Abstract

Keywords:

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1. Introduction

Chronologically, the novel application of organic synthetic strategies in constructing the one

dimensional disordered macromolecules resulted in the blossom of polymer science since 1920s.1

By the polymerisation of small building units (e.g. alkenes, amines and acids), the synthetic

organic polymers such as nylon, polyethylene etc. have found varieties of applications in daily

life.2 Polymers of Intrinsic Microporosity (PIMs) and Conjugated Microporous Polymers (CMPs)

are the recent development in the construction of nano porous organic polymers. This new field

has found startling progress in the last decade. In this context, the most important discovery

appeared in 2005 when Prof. O.M. Yaghi and co-workers developed the crystalline porous organic

polymers, i.e., the so called Covalent-organic Frameworks (COFs) with pore size ranging from 7

to 27 angstroms.3

Crystallinity and porosity are two important criteria for the designed synthesis of COF materials

besides the primary concerns of the building units and the synthetic strategies for the construction

of amorphous porous polymers. In this regard, the experience of designing principle and synthetic

strategies of other crystalline porous materials such as Metal-organic frameworks (MOFs) and

inorganic zeolites may provide insightful information. In comparison with these crystalline porous

solids, the COF materials possess the advantages of low density, rigid structures, exceptional

thermal stabilities (up to ~ 600 degree centigrade), large surface area, tunable pore size, facilely-

tailored functionality, versatile covalent-combination of building units and so on.2-3 These

advantages of COF materials give them high potential in the applications of gas adsorption, energy

storage, catalysis, drug delivery, separation, sensing and as functional devices. COFs are composed

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of light elements such as H, B, C, N and O. These light elements crystallize into periodic two-

dimensional (2D) layers or three dimensional (3D) networks by the formation of strong covalent

bonds. COFs are considered as “organic zeolites”. The synthesis and properties of 2D COFs with

layered structure are well established. The first 3D COF materials were also synthesized by Prof.

O.M. Yaghi and co-workers in 2007. A Pd-doped imine-based COF exhibited an excellent

catalytic activity towards Suzuki-Miyaura cross coupling reaction. The Pd(II) ion is doped in the

pores of a 2D imine-based COF through a coordination reaction between nitrogen atoms and Pd(II)

ions.1

2. Experimental Section

2.1 Materials and Methods

All the chemicals and reagents were purchased from commercial suppliers and used without

further purification as commercially available unless otherwise noted. All the solvents were

obtained from laboratory reagent grade. The 1H and 13C liquid NMR spectra were recorded on a

Avance-Ⅱ (Bruker) 400 MHz NMR instrument using TMS as an internal standard and CDCl3 as a

solvent. Chemical shifts are given in ppm (δ-scale) and the coupling constants are given in Hz.

PXRD patterns were obtained on a XPERT-PRO diffractometer using CuKα (λ= 1.5406 Å) with

a scan rate of o min-1. The thermal stability of the samples was evaluated by TGA under an Argon

(Ar) atmosphere over the temperature range, 40-700oC, in flowing argon at a heating rate of 20 ºC

min-1. The N2 adsorption-desorption isotherms were measured using a BEL-sorpMAX (BEL,

Japan) at 77 K. The surface areas were calculated using the BET method and the pore sizes of the

samples were calculated using the NL-DFT model. 13C CP-MAS NMR measurements were carried

out using a DELTA2 400 MHz spectrometer operating at 100 MHz for carbon NMR. Morphology
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of the polymerized materials were examined by scanning electron microscopy SEM ( ). The FT-

IR spectra were obtained from a spectrometer. Silica gel-G plates (MERCK) were used for TLC

analysis with a mixture of pet-ether and ethyl acetate as an eluent. Column chromatography was

carried out in silica gel (60-120 mesh) using pet-ether and ethyl acetate as an eluent.

