Encapsulating Au-Fe3O4 Nanodots into AIE-active Supramolecular Assemblies: Ambient Visible-light Harvesting “Dip-Strip” Photocatalyst for C?C/C?N Bond Formation Reactions

Article abstract of DOI:10.1002/asia.201801556

The present study demonstrates the development of a supramolecular porous ensemble consisting of hetero-oligophenylene derivative 6 and Au-Fe₃O₄ nanodots. Supramolecular assemblies of AIE-active hetero-oligophenylene derivative 6 served as reactors for the generation of Au-Fe₃O₄ nanodots. The as prepared supramolecular ensemble functioned as an efficient recyclable photocatalytic system for C(sp²)?H bond activation of anilines for the construction of quinoline carboxylates. Interestingly, the “dip catalyst” prepared by depositing PTh-co-PANI-6: Au-Fe₃O₄ nanodots on a filter paper served as a recyclable strip (up to 10 cycles) for C?C/C?N bond formation reaction.

Full text of DOI:10.1002/asia.201801556

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Encapsulating Au-Fe3O4 Nanodots into AIE active
Supramolecular Assemblies: Ambient Visible light Harvesting
“Dip-Strip” Photocatalyst for C-C /C–N Bond Formation Reactions
Authors: Harpreet Kaur, Mandeep Kaur, Preet Kamal Walia, Manoj
Kumar, and Vandana Bhalla
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10.1002/asia.201801556
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Encapsulating Au-Fe3O4 Nanodots into AIE active Supramolecular
Assemblies: Ambient Visible light Harvesting “Dip-Strip”
Photocatalyst for C-C /C–N Bond Formation Reactions
Harpreet Kaur, ‡ Mandeep Kaur, ‡ Preet Kamal Walia, ‡ Manoj Kumar and Vandana Bhalla*
Abstract: The present study demonstrates the development of
Moreover, most of the reported synthetic protocols for the
preparation of Au-Fe3O4 nanohybrid materials require harsh
reaction conditions such as high temperature, additives,
reducing agents and prolonged reaction time which decreases
the environment /economic advantages of the strategy.[4] In view
of the applications of magneto-plasmonics in diverse fields such
as optics, imaging, sensing, solar cells, biomedicals and
catalysis,[5] it is highly desirable to develop a rapid and
convenient protocol for their preparation.
supramolecular
oligophenylene
porous
ensemble
and
consisting
of
hetero-
derivative
6
Au-Fe3O4
nanodots.
Supramolecular assemblies of AIE active hetero-oligophenylene
derivative 6 served as reactors for the generation of Au-Fe3O4
nanodots. The as prepared supramolecular ensemble functioned as
an efficient recyclable photocatalytic system for C(sp2)−H bond
activation of anilines for the construction of quinoline carboxylates.
Interestingly, the „dip catalyst‟ prepared by depositing PTh-co-PANI-
6: Au-Fe3O4 nanodots on a filter paper which served as a recyclable
strip (upto 10 cycles) for C-C/C-N bond formation reaction.
Recently, from our lab, we reported development of
supramolecular assemblies based on derivative 1.[6] These
assemblies were then utilized as reactors and reductants for the
preparation of Au-Fe3O4 NPs having size in the range of 4-8 nm
at room temperature without using any additional reducing agent.
