Harnessing the Untapped Catalytic Potential of a CoFe2O4/Mn-BDC Hybrid MOF Composite for Obtaining a Multitude of 1,4-Disubstituted 1,2,3-Triazole Scaffolds

Disubstituted 1,2,3-Triazole Sca ﬀ olds

Article

Harnessing the Untapped Catalytic Potential of a CoFe O /Mn-BDC

Hybrid MOF Composite for Obtaining a Multitude of 1,4-

Sneha Yadav, Shivani Sharma, Sriparna Dutta, Aditi Sharma, Alok Adholeya, and Rakesh K. Sharma*

Cite This: https://dx.doi.org/10.1021/acs.inorgchem.0c00752

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sı Supporting Information

ABSTRACT: Metal−organic frameworks derived nanostructures

with extraordinary variability, and many unprecedented properties

have recently emerged as promising catalytic materials to address

the challenges in the ﬁeld of modern organic synthesis. In this

contribution, the present work reports the fabrication of an

intricately designed magnetic MOF composite based on Mn-BDC

(

manganese benzene-1,4-dicarboxylate/manganese terephthalate)

microﬂakes via a facile and benign in situ solvothermal approach.

Structural information about the as-synthesized hybrid composite

has been obtained with characterization techniques such as TEM,

SEM, XRD, FT-IR, AAS, EDX, ED-XRF, and VSM analysis. Upon

investigation of catalytic performance, the resulting material unveils

remarkable eﬃcacy toward facile access of a diverse array of

pharmaceutically active 1,2,3-triazoles from a multicomponent

coupling reaction of terminal alkynes, sodium azide, and alkyl or aryl halides as coupling partners. In addition to a wide substrate

scope, the catalyst with highly accessible active sites also possesses a stable catalytic metal center along with superb magnetic

properties that facilitate rapid and eﬃcient separation. The prominent feature that makes this protocol highly desirable is the

ambient and greener reaction conditions in comparison to literature precedents reported to date. Further, a plausible mechanistic

pathway is also proposed to rationalize the impressive potential of the developed catalytic system in the concerned reaction. We

envision that ﬁndings from our study would not only provide new insights into the judicious design of advanced MOF based

architectures but also pave the way toward greening of industrial manufacturing processes to tackle critical environmental and

economic issues.

INTRODUCTION

prevents deactivation of the catalytic system as a result of the

well separated arrangement of metal clusters by organic ligands

■

The pioneering and seminal discovery of metal organic

frameworks by a renowned chemist, Omar Yaghi, has sparked

tremendous fascination among the scientiﬁc community

worldwide. Ever since, research on the fundamental design

and exploration of this intriguing class of materials continues to

7−25

that accentuate their enduring eﬃciency.

Indeed,

integration of MOFs’ functional properties with the magnetic

properties of nanoparticles to obtain hybrid materials has

aroused broad interest, as it not only dramatically enhances

catalytic performance and durability but also facilitates

−7

expand at an impressive pace.

This upsurge of interest can

expedient separation under the inﬂuence of external magnetic

be predominantly attributed to the possibility of modifying the

organic as well as inorganic building blocks that provide

invincible strategies to produce the controlled targeted

26−31

forces.

Driven by such innovations, tremendous endeav-

ors are directed toward the quest of novel catalysts to improve

previously unexplored organic transformations. In this context,

a comprehensive literature survey reveals the scope of

advancement in click chemistry that has been creating a

−10

MOFs.

In addition, the phenomenal substructure of

MOFs also endows them with several other marvelous

attributes such as facile variability of the pore size, assorted

topologies, unprecedented high surface area, and large pore

1,12

Received: March 12, 2020

volumes.

Owing to the aforementioned remarkable

aspects, these unique architectures greatly revolutionized the

diverse emerging disciplines of catalysis, adsorption, gas

13−16

storage, sensing, and separation.

