Cu/CuxOyNPs architectured COF: a recyclable catalyst for the synthesis of oxazolidinedioneviaatmospheric cyclizative CO2utilization

Article abstract of DOI:10.1039/d0cc04835f

The present study describes the favourable construction of a crystalline covalent organic framework (COF) with exceptional surface area, tunable pore size and huge CO₂capture efficiency to facilitate a novel multicomponent cyclization by introducing CO₂into extremely reactive organic skeletons. In the presence of a catalytic Cu/Cu_xO_yNP-loaded COF, several 2-bromo-3-alkylacrylic acids combined with several amine derivatives and CO₂(0.1 MPa) are converted to the desired oxazolidinediones in excellent yields (up to 96%) under alkali-free conditions and ambient temperature.

Full text of DOI:10.1039/d0cc04835f

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DOI: 10.1039/D0CC04835F
Title of the manuscript
Cu/CuxOy NPs Architectured COF: A Recyclable Catalyst for Oxazolidinedione Synthesis via
Atmospheric Cyclizative CO2 Utilization
Authors
Somnath Sarkar,a Swarbhanu Ghosh,a Jahangir Mondala and Sk. Manirul Islam*a
Affiliations
aDepartment of Chemistry, University of Kalyani, Kalyani, Nadia, 741235, W.B., India.

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DOI: 10.1039/D0CC04835F
Cu/CuxOy NPs Architectured COF: A Recyclable Catalyst
for Oxazolidinedione Synthesis via Atmospheric Cyclizative
CO2 Utilization
Received 00th January 20xx,
Accepted 00th January 20xx
Somnath Sarkar,a Swarbhanu Ghosh,a Jahangir Mondala and Sk. Manirul Islam*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
The present study describes the favourable construction of the stacked 2D COFs retain few reasonable advantages, like several
crystalline covalent organic framework (COF) with exceptional optional monomeric units, flexible building units resulting in
surface area, tunable pore size and huge CO2 capture efficiency to tunable features of the layered crystalline materials.11 On the other
facilitate a novel multicomponent cyclization by introducing CO2 hand, owing to the comparatively intricate growth method
into extremely reactive organic skeletons. In the presence of involving crystallization, assembly and polymerization etc., it
catalytic Cu/CuxOy NPs-loaded COF, several 2-bromo-3-alkylacrylic remains a huge difficulty to generate well-organized and absolutely
acids combined with several amine derivatives and CO2 (0.1 MPa) ordered 2D stacked COF sheets so far. Generally, the construction
are converted to the desired oxazolidinediones in excellent yields processes of 2D sp2 carbon-conjugated COFs published can be
(up to 96%) under alkali-free condition and ambient temperature. categorized into two classes, bottom-up strategy and top-down
Intriguingly, the reaction described above is mostly catalyzed by strategy. Herein, Cu/CuxOy NPs can be stabilized by heteroatom
CuO and Cu2O sites present in Cu@COF-BD(OH)2.
functionalized COF pores, whereas meso/micropores of this COF
permit unrestricted access to these nanoparticles-based active
binding sites. This COF−nanoparticles composite catalyst, as a novel
catalytic system, retain definite advantages, like scalability,
reusability, easy-to-handle, and their performance can be adjusted
through a “by-design” approach.12 Additionally, Oxazolidinedione is
Atmospheric climate-warming carbon dioxide (CO2) is one of the
most significant greenhouse gases and its worldwide uncontrolled
emission into the environment and an alarming level
of atmospheric notorious CO2 have caused increasing global
concerns.1 It is a significant C1 building unit for the synthesis of
high-value chemicals due to its low-priced, abundant, and non-
poisonous nature. It has a huge potential as polymeric systems,
fuels or other compounds via the utilization of renewable energy
source.2 The mission to control atmospheric CO2 (a greenhouse gas)
has triggered the advancement of some novel cyclizative CO2-
incorporated reactions. In the previous decade, transition-metal
promoted CO2 incorporation has emerged as a feasible, sustainable
and potential strategy towards the more benign synthesis of several
valuable commodity compounds like carboxylic acid derivatives by
activating C-H bonds in organic synthesis.3 In recent times, Yoshida
et al. published that harmful CO2 could straightforwardly be
introduced by conducting a three-component reaction employing
imines and arynes, where produced zwitterionic species from the
nucleophilic attack of imine systems to arynes captured carbon
dioxide as a path to biologically and pharmaceutically active
derivatized benzoxazinone derivatives.4 Recently, Kobayashi and co-
researchers employed a comparable approach for the generation of
isocoumarin derivatives through novel NHC-Cu facilitated reactions
participating terminal alkynes, CO2 and orthoarynes.5 Therefore, the
advancement of effective strategies employing atmospheric
notorious CO2 in combination with MCR-type synthetic
methodology (multicomponent reaction) for the generation of
heterocycle systems like oxazolidinediones is value-added
chemicals for their utilities from pharmaceuticals to polymeric
systems, which could unlock a novel route to a chemical library of
several high-value chemical scaffolds.