Simultaneously, the aggregates of derivative 1 were themselves
oxidized to polythiophene species which serves as stabilizer and
shape-directing template for the assembly of Au- Fe3O4 NPs in
an ordered fashion. The as prepared polythiophene Au-Fe3O4
nanohybrid materials exhibited remarkable catalytic efficiency in
C(sp2)−H bond activation of unprotected anilines under visible
light irradiation to furnish synthetically versatile quinoline
carboxylates. Previously, a variety of catalytic systems for C-H
activation reaction have been reported which utilizes costly and
non-recyclable organometallic/Ionic liquids as catalysts.[7]
Furthermore, in most of these cases an inert atmosphere,
prolonged heating at high temperature and use of toxic CO gas
was needed for the preparation of quinolines through C-H
activation reaction which basically reduced the environmental as
well as economic benefits of the approach.[8] In comparison to
these reports, derivative 1 supported Au-Fe3O4 NPs catalyzed
the synthesis of quinolines with eco-friendly advantages (Table
S1). We believe that polythiophene species facilitated the
catalytic activity by absorbing visible radiations and transferring
the energy to active metallic center which was evident from
spectral overlap between the emission spectrum of
polythiophene species and absorption spectrum of Au-Fe3O4
nanocomposites. We hypothesized that by increasing the
emission intensity and wavelength, the extent of energy transfer
from oxidized species to metallic centre can be increased, which
will definitely improve the catalytic efficiency of the system. For
increasing the energy transfer highly fluorescent materials
emitting at longer wavelength are desirable. Recently,
aggregation induced emission (AIE) phenomena is being
explored for development of highly emissive thiolate derivatives
which serve as supporting materials for gold nanoclusters.[9]
These studies inspired us to examine the role of AIE active
materials as the supporting material in enhancing the catalytic
efficiency of the system. Hence, we planned the synthesis of
hetero-oligophenylene derivative 6 having amino/thiophene
Introduction
Among various magneto-plasmonics, gold-iron oxide (Au-Fe3O4)
nanocomposites are particularly attractive due to their
remarkable photocatalytic activities in C-C/ C-N bond formation
reactions.[1] The combination of magnetic Fe3O4 and Au
nanoparticles not only tuned the efficiency of the system but also
improve the recyclability/reusability of the catalytic system. The
photocatalytic efficiency of the system is also influenced by the
photophysical properties of the supporting organic materials.
The supporting organic materials also control various other
functions such as stability, dissolution and biocompatibility of the
metal NPs.[2] These hybrid materials comprising supporting
materials and Au-Fe3O4 nanocomposites provide an efficient
and atom economical approach for the construction of C-C/ C-N
bond formation. Over the past few years, a lot of research efforts
are centred around the development of new strategies for
improving
the
photocatalytic
efficiency
of
Au-Fe3O4
nanocomposites.[3] Though the supporting organic materials play
an important role in increasing the activity of the system yet
most of the research efforts are mainly focused at improvement
of catalytic efficiency by controlling the size and shape of the
nanomaterials and relatively less efforts are done to examine the
role of structural modification/photophysical properties of the
supporting organic materials. To investigate the role of
supporting materials in enhancing the catalytic activity of the
system, a study relating to structural modifications of stabilizing
species and catalytic efficiency of the system is needed.
[a]
Department of Chemistry, UGC Sponsored Centre for Advanced
Studies-II, Guru Nanak Dev University, Amritsar, Punjab, India.
E-mail: vanamanan@yahoo.co.in
‡ Authors are equally contributed
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10.1002/asia.201801556
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groups. We envisaged that the rotatable C-C bonds at the
periphery may endow AIE characterstics to the synthesized
derivative 6. The amino/thiophene groups were incorporated in
derivative 6 due to their known affinity for gold ions (Scheme 1).
Gratifyingly, the derivative 6 exhibited AIE characterstics and
formed fluorescent assemblies in the H2O: THF solvent mixture
which served as reactors to generate Au-Fe3O4 nanocomposites
having size in the range of (1.5-2.0 nm). To the best of our
knowledge, there is no report in literature regarding generation
of Au-Fe3O4 nanocomposites having such a small size (Table
S2). During the formation of Au-Fe3O4 NPs, assemblies of
derivative 6 were oxidized to AIE active polymeric species PTh-
co-PANI-6 which showed broad emission in the broad range of
365-640 nm. A significant overlap between absorption spectra of
Au-Fe3O4 NPs and emission spectra of the oxidized species was
observed which indicated the possibility of good energy transfer
between them. To check the validity of our hypothesis, we
examined the model reaction between aniline (10) and methyl
propiolate (11) in the presence of CO source in the presence of
PTh-co-PANI-6: Au-Fe3O4 NPs as catalyst. The reaction was
Afterwards, we analyzed the photophysical behavior of the
compound in H2O/THF solvent system. The UV-vis and
temperature dependent absorption studies of derivative 6 in
THF/H2O solvent mixture suggested the development of J-
aggregates (Figure S2-S3). In the emission studies, upon
increasing the water content in the THF solutions (0-60%), a
gradual increase in the intensity of the emission band was
observed and the emission band was red shifted from 417 to
427 nm (Figure S4). The AIE behaviour of derivative 6 was
further confirmed by viscosity dependent fluorescence studies
(Figure S5). The formation of spherical aggregates of compound
6 was confirmed by TEM studies (Figure S6).