In particular, MOF

based materials have marked a signiﬁcant breakthrough in the

arena of heterogeneous catalysis since their crystal chemistry

XXXX American Chemical Society

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Article

Scheme 1. Synthesis of CoFe O /Mn-BDC Hybrid Composite

renaissance in modern synthetic chemistry for the construction

magniﬁcent catalytic performance in one-pot “click” coupling

of terminal alkynes, aryl or alkyl halides, and sodium azide to

obtain diverse triazole motifs with extraordinary pharmaco-

logical activities that can easily be metamorphosed into highly

demanding drugs. Some of the striking aspects that render this

expeditious synthetic protocol a potentially benign and

sustainable option over already existing routes are ambient

reaction conditions, a high turnover number, economic

viability, an operationally simple procedure, an environ-

mentally benign solvent, ease in scaleup, excellent yields,

short reaction times, no use of additives, excellent durability,

and eﬀortless magnetic recovery of the catalyst. To the best of

our insight, this is the ﬁrst attempt to evaluate the catalytic

eﬃcacy of three-dimensional magnetic Mn-BDC MOF ma-

terial in the concerned one-pot “click” reaction. In view of

these considerations, we foresee that the current research work

would not only enlighten the scientiﬁc community about the

rational design of advanced MOF based architectures but also

outline new directions in medicinal ﬁelds to access novel

generic drugs in an eco-friendly manner.

32−35

of ubiquitous carbon−heteroatom bonds.

Among various

modular click approaches, Huisgen cycloaddition involving

terminal alkynes and azides as substrates is the well-known

synthetic route to furnish 1,2,3-triazoles with magniﬁcent

36−39

biological and therapeutic activities.

Even a few triazole

derivatives, for example, cefatrizine, tert-butyldimethylsilylspir-

oaminooxathioledioxide, and Tazobactam, possess anticancer,

40−43

antiviral, and antibiotic properties.

However, the premier

cycloaddition route encountered serious drawbacks of diﬃcult

isolation and handling of toxic organic azides, which have

prompted chemists and engineers to design other synthetic

reaction pathways. Consequently, an alternative one pot

strategy has been explored wherein in situ organic azide

facilitates the access of entwined structures via click coupling

among terminal alkynes, sodium azide, and alkyl/aryl

4−52

halides.

Despite intensive eﬀorts, none of the aforemen-

tioned methodologies have the potential to entirely address the

formidable challenges often encountered in practical implica-

tions in pharmaceutical and medicinal industries. Severe

limitations associated with these reported metal catalyzed

transformations include harsh reaction conditions, a high

temperature, low product yield, the use of additives, metal

contamination, toxic solvents, catalyst reusability, leaching of

active species, and many more. Therefore, the current status

reveals the imperative need to explore new catalytic materials

which can not only eﬀectively deal with the aforesaid issues but

also simultaneously meet the criteria of sustainability.

EXPERIMENTAL SECTION

■

Materials and Reagents. Benzene 1,4 dicarboxylic acid (1,4-

BDC) was procured from Tokyo Chemical Industry (TCI) Pvt. Ltd.

Ferric chloride hexahydrate, cobalt chloride hexahydrate, and

manganese chloride tetrahydrate were all obtained from Sisco

Research Laboratories (SRL) Pvt. Ltd. The rest of the reagents and

starting precursors were purchased from Spectrochem Private

Limited.

In our persistent research interests in exploring benign

strategies for obtaining organic−inorganic composites and

their exploitation as potent adsorbents and catalytic

Instrumentation. A PerkinElmer Spectrum 2000 was used to

record Fourier transform infrared (FT-IR) plots of all the developed

−1

materials in the range of 4000−400 cm using KBr. The size and

3−59

systems,

we hereby elucidate the fabrication of a hybrid

shape of developed composites were determined through trans-

mission electron microscopy (TEM) micrographs obtained from FEI

CoFe O /Mn-BDC MOF composite endowed with super-

paramagnetic properties through a facile in situ solvothermal

approach. The developed intricately designed material unveils

TECHNAI G T20 at 200 kV. In addition, scanning electron

microscopy (SEM) images of synthesized materials were captured

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

recorded in the range of 4000 −400 cm . Figure 1 represents

Article

through a Jeol scanning electron microscope. Both compositional

analysis as well as elemental mapping of fabricated composites was

acquired from EDX equipment ﬁtted with a SEM instrument. A

Bruker D8 Advance instrument was employed to obtain powder X-ray

diﬀraction data of designed materials in the 2θ range of 5−80°

sulfate. Finally, GC-MS analysis of triazole products was carried out to

authenticate their successful synthesis.