a
high-value constituent of numerous molecules possessing
biological activity. series of value-added pharmaceuticals
A
consisting of these moieties are being utilized for numerous types
of functions (such as therapeutic purposes) (Scheme 3).
Scheme 1. Schematic illustration of the cyclizative CO2-incorporated reaction.
Scheme 2. Generation of oxazolidinediones facilitated with a potential Cu/CuxOy NPs
embedded COF under benign conditions.
Herein, we introduced the fruitful production of oxazolidinedione
derivatives from amine derivatives and derivatized 2-bromo-3-
alkylacrylic acids employing CO2 as a C1 source in the presence of a
definite amount of catalytic Cu/CuxOy NPs-grafted COF. According
to the best of our knowledge, it will be the first report of CO2-
incorporated multicomponent cyclization with Cu/CuxOy NPs
architectured covalent organic framework, (Cu@COF-BD(OH)2), as a
potential heterogeneous catalyst under alkali-free conditions
(sustainable approach). Characterizations of parent COF-BD(OH)2
and resultant Cu@COF-BD(OH)2 are performed by analyzing
thermogravimetry (TG), N2 adsorption−desorption analysis, Fourier
transform infrared (FT-IR) spectrum, elemental analysis,
transmission electron microscopy (TEM), powder X-ray diffraction
(PXRD), scanning electron microscopy (SEM) and X-ray
photoelectron spectroscopy (XPS). The schematic illustration of the
construction method involved in developing 2D COF-BD(OH)2 is
presented in Scheme 3.
Covalent organic frameworks (COFs) are an emerging kind of π-
bonded, stacked and layered polymeric agents featuring excellent
crystallinity, which have displayed widespread utilities in energy
storage,6 gas adsorption,7 metal ions isolation and recovery,8
chemical sensing,9 and catalysis,10 etc. Compared with some
exfoliated 2D nanomaterials of inorganic nature or graphene, the
a. Department of Chemistry, University of Kalyani, Kalyani, Nadia, 741235, W.B., India.
† Electronic Supplementary Information (ESI) available: Experimental, results and
discussion, characterizations of the materials and 1H and 13C NMR of the pure
products. See DOI: 10.1039/x0xx00000x
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Scheme 3. Some illustrations of biologically active derivatized oxazolidinediones and schematic illustrations of the construction method involved in developing 2D COF-BD(OH)2
material and the preparation process of Cu/CuxOy NPs embedded COF catalyst.
The distribution of pore size of the COF-NPs composite determined
with the help of NLDFT method employing N2 at a definite
temperature (77 K) confirmed the existence of micropores having
pore dimension (ca. 1.8 nm).14 As described in Figure 1(a-c), SEM
(scanning electron microscopy) pictures of this COF-NPs composite
suggest that a curled irregular arrangement is made up
of interconnected twisted rods inside the nanoscale range (coral-
like microscopic arrangement).15 As presented in Figure S11 (a-d),
the TEM pictures of COF-BD(OH)2 suggested structural morphology
of interlinked twisted wires (see ESI for details). As described in
Figure S11 (c-d), the clearly visible borders in mentioned TEM
pictures of COF-BD(OH)2 illustrating intensely conjugated layered-
sheet arrangement exists in this highly ordered parent COF owing
to the presence of aromatic π−π interactions.16 COF-BD(OH)2
displayed layered-sheet arrangement observed by TEM, which is in
agreement with the SEM pictures. PXRD pattern of the parent COF
agrees well with HR-TEM pictures. As described in Figure 2 and 1,
TEM and SEM pictures display that the structural morphology of
Cu@COF-BD(OH)2 composite catalyst can keep the same as the
morphology of COF-BD(OH)2. EDAX experiments illustrated the
existence of O, N and C as displayed in Figure S13 and S14 (see
ESI for details). EDX also suggested the loading of copper in the
COF-NPs composite to be at 6.4 wt%, which is in agreement with
the copper loading (6.8 wt %) measured from the ICP experiment.