To ascertain the applicability of aggregates of derivative 6 for
preparation of Au-Fe3O4 nanocomposites, we followed the
procedure as reported earlier.[8] In the absorption studies, the
simultaneous addition of Au3+ and Fe3+ ions (15 equiv.) to the
solution of derivative 6, SPR band of Au NPs appeared at 550
nm (after 25 mins) which was gradually shifted to 570 nm. The
intensity of the level-off tail was also increased, thus, signifying
the preparation of Au-Fe3O4 magnetic nanocomposites (Figure
S7).[11] The color of the solution was also changed from colorless
to yellow to purple and finally turned to reddish brown (Figure
S8). The entire process was complete within 45 mins.
The TEM and HRTEM image of derivative 6 in the presence of
Au3+ and Fe3+ ions (15 equiv.) revealed the existence of
spherical PTh-co-PANI-6: Au-Fe3O4 magnetic nanocomposites
encapsulated into the network of polymeric species (Figure 1,
S9). The DLS studies demonstrated the size of formed Au-Fe3O4
nanodots in the range of 1.5-2.0 nm (Figure S10). The powder
XRD analysis of Au-Fe3O4 nanodots displayed diffraction peaks
for fcc lattice of Fe3O4 NPs and Au NPs (Figure S11).[12] The
XPS analysis of the PTh-co-PANI-6: Au-Fe3O4 nanodots
confirmed the presence of Au (0) ( Au4f, 85.9 and 88.9 eV)and
Fe3+ and Fe2+ species (Fe2p, 710.8 and 724.5 eV) in the Au-
Fe3O4 lattice.[13] Additionally, peaks were detected for S2p, C1s,
O1s and N1s which were due to organic residue (Figure S12).
The appearance of band at 630 cm-1 in the Raman spectrum
relates to the A1g vibration mode of Fe3O4 NPs (Figure S13).[11]
The DT-TGA analysis of PTh-co-PANI-6: Au-Fe3O4
nanomaterials suggested a nonlinearly weight loss from 200 to
600 °C. From the measurements for weight loss, the amount of
PTh-co-PANI coating layer on Au-Fe3O4 nanodots was found to
be approximately 32% (Figure S14). From hysteresis
measurements, the magnetic nature of Au-Fe3O4 nanodots was
estimated (Figure S15, Table S3).
complete in 5 hrs to furnish the desired product in 87% yield. In
[6]
the presence of previously reported catalytic system,
the
reaction was complete in 6 hrs to give the final product in 80%
yield. This study validates our assumption that by making
assemblies more emissive, increasing the emission intensity and
wavelength of assemblies, extent of energy transfer and finally
catalytic efficiency of the system can be enhanced. Further,
PTh-co-PANI-6: Au-Fe3O4 nanodots were deposited on a filter
paper to prepare a “dip- catalyst”. The “dip- catalyst” serves as a
reusable strip for carrying out the C(sp)–H activation and it
showed recyclability up to 10 cycles. To the best of our
knowledge, this is the first report regarding study of influence of
structural features and photophysical properties of supporting
materials on the photocatalytic efficiency of the system. Further,
this is the first report of utilization of Au-Fe3O4 based „dip strip‟
photocatalyst for the preparation of quinoline derivatives via C-H
activation reaction.
Results and Discussion
Initially, precursor 4 was prepared via Diels-Alder reaction
between derivatives 2[10] and 3. Further, precursor 4 and boronic
ester 5 undergo Suzuki- Miyaura cross coupling reaction to
deliver the target derivative 6 in 76% yield (Scheme 1). The
structure of this derivative 6 was elucidated by different
spectroscopic techniques (Figure S1).