RESULTS AND DISCUSSION

■

The ﬁnal catalyst was prepared as per Scheme 1. The ﬁrst step

involved in the fabrication of the overall composite is the

synthesis of CoFe O through a solvothermal preparation

−1

working at a scanning rate of 3° min . For dispersion, developed

nanoparticles were sonicated using a Tekmar Sonic Disruptor (model

TM300). Flame atomic absorption spectroscopy was employed to

calculate loading of the manganese in the ﬁnal catalyst using

N3180021 PinAAcle 500. Prepared nanoparticles and hybrid

composites were subjected to vibrating sample magnetometry analysis

wherein the magnetic ﬁeld was varied from −10000 to 10000 Oe at

room temperature (r.t.) via EV-9, Microsense, ADE. Successful

synthesis of triazoles was aﬃrmed using GC-MS analysis on an

Agilent gas chromatogram (6850 GC) with a HP-5MS 5%

phenylmethyl siloxane capillary column (30.0 m × 250 μm × 0.25

μm) and a quadrupole mass ﬁlter equipped with a 5975 mass selective

detector (MSD) using helium as the carrier gas. A JEOL JNM-EXCP-

route. After that, the synthesized CoFe O nanoparticles were

added into the precursor salts of MOF to yield the CoFe O /

Mn-BDC hybrid composite. The ﬁnal catalyst was then

subjected to a series of characterization techniques including

SEM, FT-IR, TEM, EDX, ED-XRF, XRD, VSM, and AAS.

Catalyst Characterizations. In order to aﬃrm the

presence of a functional group in the fabricated materials,

these samples were subjected to FT-IR analysis, and data were

−1

00 instrument was used to record H and C NMR of obtained

triazole derivatives.

Synthesis of Catalyst. Preparation of CoFe O . The developed

magnetic MOF composite was synthesized in a stepwise manner, out

of which the ﬁrst step included the synthesis of CoFe O using a

solvothermal synthetic strategy. In a typical procedure, 148.7 mg of

CoCl ·6H O and 337.9 mg of FeCl ·6H O were dissolved

homogeneously in 10 mL of ethylene glycol at 50 °C under magnetic

stirring. Thereafter, sodium acetate (900 mg) and PEG-6000 (500

mg) were sequentially mixed into the above solution while stirring.

After being continuously stirred for 30 min, the as obtained

homogeneous mixture was subsequently transferred to an autoclave

maintained at 160 °C for 16 h. The resulting black colored CoFe O

precipitate was isolated via an external magnet, which was further

washed several times using double-deionized water and eventually

dried at 60 °C for 6 h.

Preparation of Manganese Terephthalic Acid Metal Organic

Framework (Mn-BDC). Mn-BDC was synthesized using a procedure

reported by Shen and co-workers. First of all, MnCl ·4H O (0.76 g)

and 1,4-BDC (0.83 g) were added to a round-bottom (R.B.) ﬂask

containing 40 mL of DMF and kept under magnetic stirring. This step

was followed by the addition of 10 mL of methanol, and the resulting

solution was kept under stirring for a further 10 min to obtain a

homogeneous solution. The solution so obtained was transferred to

an autoclave held at 120 °C for 24 h. The so formed solid powder was

ﬁltered, washed using methanol, and ﬁnally dried at 110 °C for 24 h in

an oven.

Figure 1. FTIR spectral plot of (a) CoFe O , (b) Mn-BDC, and (c)

CoFe O /Mn-BDC.

FTIR spectra of CoFe O , Mn-BDC, and CoFe O /Mn-BDC.

The CoFe O spectrum reveals the presence of typical Fe−O

2 4

−1

Preparation of MOFs Decorated CoFe O₄Nanoparticles

and Co−O vibrations centered at around 609 and 872 cm . In

addition, the existence of surface hydroxyl (OH) groups on

CoFe O is conﬁrmed by the presence of a broad band at

(

CoFe O /Mn-BDC). The CoFe O /Mn-BDC hybrid composite was

2 4 2 4

^s^yⁿ^t^h^e^sⁱ^z^e^d^u^sⁱⁿ^g^a^f^a^cⁱ^l^e^p^r^o^c^e^d^u^r^e⁽^S^c^h^e^m^e¹⁾^.^F^o^r^t^hⁱ^s^,^Mⁿ^C^l2^·

H O (0.76 g) and 1,4-BDC (0.83 g) were added into an R.B. ﬂask

−1 60,62

around 3420 cm .