XPS experiments demonstrate the existence of Cu+ (Cu2O) along
Fig. 1 PXRD patterns of COF-BD(OH)2 and Cu@COF-BD(OH)2 composite catalyst, FE-SEM
pictures of Cu@COF-BD(OH)2 composite catalyst at several magnifications (a-c).
with a certain amount of Cu2+ (CuO) in the COF-NPs composite
The powder X-ray diffraction patterns of the parent COF-
BD(OH)2 and Cu/CuxOy NPs embedded COF is presented in Fig. 1,
demonstrating that the microporous layered sheets display
absolutely ordered hexagonal 2D arrangement. The PXRD pattern of
the as-obtained COF-BD(OH)2 exhibits a significant diffraction peak
of high intensity, which is located at a diffraction angle (2θ) of 3.3°
corresponding to the (100) facet, demonstrating the excellent
crystallinity due to lower rotational freedom of the building units
(Figure 1). The resultant COF-NPs composite exhibits the main peak
of elevated intensity situated at a diffraction angle (2θ) of 3.3o,
caused by the (100) facet. One minor hump-shaped peak of poor
intensity, caused by the (001) facet, situated at 27.3o, and the
existence of this distinct peak is ascribed to a special interaction
arising from π−π stacking among the aromatic rings present in the
ordered layered-sheet COF, suggesting exactly ordered periodicity
of the as-obtained COF-BD(OH)2.13 The particle sizes (crystallite size)
of Cu NPs were calculated to be within the range of 14 to 17
nm determined from the Scherrer’s equation (Table S7, ESI†).
Employing Debye-Scherer formula, the determined crystallite sizes
are found to be 25.03ꢀnm and 24.69 nm for the (002) facet (CuO)
and (111) facet (CuO), respectively. The TEM results are in good
accordance with the calculated values obtained from the Scherrer’s
equation. Employing Debye-Scherrer equation, the crystallite sizes
of Cu2O are determined to be in the range of 18.5±1.5 nm (Table S8,
ESI†). As presented in Figure 3(h), The N2 desorption/adsorption
isotherm of the microporous π-bonded stacked Cu@COF-BD(OH)2
displays usually the copious features of type I with few additional
natures of type IV pattern. The surface area obtained from BET
experiment and observed pore volume of Cu@COF-BD(OH)2
composite catalyst are 192.31 m2g-1 and 0.201 ccg-1, respectively.
named Cu@COF-BD(OH)2. The XPS survey scan of Cu@COF-BD(OH)2
is presented in Figure 3a which demonstrates the existence of
oxygen, nitrogen, carbon and Cu species existing in the intensely
conjugated COF-based copper material.
Figure 2. The UHR-TEM pictures of Cu@COF-BD(OH)2 material displaying the distinct
lattice fringes owing to the existence of different copper species at different scales (a)
100 nm, (b) 50 nm, (c) 20 nm, (d) 10 nm, (e) 20 nm, (f) 2 nm, (g) 5 nm and (h) SAED
pattern of Cu@COF-BD(OH)2. The inset describes the distribution of particle size
determined from TEM image.
The Cu 2p XPS signal has been subjected to deconvolute (Figure 3f),
which displays 2p3/2 bands with binding energies of 934.8 and 932.6
eV, which are assigned to the CuO (Cu2+) and Cu2O (Cu+) in the
Cu/CuxOy NPs embedded COF, respectively.17 As described in Figure
3c, the significant Cu LMM peak appeared at 570.4 eV is ascribed to
the copper species featuring lower oxidation state (Cu2O) in
addition to the Auger parameters of the copper 2p3/2. Additionally,
O 1s, N 1s and C 1s narrow scan (Figure 3) demonstrate the
structural morphology of Cu/CuxOy NPs anchored COF.