During the formation of Au-Fe3O4 nanodots the aggregates of
derivative 6 were oxidized to PTh-co-PANI. To understand this
process, a reaction was performed between derivative
6
(B)
(A)
(H2O/THF) and Au3+ and Fe3+ ions at room temperature and
after one hour, reaction mixture was left for slow evaporation at
room temperature . The as formed magnetic Au-Fe3O4 nanodots
were filtered and then washed with organic solvents (CHCl3 and
THF). The residue filtrate was allowed to evaporate to obtain the
solid organic material and formed the oxidized species PTh-co-
PANI-6 (Figure 1).
3
5
Ph2O,
240oC
2
4
6
1
Scheme 1. (A) Structure of derivative 1 and (B) Synthesis of derivative 6.
1
As per H NMR studies of the oxidized material (PTh-co-PANI-
6), the signals in the aromatic region were shifted and
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10.1002/asia.201801556
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broadened which suggested the formation of polythiophene and
polyaniline species PTh-co-PANI-6 (Figure S16).[14] The ESI-MS
spectrum exhibited peak at m/z = 2907.0722 which is in
accordance with the theoretical molecular mass of polyaniline
and polythiophene species [C200H138N8S8H]+ (Figure S17). The
powder XRD analysis of this sample showed the characteristic
peaks suggesting the formation of polyaniline species[15] and
polythiophene species (Figure S18).[16] The IR spectrum of the
oxidized species also supported the formation of
The emission spectrum of oxidised species PTh-co-PANI-6
showed broad band in the region of 365 to 640 nm (λex=350
nm). The intensity of emission band of PTh-co-PANI-6 was
reduced (71%) when bare Au-Fe3O4 NPs (5 mol %) were added
to this solution. This outcome clearly supported the possibility of
energy transfer between oxidised species and metallic centre
(Figure S25). To get insight into the photostability of the organic
support, we exposed the solution of PTh-co-PANI-6 in H2O/THF
(6:4) mixture to visible radiations under lab conditions. We
recorded the emission spectra of PTh-co-PANI-6 after 3 and 5
hrs and decrease in fluorescence intensity was observed (11%
after 3 hrs, 55.6% after 5hrs) (Figure S26).
(A)
(B)
These studies encouraged us to explore the photocatalytic
efficiency of the generated Au-Fe3O4 nanocomposites in the
C(sp2)-H activation and C(sp)-N coupling reactions in the
presence of visible light. The reaction between aniline (10) and
methyl propiolate (11) was chosen as the model reaction. The
= Au NPs
reaction was performed using H2O as
a
solvent,
= Fe3O4 NPs
paraformaldehyde as CO source and PTh-co-PANI-6: Au-Fe3O4
nanodots as the catalytic system (Scheme 3). The reaction was
accomplished in 5 hrs to furnish target qunioline carboxylate
derivative (12a) in 87% yield. Next, we performed the same
reaction in the presence of PTh-7: Au-Fe3O4 nanocomposites as
the catalytic system. In this case, the reaction afforded the
preferred product in 77% yield after 7 hrs. Under the optimized
reaction parameters, the best yield i.e. 87% was obtained in the
case of PTh-co-PANI-6: Au-Fe3O4 nanodots which may be
attributed to smaller size and porous morphology of the catalytic
system (Table S4). Through these optimal reaction conditions,
the scope of various substituted anilines and alkynes was
examined using PTh-co-PANI 6: Au-Fe3O4 as the catalytic
system. To our delight, aryl amines bearing electron-rich (-Me)/
electron-withdrawing group (-Cl) and electron- deficient alkynes
(11) all reacted well to afford the C−H activation products (12a-
d) in moderate to excellent yields (Scheme 3).