Further, in the FTIR spectrum of Mn-

containing 40 mL of DMF under magnetic stirring to form a

homogeneous solution. After this, 10 mL of methanol was added, and

the resulting solution was stirred for another 10 min to obtain a

−1

BDC, the appearance of two peaks at 1390 and 1560 cm

corresponds to stretching vibrations (symmetric and asym₋-

metric, respectively) in the organic ligands due to COO

homogeneous solution. After that, synthesized CoFe O nanoparticles

−1

groups. In addition to this, the existence of a peak at 748 cm

(

0.4 g) were introduced into the above solution, and the overall

clearly illustrates the eﬀective coordination of manganese ions

to 1,4-BDC. Furthermore, a comparison of the FTIR spectra of

cobalt ferrite and the ﬁnal catalyst successfully conﬁrms the

decoration of Mn-BDC MOF with inverse spinel CoFe O .

assembly was then subjected to ultrasonication for 30 min. Eventually,

the obtained solution was transferred to an autoclave and held at 120

C for 24 h. Finally, the obtained composite was magnetically

separated, washed using methanol, and dried at 110 °C for 24 h in an

oven.

The ﬁnal catalyst spectra exhibit that bands at 1560, 1390, and

−

Procedure for CoFe O /Mn-BDC Mediated Synthesis of 1,4-

Disubstituted 1,2,3-Triazoles. Terminal alkyne (1 mmol), sodium

748 cm are ascribed to the MOF, while the band around 617

−1

cm is due to the Fe−O vibrations of the CoFe O .

azide (1 mmol), aryl or alkyl halide (1 mmol), and CoFe O /Mn-

Knowledge of the structural integrity and crystallinity of

developed hybrid composites was gained through XRD

BDC (25 mg) were added to an R.B. ﬂask containing water (2 mL)

and stirred at 50 °C for the appropriate time period. The reaction was

simultaneously monitored via TLC, and once the reaction was

completed, the obtained reaction mixture was allowed to cool to room

temperature. Thereafter, the catalyst was magnetically separated

followed by extraction of the reaction mixture with ethyl acetate and

water; the so formed organic layer was dried using anhydrous sodium

analysis (Figure 2) of CoFe O , Mn-BDC, and CoFe O /

Mn-BDC. The CoFe O XRD pattern reveals the presence of

diﬀraction peaks at 2θ = 30.4°, 35.7°, 43.4°, 53.7°, 57.2°, and

62.7° which correspond to the (220), (311), (400), (422),

(511), and (440) planes. The observed 2θ diﬀraction values

Inorg. Chem. XXXX, XXX, XXX−XXX

CoFe O nanoparticles onto the Mn-BDC.

Article

TEM and SEM are considered to be one of the highly

powerful techniques that throw light not only on morpho-

logical features but also on the size of designed composites.

TEM and SEM images of these hybrid materials have been

provided in Figure 3. A TEM image of CoFe O (Figure 3d)

divulges the formation of spherical shaped nanoparticles having

a diameter of approximately 200 nm. CoFe O SEM analysis

(

Figure 3a) also discloses the fabrication of monodisperse

nanoparticles with a spherical morphology. In addition, SEM

and TEM images of bare Mn-BDC (Figure 3b and e) clearly

show that the synthesized MOF has a homogeneous laminar

microﬂake-like structure. Moreover, the SEM image of

CoFe O /Mn-BDC (Figure 3c) shows the presence of

dispersed magnetic inverse spinel cobalt ferrite nanoparticles

on the surface of bare Mn-BDC, which further validates the

successful preparation of the hybrid heterostructures.

EDX with elemental mapping was employed for the

compositional analysis of the synthesized composites.

Elemental mapping images of the hybrid CoFe O /Mn-BDC

material reveals that it is composed of ﬁve elements, namely,

Figure 2. XRD spectral plot of (a) CoFe O , (b) Mn-BDC, and (c)

CoFe O /Mn-BDC.