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Figure 3. XPS survey scan measurement on Cu@COF-BD(OH)2 (a), C 1s narrow scan (b), XPS Cu LMM spectra (c), N 1s narrow scan (d), O 1s narrow scan measurement (e) on
Cu@COF-BD(OH)2 composite catalyst; the XPS spectrum of Cu@COF-BD(OH)2 illustrating the bands corresponding to metallic copper NPs and copper oxide NPs featuring different
oxidation states (Cu1+ and Cu2+) and the “#” represent the shake-up photo emission bands suggesting Cu2+ (f), Cu 2p3/2 XPS core level spectra (g), and the N2 sorption profile of
Cu@COF-BD(OH)2 composite catalyst (h); pore size distribution of Cu@COF-BD(OH)2 (i), calculated by using NLDFT method.
The C 1s core level peak by conducting peak deconvolution free condition (Table S1, entries 22, ESI†). The substrate scope of
displayed that bands with binding energies of 289.2, 286.02 and CO2-incorporated cyclizative multicomponent reaction of some
284.5 eV for Cu@COF-BD(OH)2 are ascribed to the carbon atoms of derivatized bromoacrylic acids with several amines was also
C=O, C-O/C-N and C-C, C=C and C-H, respectively.35 The N 1s signal investigated under the optimal conditions and the outcomes
illustrates a band with binding energy of 399.9 eV corresponding to obtained are presented in Table 1. Several amine derivatives and
the enamine nitrogen atoms (Figure 3d). The band located at 400.8 different as-prepared 2-bromo-3-alkylacrylic acids were employed
eV corresponds to the existence of poor Cu−N attachment due to to synthesize different derivatized products under the application of
an interaction between copper species and enamine nitrogen the optimal conditions: 40 mg of Cu@COF-BD(OH)2 catalyst, 10 h,
atoms. The prominent copper 2p XPS spectra display bands at the 25oC, 6 ml DMF solvent.
binding energies of 932.6, 934.8, 952.2, and 954.1 eV, which are Table 1. Copper-facilitated production of several oxazolidinedione
consistent with the Cu 2p3/2 and Cu 2p1/2 levels of the copper NPs derivatives via CO2-incorporated cyclizative multicomponent
and copper featuring lower oxidation state from Cu2O (Figure 3f reactions with a detailed substrate scope.a
and 3g).18 Furthermore, two unique satellite peaks located at 964
and 944 eV are ascribed to the copper species featuring higher
oxidation state. The prominent shake-up satellite arrangements and
strong Cu 2p3/2 peak were subjected to deconvolute into four
distinct bands, as presented in Fig. 3g. Two clearly visible peaks
located at 932.6 and 934.8 eV could be attributed to Cu (I) from
Cu2O NPs and Cu(II) from CuO phases, respectively. The XPS
outcomes suggest that the catalyst is composed of CuO, Cu2O and
Cu. Cu0 and Cu+ (Cu2O) cannot be resolved by this deconvolution
because their respective binding energies are fairly close and are
different by around 0.1 eV (Fig. S28, ESI†). Cu2O and Cu metal are
best distinguished from the x-ray-excited Cu LMM Auger spectra.
Two overlapping bands at about 568.08 and 570.40 eV in the XAES
spectra are related to Cu0 and Cu+, respectively, and the
deconvolution outcomes of these bands are utilized to estimate the
molar ratios of different copper ions (XCu+ = Cu+/(Cu0 + Cu+)) (Fig.
S29, ESI†).19
Scheme 4. Generation of the desired oxazolidinedione through CO2-incorporated
cyclizative multi component reaction of bromoacrylic acid with aromatic amine.