(C)
(D)
Au- Fe3O4 NPs Porous network of
PTh-co-PANI-6
Figure 1. (A) Schematic representation of formation of PTh-co-PANI-6 (B)
Structure of polymeric species and TEM images of Au-Fe3O4 nanocomposites
encapsulated into polymeric species with scale bars of (C) 50 nm (D) 20 nm.
polythiophene and polyaniline species (Figure S19).[17] To check
the porosity of the nanodots, the BET measurements were taken
which detected the surface area of 34.46 m2/g and pore volume
0.03 cm3/g.[18]
To get visualization into the influence of structural modifications
on the size/shape of generated nanomaterials, we also
synthesized derivative 7 having aldehyde groups (Scheme 2,
Figure S20). Derivative 7 showed the AIE characteristics and
served as reactors to generate PTh- 7: Au-Fe3O4
Au-Fe3O4 NPs,
1
hν
nanocomposties (Figure S21-S22). The H NMR and IR studies
CO source
12a
of the oxidized product showed the presence of aldehyde groups
which suggested that aldehyde moieties are not involved in the
reduction process (Figure S23). The TEM image also suggested
the formation of PTh- 7: Au-Fe3O4. Interestingly, its size was
found to be relatively large 20-30 nm from DLS studies (Figure
S24). We believed that, oxidised species PTh-co-PANI-6 due to
the presence of higher number of binding sites (-NH2/thiophene)
could uniformly coat the as prepared nanohybrid materials and
could restrict their growth as a result of which nanomaterials of
smaller size are generated.
10
11
12b
12c
12d
4.5/83
5/73
Time(h)/Yield(%)=4.5/87
Scheme 3. C(sp2)-H activation reaction between aniline (10, 1 mmol), methyl
propiolate (11, 1 mmol) and paraformaldehyde (2.5 mmol) catalyzed by PTh-
co-PANI-6 encapsulated Au-Fe3O4 nanocomposites under photocatalytic
conditions (irradiation of 60 W tungsten filament bulb).
(B)
(A)
To explore the reaction mechanism of C(sp2)-H activation
reaction, the model reaction for C(sp2)-H activation was
performed in the presence of TEMPO, however, the reaction did
not provide the desired product. Fortunately, we could isolate
the ortho-adduct between aniline and TEMPO whose structure
was confirmed by 1H NMR spectra (Figure S27). The above
studies clearly recommended that the generated radical species
Au3+ +Fe3+
(25 equiv.)
7
PTh 7: Au-Fe3O4
Scheme 2. (A) Schematic diagram (B) TEM image depicting the formation of
polythiophene species PTh 7: Au-Fe3O4 nanocomposites; (scale 20nm).
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were essential for carrying out the C(sp2)-H activation to yield
quinoline carboxylates (Figure S28).
Au-Fe3O4 NPs
Next, we prepared „dip strip‟ by dipping the filter paper into the
solution of PTh-co-PANI-6: Au-Fe3O4 nanodots. The SEM
image of the filter paper indicates the coating of the paper strip
by the nanomaterial (Figure S29). The „dip-strip‟ catalyst was
used for the model reaction between aniline (10) and methyl
propiolate (11) under optimized parameters. The reaction was
accomplished in 5 hrs to provide the desired product in 89%
yield. The dip catalyst in the catalytic reaction was recovered
and reused as such for the next reaction. After the 10th cycle,
yield of target product decreased to 60% (Figure S30).
Further, we studied the catalytic activity of the PTh-co-PANI-6:
Au-Fe3O4 nanodots in the reaction between aniline and
activated/ unactivated alkynes in the absence of CO source
under photocatalytic conditions and at room temperature. The
C(sp)-N coupling reaction between aniline (10) and methyl
propiolate (11) in the absence of CO source was chosen as the
model reaction (Scheme 4).
hν, H2O
15a
10
14
Scheme 5. Hydroamination reaction between aniline (10, 1 mmol), phenyl
acetylene (14, 1.2 mmol) catalyzed by PTh-co-PANI-6 encapsulated Au-
Fe3O4 nanodots under photocatalytic conditions.
2, Table S7). The model reaction was completely inhibited when
performed in the absence of catalyst (entry 3, Table S7). We
also checked the scope of substituted phenylacetylenes and the
reaction proceeded faster with the electron rich phenylacetylene
(entries 1-7, Table S6). The exclusive formation of desired
Markovnikov type acetophenones may be accredited to the
construction of a more stable imine and ability of the catalytic
system to activate phenyl acetylene.