Co, Fe, O, Mn, and C (Figure 4). On the basis of results

obtained from elemental analysis, the loading of CoFe O

nanoparticles in the hybrid composite was found to be

approximately 36% (Table S1). In addition, the EDX spectrum

are in good agreement with the CoFe O data in JCPDS (card

number: 22-1086; Figure S1 ). Additionally, in the XRD

spectra of Mn-BDC, diﬀraction peaks at 9.4°, 14.2°, 18.8°,

of CoFe O shows distinct peaks of Co, Fe, and O, while the

9.3°, 24.4°, 28.2°, 29.4°, and 33.6° match with a simulated

EDX spectrum of CoFe O /Mn-BDC indicates the appearance

XRD plot generated utilizing previously reported single crystal

of well-deﬁned peaks of Mn and C in addition to Co, Fe, and

O, which further provides a concrete proof of the overall

X-ray data and thus con ﬁ rm the successful synthesis of the

Mn-BDC framework (Figure S2). It is also evident from the

PXRD spectra of Mn-BDC that it possesses a crystalline

structure. Finally, the emerging peaks from the XRD spectrum

of the CoFe O /Mn-BDC composite belong to both CoFe O

synthetic process (Figure 5). Moreover, ED-XRF of CoFe O /

2 4

Mn-BDC also shows peaks of Mn, Co, and Fe further

providing a vital clue for the synthesis of a hybrid

heterostructure. In addition, quantitative estimation of the

ﬁnal hybrid catalytic system was carried out using the AAS

and Mn-BDC, suggesting the successful decoration of

Figure 3. SEM micrographs of (a) CoFe O , (b) Mn-BDC, and (c) CoFe O /Mn-BDC and TEM micrographs of (d) CoFe O , (e) Mn-BDC, and

(

f) CoFe O /Mn-BDC.

2 4

Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Figure 4. (a) SEM of CoFe O /Mn-BDC hybrid composite and the corresponding elemental mapping analysis of (b) C, (c) O, (d) Mn, (e) Fe,

and (f) Co in the catalyst.

technique, which reveals that 0.499 mmol/g of manganese is

present in CoFe O /Mn-BDC.

using CoFe O /Mn-BDC as the catalyst, but the results were

2 4

not satisfactory (entries 4−6). The solvent screening studies

indicate that water behaves as the best solvent for this reaction.

Furthermore, reaction was carried out for discrete time

periods, yet the results were very inferior (entries 7 and 8).

Next, the variation in amount of catalyst in the concerned

reaction was investigated (entry 9). As evident through GC-

MS, conversion percentage was found to decrease on

decreasing the amount of catalyst. Further assessment of the

temperature conditions were carried out (entries 10 and 11).

Both an increase and decrease in temperature resulted in lower

conversion percentage. A variety of metal salts were further

screened for their ability to stimulate the multicomponent click

reaction. Adversely, the metal salts were totally ineﬀective in

promoting the reaction (entries 12 and 13). Apart from this,

the test reaction was also carried out with bare Mn-BDC,

which also results in good conversion percentage (entry 14).

Thus, the optimal reaction conditions were considered to

include phenylacetylene (1 mmol), sodium azide (1 mmol),

benzyl bromide (1 mmol), CoFe O /Mn-BDC (25 mg). and

VSM analysis was employed to study magnetic properties of

CoFe O , Mn-BDC, and CoFe O /Mn-BDC under a magnetic

ﬁeld varied from −10,000 to 10,000 Oe at r.t. (Figure 6).

Further, superparamagnetic behavior of synthesized compo-

sites is conﬁrmed by the magnetic hysteresis curves, exhibiting

no obvious remanence and coercivity. In addition, it is found

that the CoFe O saturation magnetization (Ms) value is 57

emu/g, while Mn-BDC does not possess any magnetic

character. However, upon integration with nonmagnetic Mn-

BDC, a decrease in CoFe O saturation magnetization is

observed from 57 to 22 emu/g. Nevertheless, the saturation

magnetization value of CoFe O /Mn-BDC is suﬃcient enough

as it allows its complete, eﬃcient, and rapid removal via an

external magnetic force.