Initially, we were inspired by the outcome published on the
alkali mediated atmospheric cyclization reaction of CO2,
bromoacrylic acids and amines for the generation of
oxazolidinediones type bioactive drugs (Scheme 1).20 We expected
that these value-added compounds could be generated by catalytic
Cu/CuxOy NPs embedded COF under sustainable conditions (Scheme
2).21 To establish our present hypothesis, 2-bromo-3-phenylacrylic
acid 1b and aniline 2b*are employed as model substrates for the
aReaction conditions: 2-bromo-3-alkylacrylic acids (1.0 mmol), amines (1.2 mmol),
sustainable synthesis of oxazolidinedione (3bb*) in the presence of
catalytic COF-NPs composite under atmospheric CO2 (0.1 MPa)
(Scheme 4). We next tested the influences of several parameters on
the advancement of the CO2-incorporated cyclization reaction
including catalytic systems, amount of the investigated catalyst,
reaction temperatures, solvents, bases and reaction times (Table
S1, ESI†). The use of Cu/CuxOy NPs embedded COF as a potential
catalytic system provided an excellent yield in the presence of
atmospheric CO2 (0.1 MPa) under ambient temperature and alkali-
Cu@COF-BD(OH)2 catalyst (40 mg), CO2 (0.1 MPa), DMF (6 mL). bIsolated yield.
Seven kinds of bromoacrylic acids with phenyl (1b), p-
methoxyphenyl (1a), p-tolyl (1c), m-tolyl (1d), p-chlorophenyl (1e),
3,5-dimethylphenyl (1f) and 4-hydroxyphenyl (1g) parts were
initially generated by conducting multi steps processes (See
Supporting Information for additional information). The as-obtained
bromoacrylic acid derivatives were allowed to react with aromatic
and aliphatic amine derivatives under identical conditions.
Combination of CO2, ammonia and derivatized bromoacrylic acids
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did not provide the desired oxazolidinedione derivatives (3ed* and system under alkali-free conditions to generate several derivatized
3cd*) even at higher temperature (80oC) and a prolonged time of oxazolidinediones in satisfactory-to-excellent yields. A series of
the reaction did not improve the yields. Moreover, we have tried to aromatic amine derivatives as well as bromoacrylic acids can be
generate the oxazolidinediones from several aromatic amines, and converted in excellent yields to the value-added oxazVoieliwdiAnrteicdleioOnnleinse.
DOI: 10.1039/D0CC04835F
relatively satisfactory to excellent yields, which grew from 36% Related experiments and DFT calculations are employed to explore
(3ff*) to 96% (3aa* and 3bb*) as summarized in Table 1. Typically, p- the mechanistic study on copper-facilitated CO2 capture reaction.
methoxy substituent (electron donating capacity) on aromatic Our findings demonstrate that COF-NPs composite can unlock a
amine derivatives afforded the desired oxazolidinediones (3aa*, novel route for accelerating the catalytic multicomponent reactions
3ba*, 3da*, 3ea* and 3ga*) with excellent yields in the range of 81% in the field of next-generation selective CO2 capture.
(3da*, 3ga*)-96% (3aa*). For effective comparison, m-Cl substituent
SMI thankfully acknowledges the Department of Science and
(electron withdrawing capacity) on the aromatic amine afforded the Technology DST-SERB (project reference no. EMR/2016/004956),
desired oxazolidinedione (3ff*) with only 36% yield. Surprisingly, p- New Delhi, Govt. of India, and the Board of Research in Nuclear
Cl substituent on the aromatic amine afforded the desired Sciences (BRNS), project reference no: 37(2)/14/03/2018-
oxazolidinedione (3ag*) with 76% yield. Similarly, the other groups BRNS/37003, Govt. of India for providing financial support.
such as p-NO2 (2c*) and p-CH3 (2e*) on the amines afforded the
Notes and references
desired oxazolidinediones with satisfactory yields of 68% (3cc*),
1
M. Pagani, Z. Liu, J. LaRiviere and A. C. Ravelo, Nat. Geosci.,
2010, 3, 27.
93% (3ee*) and 79% (3be*). On the other hand, the derivatized
bromoacrylic acids featuring phenyl (1b), p-methoxyphenyl (1a), p-
tolyl (1c), m-tolyl (1d), p-chlorophenyl (1e), 3,5-dimethylphenyl (1f)
and 4-hydroxyphenyl (1g) groups on alkene systems provided
moderate to excellent yields in the range of 36% (3ff*)-96% (3aa*
and 3bb*), independent of the electron-donating or electron-
withdrawing capacities of the substituents on the aromatic rings.