Au-Fe3O4 NPs
Conclusions
hν . H2O
13a
11
10
In conclusion, we have designed and synthesized AIE active
and fluorescent aggregates of hetero-oligophenylene derivative
6 which served as reactors for the formation of PTh-co-PANI-6:
Au-Fe3O4 nanocomposites. The supramolecular porous
ensemble PTh-co-PANI-6: Au-Fe3O4 served as an effective and
recyclable catalytic system for C(sp2)−H bond activation under
smooth and eco-friendly conditions. Further, PTh-co-PANI-6:
Au-Fe3O4 nanocomposites were deposited on a filter paper to
prepare a “dip-strip” which served as a reusable strip (upto 10
cycles) for carrying out the C-C/C-N bond formation reaction.The
work being presented in the manuscript demonstrate the
important role of AIE active supporting material in enhancing the
efficiency of Au-Fe3O4 based photo catalytic system.
Scheme 4. C(sp)-N coupling reaction between aniline (10, 1 mmol), methyl
propiolate (11, 1.2 mmol) catalyzed by PTh-co-PANI-6: Au-Fe3O4 magnetic
nanodots under photocatalytic conditions.
In this reaction, water was used as a sole reaction media in this
C(sp)-N coupling reaction. Under the photcatalytic conditions,
reaction was accomplished in 20 mins and afforded the β-amino
acrylate derivative (13a) in 88% yield (entry 1, Table S5). Very
instrestingly, when the same procedure was repeated at room
temperature, it took 35 mins for completion. We examined the
substrate scope of the reaction with regard to substituted
anilines and alkynes at room temperature (Table S5). Under
improved reaction parameters, substitution at both C2 and C4
positions of anilines was also well-tolerated (entry 2, Table S4).
Notably, substrates having electron-donating/withdrawing
groups at the C2 and C4 position with respect to amino group
readily undergo the reaction (entries 3-6, Table S5). We also
examined the recyclability of catalytic system in model reaction.
Being magnetic catalyst it could be recycled and reused upto
13th cycle with continuous reduction in the reactivity of the
catalyst. After the 13th cycle, the yield of the final product was
decreased up to 52% (Figure S31).
Acknowledgements
V.B. is thankful to SERB, New Delhi (ref no. EMR/2014/000149)
for financial support. Mandeep Kaur is thankful to UGC (New
Delhi, India) for Senior Research Fellowship (SRF). We are also
thankful to “University with Potential for Excellence” (UPE)
project.
Keywords: AIE active hetero-oligophenylenes • Supramolecular
porous ensemble • Au-Fe3O4 nanodots • Recyclable „dip
catalyst‟ • C(sp2)−H bond activation.
On the other hand, the model reaction between aniline (10) and
phenylacetylene (14) under photocatalytic conditions in the
presence of PTh-co-PANI-6: Au- Fe3O4 nanodots furnished the
acetophenone (15a) (hydroamination reaction) as the product
(Scheme 5).
We also examined the reaction of –o/-m/-p substituted anilines
with phenylacetylene and all of the substituted anilines on
reaction with phenylacetylene yielded acetophenone (entries 2-5,
Table S6). Interestingly, when the model reaction was executed
without aniline the reaction did not yielded acetophenone (entry
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10.1002/asia.201801556
Chemistry - An Asian Journal
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The
supramolecular
as
prepared
AIE
active
could
Harpreet Kaur, ‡ Mandeep Kaur, ‡ Preet
Kamal Walia, ‡ Manoj Kumar and
Vandana Bhalla
ensemble
harvest ambient visible light and can
be utilized as efficient and recyclable
“dip strip” photocatalyst for (sp2)−H
bond activation for the construction of
quinoline carboxylates via C−H
activation.
Au3+ + Fe3+ ions
(15 equiv.)
C(sp2)-H activation
C(sp)-N coupling
= Au NPs
= Fe3O4 NPs
Hydroamination
= Au- Fe3O4
Aerial conditions
Room temperature
Photocatalytic
AIE active
supramolecular
assemblies
= PTh-co-PANI-6
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