Activity of CoFe O /Mn-BDC in Click Coupling

Reaction to Aﬀord 1,4-Disubstituted 1,2,3-Triazoles.

Catalytic competence of the newly fabricated CoFe O /Mn-

BDC hybrid composite was explored in the multicomponent

click protocol to access 1,4-disubstituted 1,2,3-triazoles. In

addition, the eﬀects of several thermodynamic and kinetic

parameters including time, solvent, temperature, and amount

of catalyst were studied for multicomponent click coupling.

In our preliminary reactivity tests, phenylacetylene and

benzyl bromide were chosen as model substrates, and the

results are compiled in Table 1. Initially the model reaction

was performed in water at 50 °C for 2 h without a catalyst.

However, the reaction failed to occur, further necessitating the

need of a catalyst (entry 1, Table 1). After the addition of

CoFe O /Mn-BDC into the same reaction system, 100%

water as the solvent at 50 °C for 2 h.

Substrate Scope. In a quest to broaden the versatility of

the designed hybrid composite, its catalytic eﬃciency has been

assessed for a wide array of substituted phenylacetylenes and

aryl halides under the optimized parameters (Table 2). Several

features of this simple and inexpensive protocol are worth

applauding. To our delight, when various terminal alkynes

were subjected to the reaction under optimized conditions,

triazole products were obtained with excellent conversion

percentage. Next, the scope of a series of aryl halides was

explored in the concerned reaction. The results revealed that

the reaction also proceeded well with substituted benzyl

chloride and benzyl bromide. The unsubstituted phenyl-

acetylene gave 100% conversion percentage, while with the

substituted phenylacetylenes, the conversion percentage

conversion percentage was detected after 2 h (entry 2).

Additionally, CoFe O₄nanoparticles also catalyzed the

reaction with lower conversion percentage (entry 3). We

further examined other solvents under the same conditions

Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Figure 5. EDX of (a) CoFe O , (b) CoFe O /Mn-BDC, and (c) EDXRF of CoFe O /Mn-BDC hybrid composite.

decreased with the increasing electron donating capability of

the substituents. This is evident from Table 2, entries 3, 8, and

Mechanistic Pathway. Scheme 2 illustrates a plausible

mechanistic pathway for the concerned reaction using

CoFe O /Mn-BDC as the catalyst. Initially, coordination

0, which show that the conversion percentage is 96%, 24%,

and 9% for 4-tert butyl phenylacetylene, 4-methyl phenyl-

acetylene, and 4-methoxy phenylacetylene, respectively.

Furthermore, the protocol was extended to aliphatic halides

such as n-butyl bromide, which gave satisfactory results.

Notably, the present click reaction not only exhibits wide

substrate scope and high conversion percentage but also solely

ends up in the formation of 1,4-disubstituted 1,2,3-triazoles.

between the magnetic Mn-BDC MOF based catalyst and the

terminal alkyne forms a manganese coordinated acetylene

complex (A), which is a better dienophile than acetylene itself.

Simultaneously, alkyl halide upon in situ reaction with sodium

azide results in the generation of an alkyl azide intermediate,

which subsequently interacts with complex A to form complex

B. This complex (B) further undergoes a 1,3-dipolar

Inorg. Chem. XXXX, XXX, XXX−XXX

Article

was conﬁrmed through GC-MS. Once the CoFe O /Mn-BDC

was taken out from the reaction media, there was no further

increment in conversion percentage, which clearly debarred the

probability of leached manganese metal from CoFe O /Mn-

BDC.

Reusability and recyclability are the two most desired and

indispensable parameters from an industrial and commercial

perspective. Therefore, recyclability of the developed

CoFe O /Mn-BDC hybrid catalyst was tested in the

concerned reaction using phenylacetylene and benzyl bromide

as representative substrates. Thereafter, CoFe O /Mn-BDC

was retrieved under the inﬂuence of external magnetic forces

upon the completion of the reaction, which was further washed

with acetone and dried in an oven. Subsequently, the recovered

CoFe O /Mn-BDC was utilized again in the same reaction as

shown in Figure 7, which clearly signiﬁes the retainment of its

catalytic eﬃcacy up to ﬁve consecutive runs. Further, the high

stability of the designed hybrid catalytic system is evident from

SEM, VSM, and XRD (Figures S3, S4, and S5, respectively) of

recovered CoFe O /Mn-BDC, which reveals that its morphol-

ogy, magnetization, and crystallinity remained unchanged after

catalysis.