2
(a) K. Huang, C. -L. Sun and Z. -J. Shi, Chem. Soc. Rev., 2011, 40,
2435; (b) M. Cokoja, C. Bruckmeier, B. Rieger, W. A. Herrmann
and F. E. Kühn, Angew. Chem. Int. Ed., 2011, 50, 8510.
(a) K. Sasano, J. Takaya and N. Iwasawa, J. Am. Chem. Soc., 2013,
135, 10954; (b) L. Zhang, J. Cheng, T. Ohishi and Z. Hou, Angew.
Chem. Int. Ed., 2010, 49, 8670.
(a) H. Yoshida, H. Fukushima, J. Ohshita and A. Kunai, J. Am.
Chem. Soc., 2006, 128, 11040; (b) H. Yoshida, T. Morishita and J.
Ohshita, Org. Lett., 2008, 10, 3845.
W. -J. Yoo, T. V. Q. Nguyen and S. Kobayashi, Angew. Chem. Int.
Ed., 2014, 53, 10213.
(a) S. B. Alahakoon, C. M. Thompson, G. Occhialini and R. A.
Smaldone, ChemSusChem, 2017, 10, 2116; (b) S. Chandra, D. Roy
Chowdhury, M. Addicoat, T. Heine, A. Paul and R.
Banerjee, Chem. Mater., 2017, 29, 2074.
Y. Zeng, R. Zou and Y. Zhao, Adv. Mater., 2016, 28, 2855.
N. Huang, L. Zhai, H. Xu and D. Jiang, J. Am. Chem. Soc., 2017,
139, 2428.
M. R. Rao, Y. Fang, S. De Feyter and D. F. Perepichka, J. Am.
Chem. Soc., 2017, 139, 2421.
3
4
22
Encouraged by previously reported works, we investigated
DFT calculations which were employed to explore the reason
underlying superior catalytic performance (Fig. 4). From DFT study,
it is found that Cu@COF-BD(OH)2 activates the bromoacrylic acid
for the reaction and also stabilizes the adduct to form the
intermediate and plays a vital role in the cyclization to generate the
product (Fig. S1 and S2, ESI†). Based on DFT calculation and the
5
6
23
literature reports, we have proposed a hypothetical catalytic
mechanism of the title reaction (Figure S2, ESI†). Absorption energy
of Cu ion featuring an oxidation state of +1 is about -31.37 kcal/mol.
Absorption energy of Cu ion featuring an oxidation state of +2 is -
7
8
+
2
38.12 kcal/mol. It has been observed that Cu is stabilized by the
carbonyl group existing in the structure of COF while Cu1+ is
stabilized by Vander Waals force of interaction (Figure S1(i) , ESI†).
The overall reaction energy for the entire reaction cycle is
determined to be exothermic by -1.09 eV.
9
10 Q. Sun, B. Aguila, J. Perman, N. Nguyen and S. Ma, J. Am. Chem.
Soc., 2016, 138, 15790.
11 (a) J. L. Segura, M. J. Mancheño and F. Zamora, Chem. Soc. Rev.,
2016, 45, 5635; (b) R. P. Bisbey and W. R. Dichtel, ACS Cent. Sci.,
2017, 3, 533.
12 D. Mullangi, V. Dhavale, S. Shalini, S. Nandi, S. Collins, T. Woo, S.
Kurungot and R. Vaidhyanathan, Adv. Energy Mater., 2016, 6,
1600110.
To get hidden information about heterogeneous nature of
Cu@COF-BD(OH)2, we have conducted ICP-AES experiment of the
resultant filtrate and recovered Cu@COF-BD(OH)2. We did not
detect any noticeable copper trace in the filtrate and resultant
Cu@COF-BD(OH)2 catalyst retains almost the same copper loading
as that of fresh catalyst (≈6.80 wt%). All these observations
undoubtedly revealed the heterogeneous nature of Cu@COF-
BD(OH)2. The AAS observation corroborates well with the ICP-AES
observation because only negligible amounts of leached Cu (≈6
ppm) were detected in the resultant solution collected by hot
filtration experiment. These outcomes obtained certainly indicated
that the as-obtained Cu@COF-BD(OH)2 catalytic system is a true
heterogeneous in nature. This suggests that this COF-NPs
composite is a zero-leaching catalytic system of heterogeneous
nature (see ESI for details).
