the proper energy level location
between the CB of St-MOP and the LUMO of arylbromides.
According to thermogravimetric analysis, the St-MOP@Pd-2
(
b)
o
was thermally stable up to 201 C. (Fig. 7a) The recyclability of
St-MOP@Pd-2 was investigated for visible light-driven
Suzuki-Miyaura coupling of 1-acetyl-4-bromobenzene and
phenylboronic acid. (Fig. 7b) In the first, second, third, fourth,
and fifth runs, the St-MOP@Pd-2 (0.14 mol% Pd) showed
excellent yields of 93, 93, 92, 90, and 90%, respectively. The
St-MOP@Pd-2 recovered after five successive recycle tests
Fig. 6 (a) Model systems for the simulation, simulated conduction
band (CB) and valence band (VB) energy levels of St-MOP, and
HOMO and LUMO energy levels of aryl bromides, aryl boronic acids,
and aryl borates. (b) A possible reaction mechanism of visible light-
driven Suzuki-Miyaura coupling by St-MOP@Pd.
6
| J. Name., 2012, 00, 1-3
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CP al et aa lsy es i ds oS c ni eo nt c ae d &j uTs et c mh na or lgo i ng sy
Journal Name
ARTICLE
were investigated by SEM, XPS, and IR spectroscopy, showing phenylboronic acid at room temperature for 48 h, correVsiepwoAnrdticilnegOntolinae
the complete retention of the original morphology and chemical TON of 170 and a TOF of 4 h-1.17d
DOI: 10.1039/D0CY00997K
structure. (Fig. 7c-d and S7 in the ESI)
In comparison, the St-MOP@Pd-2 (0.14 mol% Pd) in this work
showed a 92% yield in the visible light-driven Suzuki-Miyaura
coupling of 1-acetyl-4-bromobenzene with phenylboronic acid at
(a)
(b)
o
-1
2
5 C after 3 h, corresponding to a TON of 657 and a TOF of 219 h .
The highly efficient photocatalytic performance of St-MOP@Pd-2 is
attributable to its harmony between the efficient visible light-
harvesting material (St-MOP) and Pd NPs.
o
2
01 C
Conclusions
This work shows that Stille coupling reaction provides
interesting MOP chemistry. As far as we are aware, St-MOP is
the first example of MOP materials based on Stille coupling.
First, the size of synthesized St-MOP particles was sensitive to
the amount of Pd catalysts and hence could be systematically
controlled. As the amount of Pd catalysts increased, the size of
St-MOP particles was reduced, which is attributable to
enhanced nuclei in the early growth stage. Second, interestingly,
Pd NPs were in situ deposited on the St-MOP particles to form
St-MOP@Pd in one pot. The amount of Pd NPs could be
controlled by Pd catalysts. Third, the St-MOP@Pd materials
were functional as a visible light-driven photocatalyst. The St-
MOP showed visible light absorption at 450 nm and emission at
(
c)
(d)
Before
Before
After
2
00 nm
After
200 nm
5
22 nm. The emission was quenched by Pd NPs, indicating
efficient visible light-induced electron transfer from St-MOP to
Pd NPs. Among St-MOP@Pd materials, the St-MOP@Pd-2
MOP@Pd-2 (0.14 mol% Pd) in the visible light-driven Suzuki- with an optimal amount of St-MOP and Pd NPs showed
Fig. 7 (a) A TGA curve of St-MOP@Pd-2. (b) Recyclability tests of St-
Miyaura coupling. Reaction conditions: 1-acetyl-4-bromobenzene
0.500 mmol), phenylboronic acid (0.625 mmol), K CO (0.750
mmol), MeOH, 25 C, 5 h, white LED irradiation (0.9 mW/cm ). (c)
SEM images and (d) IR spectra of St-MOP@Pd-2 before and after
five recyclability tests.
efficient photocatalytic activities in the visible light-driven
Suzuki-Miyaura coupling. We believe that more various
functional MOP materials and new chemistry can be developed
based on Stille coupling.
(
2
3
o
2
The photocatalytic performance of the optimal St-MOP@Pd-2 can Conflicts of interest
be compared with those of recent polymer@Pd materials in the There are no conflicts to declare.
literature.16-17 (Table S2 in the ESI) At first, Li and coworkers
reported that g-C
3
N
4
@Pd (1.87 mol% Pd) showed a 97% yield in the Acknowledgements
visible light-driven Suzuki-Miyaura coupling of iodobenzene with
phenylboronic acid at 25 C for 1 h, corresponding to a TON of 52
This work was supported by the National Research Foundation
of Korea (NRF) grant (No. 2020R1A2C200431011) funded by
the Korea government (MSIT). K.C.K acknowledges the
financial support by Basic Science Research Program
o
and a TOF of 52 h-1.16 Zhang and coworkers prepared conjugated
microporous poly(benzoxadiazole) network with Pd NPs (0.56
mol% Pd), showing a 96% yield in the visible light-driven Suzuki-
Miyaura coupling of 1-bromo-4-fluorobenzene with phenylboronic
acid at room temperature after 4 h, corresponding to a TON of 171
and a TOF of 43 h-1.17a The same catalyst showed a 76% yield in the
reaction of 1-acetyl-2-bromobenzene with phenylboronic acid at
room temperature for 16 h, corresponding to a TON of 136 and a
TOF of 8 h-1.17a
Polydopamine nanofilms with Pd NPs (0.56 mol% Pd) prepared by
Xie, Wang, and coworkers showed a 95% yield in the visible light-
driven Suzuki-Miyaura coupling of methyl 4-bromobenzoate with
phenylboronic acid at room temperature for 2 h, corresponding to a
TON of 170 and a TOF of 85 h-1.17b Recently, Li, Lang, and
coworkers prepared conjugated nanoporous polycarbazole with Pd
NPs (0.50 mol% Pd), showing a 85% yield in the visible light-driven
Suzuki-Miyaura coupling of 1-acetyl-4-chlorobenzene with
(
2016R1A6A3A11933303) through the NRF of Korea funded
by the Ministry of Education.
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DOI: 10.1039/D0CY00997K
Page 9 of 9
Catalysis Science & Technology
Table of Contents
9
5
Stille coupling results in the in situ deposition of Pd NPs on microporous organic polymer, showing excellent performance in the
visible light-driven Suzuki-Miyaura coupling.
5
6
6
7
7
8
8
9
5
0
5
0
5
0
5
0
5
1
1
2
2
3
3
4
4
5
0
5
0
5
0
5
0
5
0
1
00