Figure 6. VSM of (a) CoFe O , (b) Mn-BDC, and (c) CoFe O /Mn-

BDC hybrid composite.

cycloaddition reaction to generate complex C. Finally, complex

C aﬀords the desired 1,2,3-triazole moieties (D) with the

Comparison of CoFe O /Mn-BDC Activity with Re-

ported Catalytic Materials. A critical comparison of the

regeneration of CoFe O /Mn-BDC.

CoFe O /Mn-BDC catalyzed protocol was made with those

Heterogeneity and Recyclability Tests. With the aim of

determining the intrinsic stability of the designed CoFe O /

already reported in the literature, and the results are presented

in Table S2. A thorough analysis of reports related to the

concerned reaction concludes that this is ﬁrst ever MOF

composite catalyzed synthetic route to aﬀord 1,4-disubstituted

1,2,3-triazoles. Indeed, it is splendid to say that the developed

catalyst displayed its supremacy over the literature precedents

when compared on the basis of substrate scope, turnover

number, catalyst retrievability, and optimized parameters like

time, temperature, etc. In addition, CoFe O /Mn-BDC

Mn-BDC hybrid catalyst, a standard heterogeneity test was

conducted in which the test substrates (phenylacetylene and

benzyl bromide) were again subjected to optimized reaction

conditions. Thereafter, CoFe O /Mn-BDC was magnetically

removed (after half the reaction time), while the reaction was

further allowed to proceed for a prolonged duration. The

absence of a leached catalytic metal center in the supernatant

Table 1. Optimization of the Reaction Parameters

entry

catalyst

no catalyst

amount of catalyst (mg)

solvent (mL)

temp. (°C)

time (h)

conversion (%)

water

t-butanol

ethanol

acetonitrile

water

0.5

CoFe O /Mn-BDC

100

CoFe O

CoFe O /Mn-BDC

CoCl ·6H O

water

FeCl ·6H O

100

Mn-BDC

Reaction conditions: Phenylacetylene (1 mmol), sodium azide (1 mmol), benzyl bromide (1 mmol), catalyst (x mg) and solvent (2 mL).

Conversion percentages were determined via GC-MS.

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Article

Table 2. Synthesis of 1,4-Disubstituted 1,2,3-Triazoles Using CoFe O /Mn-BDC

Reaction conditions: Terminal alkyne (1 mmol), sodium azide (1 mmol), aryl/alkyl halide (1 mmol), CoFe O /Mn-BDC (25 mg), water (2 mL),

0 °C. Conversion percentages were obtained from GC-MS. TON represents no. of moles of obtained product per mole of catalyst.

retained its integral structure as well as catalytic potential even

catalytic performance of CoFe O /Mn-BDC is explored in

2 4

after ﬁve subsequent catalytic runs.

click coupling to aﬀord 1,4-disubstituted 1,2,3-triazoles. The

adopted methodology being simple and operationally facile

furnished several biologically and pharmaceutically signiﬁcant

molecules containing a triazole framework with satisfactory

yield. On the basis of previous references pertaining to the

concerned reaction, a tentative mechanism illustrating the role

of the MOF based catalyst has been proposed. Furthermore,

wider functional group tolerance, facile conditions, good

CONCLUSION

■

In conclusion, a magnetically retrievable Mn-BDC hybrid

MOF catalyst has been fabricated using a solvothermal

synthetic route and subsequently characterized with a

multitude of advanced physicochemical tools including TEM,

SEM, VSM, FTIR, XRD, EDX, ED-XRF, and AAS. Thereafter,

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

The Supporting Information is available free of charge at

Article

Scheme 2. Illustration of Plausible Mechanistic Route for the CoFe O /Mn-BDC Mediated Synthesis of 1,4 Disubstituted

,2,3-Triazoles

ASSOCIATED CONTENT

sı Supporting Information

https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00752.