13 (a) Y. Tian, S. -Q. Xu, R. -R. Liang, C. Qian, G. -F. Jianga and X.
Zhao, CrystEngComm, 2017, 19, 4877; (b) S. Karak, S.
Kandambeth, B. P. Biswal, H. S. Sasmal, S. Kumar, P. Pachfule
and R. Banerjee, J. Am. Chem. Soc., 2017, 139, 1856.
14 H. S. Sasmal, A. Halder, S. Kunjattu H, K. Dey, A. Nadol, T. G.
Ajithkumar, P. Ravindra Bedadur and R. Banerjee, J. Am. Chem.
Soc., 2019, 141, 20371.
15 S. Karak, S. Kumar, P. Pachfule and R. Banerjee, J. Am. Chem.
Soc., 2018, 140, 5138.
16 (a) A. Khayum, M. Ghosh, V. Vijayakumar, A. Halder, M.
Nurhuda, S. Kumar, M. Addicoat, S. Kurungot and R. Banerjee,
Chem. Sci., 2019, 10, 8889; (b) A. K. Mohammed, V.
Vijayakumar, A. Halder, M. Ghosh, M. Addicoat, U. Bansode, S.
Kurungot and R. Banerjee, ACS Appl. Mater. Interfaces, 2019, 11,
30828.
17 J. F. Moulder, Handbook of X-ray photoelectron
spectroscopy. Physical electronics, 1995, 230.
18 (a) P. Muthukumar, V. V. Kumar, G. R. K. Reddy, P. S. Kumar and
S. P. Anthony, Catal. Sci. Technol., 2018, 8, 1414; (b) M. Deo, S.
Mujawar, O. Game, A. Yengantiwar, A. Banpurkar, S. Kulkarni, J.
Jog and S. Ogale, Nanoscale, 2011, 3, 4706.
19 M. C. Biesinger, L. W. Lau, A. R. Gerson and R. S. C. Smart, Appl.
Surf. Sci., 2010, 257, 887.
20 (a) S. Sharma, A. K. Singh, D. Singh and D. -P. Kim, Green Chem.,
2015, 17, 1404; (b) S. H. Kim, K. H. Kim and S. H. Hong, Angew.
Chem. Int. Ed., 2014, 53, 771: (c) S. L. Peterson, S. M. Stucka and
C. J. Dinsmore, Org. Lett., 2010, 12, 1340; (d) M. Yoshida, Y.
Komatsuzaki and M. Ihara, Org. Lett., 2008, 10, 2083.
21 T. Ishida, S. Kikuchi and T. Yamada, Org. Lett., 2013, 15, 3710.
22 J. Han, X. Sun, X. Wang, Q. Wang, S. Hou, X. Song, Y. Wei, R.
Wang and W. Ji, Org. Lett., 2020, 22, 1480.
23 (a) Q.W. Song, Z.H. Zhou and L.N. He, Green Chem., 2017, 19,
3707; (b) G. Fiorani, W. Guo and A.W. Kleij, Green Chem., 2015,
17, 1375; (c) M. North, R. Pasquale and C. Young, Green
Chem., 2010, 12, 1514.
Figure 4. Energy profile diagram for different transition states and
intermediates for the generation of oxazolidinediones.
In summary, we have developed a cyclizative CO2-incoporated
multicomponent reaction facilitated by Cu/CuxOy NPs embedded
COF catalyst for oxazolidinedione production. This cyclizative
reaction employed COF-NPs composite as a potential catalytic
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DOI: 10.1039/D0CC04835F
Cu/CuxOy NPs Architectured COF: A Recyclable Catalyst
for Oxazolidinedione Synthesis via Atmospheric Cyclizative
CO2 Utilization
Somnath Sarkar,† Swarbhanu Ghosh,† Jahangir Mondal† and Sk. Manirul Islam*,†
†Department of Chemistry, University of Kalyani, Kalyani, Nadia, 741235, W.B., India.
E-mail: manir65@rediffmail.com
This work emphasizes the utility of COF in establishing a heterogeneous catalytic
system for the generation of value-added oxazolidinediones under alkali-free condition
(sustainable approach).