■

Comparison of CoFe O PXRD with the database in

JCPDS, Mn-BDC simulated XRD, characterizations

SEM, VSM, and XRD) of the recovered CoFe O /

(

Mn-BDC, elemental mapping data of CoFe O /Mn-

BDC, comparison of CoFe O /Mn-BDC catalytic

activity, GC-MS spectra of the synthesized products,

H and C NMR of obtained triazoles (PDF)

AUTHOR INFORMATION

Corresponding Author

■

Rakesh K. Sharma − Green Chemistry Network Centre,

Department of Chemistry, University of Delhi, New Delhi

10007, India; orcid.org/0000-0003-4281-876X ;

Phone: 011-276666250; Email: rksharmagreenchem@

hotmail.com ; Fax: +91-011-27666250

Figure 7. Recycling studies for the concerned reaction [reaction

conditions: phenylacetylene (1 mmol), sodium azide (1 mmol),

benzyl bromide (1 mmol), CoFe O /Mn-BDC (25 mg), water (2

Authors

mL), 50 °C, 2 h].

Sneha Yadav − Green Chemistry Network Centre, Department

of Chemistry, University of Delhi, New Delhi 110007, India

Shivani Sharma − Green Chemistry Network Centre,

Department of Chemistry, University of Delhi, New Delhi

110007, India

Sriparna Dutta − Green Chemistry Network Centre, Department

of Chemistry, University of Delhi, New Delhi 110007, India

Aditi Sharma − Green Chemistry Network Centre, Department

of Chemistry, University of Delhi, New Delhi 110007, India

turnover number, and atom economy are some of the

intriguing features of this protocol that make it economically

compatible and competitive in comparison to those already

reported in the literature. In addition, CoFe O /Mn-BDC in

addition to facile retrievability through external magnetic

forces can also be eﬀectively reutilized for ﬁve subsequent

catalytic runs.

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Method for the Dimethyl Oxalate Hydrogenation Reaction. ACS

Article

Alok Adholeya − TERI-Deakin Nanobiotechnology Centre,

Catal. 2018, 8, 3382−3394.

TERI Gram, The Energy and Resources Institute, Gurugram

(16) Qu, B. T.; Lai, J. C.; Liu, S.; Liu, F.; Gao, Y. D.; You, X. Z. Cu-

22102, India

and Ag-Based Metal −Organic Frameworks with 4-Pyranone-2, 6-

dicarboxylic Acid: Syntheses, Crystal Structures, and Dielectric

Properties. Cryst. Growth Des. 2015, 15, 1707−1713.

Complete contact information is available at:

https://pubs.acs.org/10.1021/acs.inorgchem.0c00752

(17) Hinde, C. S.; Webb, W. R.; Chew, B. K.; Tan, H. R.; Zhang, W.

Notes

H.; Hor, T. A.; Raja, R. Utilisation of gold nanoparticles on amine-

functionalised UiO-66 (NH -UiO-66) nanocrystals for selective

tandem catalytic reactions. Chem. Commun. 2016, 52, 6557 −6560.

18) Yuan, J.; Fracaroli, A. M.; Klemperer, W. G. Convergent

The authors declare no competing ﬁnancial interest.

Synthesis of a Metal −Organic Framework Supported Olefin Meta-

ACKNOWLEDGMENTS

■

thesis Catalyst. Organometallics 2016, 35, 2149−2155.

(19) Genna, D. T.; Wong-Foy, A. G.; Matzger, A. J.; Sanford, M. S.

Heterogenization of homogeneous catalysts in metal −organic frame-

works via cation exchange. J. Am. Chem. Soc. 2013, 135, 10586−

10589.

One of the authors, Sneha Yadav, thanks the Council of

Scientiﬁc & Industrial Research (CSIR), New Delhi, India, for

a Senior Research Fellowship and also acknowledges USIC-

CLF, DU for characterizations including XRD, SEM, EDX,

FTIR, VSM analyses, and TERI (Gurugram, India) for TEM

analysis.

(20) Breeze, M. I.; Clet, G.; Campo, B. C.; Vimont, A.; Daturi, M.;

Greneche, J.-M.; Dent, A. J.; Millange, F.; Walton, R. I. Isomorphous

Substitution in a Flexible Metal −Organic Framework: Mixed-Metal,

Mixed-Valent MIL-53 Type Materials. Inorg. Chem. 2013, 52, 8171−

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