2.2 Synthesis of 2,4,6-trihydrazino-1,3,5-triazine (THDT)

Compound 2,4,6-trihydrazino-1,3,5-triazine (THDT) was firstly synthesized by following method:

adding 2,4,6-trichloro-1,3,5-triazine (3.7 g, 20 mmol) to a stirred aqueous solution of

NH2NH2.H2O (85%, 30 mL). After the reaction mixture was stirred and refluxed for 3 h, then

cooled and filtered to give a white solid. The solid product was then washed with water and air-

dried, yield, 3.0 g (87%). IR (ATR): 3310 (s), 2919 (w), 1566 (s), 1433 (s), 1220 (m), 1172 (m),

1121 (m), 1071 (s), 934 (s), 801 (s), 729 (m), 616 (m), 488 (w).

2.3 Synthesis of triazine based COF (THDT-COF)

In a 100 mL Schlenk flask, a mixture of 2,4,6-trihydrazino-1,3,5-triazine (THDT) (0.5 gm, 2.92

mmol) and Isophthalaldehyde (0.59 gm, 4.38 mmol) was dissolved in a dry DMF (20 mL) at a

room temperature under an inert atmosphere. The mixture was heated at 150 ºC for 2 days and

cooled to a room temperature. Yellow precipitate was collected and washed with water, methanol

and acetone. Yield 72%

2.4 Synthesis of Pd/THDT-COF

In a 25 mL round bottomed flask, a mixture of THDT-COF (25 mg) and palladium acetate (15 mg)

in DCM (10 mL) and acetone (1 mL) was stirred for 24 hrs at a room temperature. Then it was

filtered and washed with water, hot water, methanol, THF, DCM and acetone to remove any trace

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amount of unreacted palladium acetate. It was then dried in the oven at 353 K overnight. In this

Pd catalyst, Pd content = 0.0015 wt% was determined by ICP-AES analysis.

(a)

THDT

(b)

THDT-COF

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(c)

Pd/THDT-COF

Scheme 1. Schematic representation for the (a) synthesis of THDT, (b) THDT-COF and (c)

Pd/THDT-COF.

3. Results and Discussion

3.1. FT-IR spectroscopy

The IR spectrum of THDT shows a strong C=N stretching absorption band at 1575 cm-1 which

clearly confirmed the formation of imine bond. The core triazine ring stretch appeared at 1519 and

1384 cm-1. All the aromatic ring containing C-H bonds appeared stretching frequency at 2923

cm-1. The bands observed at 3394 cm-1 for THDT-COF could be attributed to the N-H stretching

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frequency, whereas the C=N stretching frequency is shifted by 11 cm-1 and appeared at 1564

cm-1 for Pd/THDT-COF, indicating that the palladium acetate successfully coordinating with

imine bond containing proximal nitrogen atom in the network.

Figure 1. FT-IR spectra of THDT-COF, Pd/THDT-COF.

3.2. NMR spectroscopy

The idea about the chemical environment of different carbon atoms present in the polymeric

network of THDT-COF is obtained from the 13C CP MAS NMR spectroscopic analyses. The 13C

CP MAS NMR spectrum of the polymer is shown in Figure 2, which exhibits strong resonance

signals at 164, 145, 134, 130, 129, 127 ppm, corresponding to carbons in different chemical

environments as shown in the framework structure of Figure 2 (inset). The formation of the triazine

ring is confirmed from the signal at 164 ppm, whereas the peak at 145 ppm confirms the formation

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of the imine bond. The peaks at 134, 130, 129 and 127 ppm are originated from aromatic carbons

in different chemical environments in the benzene ring.

Figure 2. Solid-state 13C CP MAS NMR spectrum of THDT-COF.

Thermogravimetric analysis

TGA of THDT-COF and Pd/THDT-COF were performed, temperature up to 700 ºC, heating flow

rate 20 ºC/min in argon atmosphere shown in Figure 3. As shown in Figure 3, the decomposition

starts at 301 and 298 ºC for THDT-COF and Pd/THDT-COF respectively, which clearly confirmed

the Pd(OAC)2 coordinated to the THDT organic frameworks.

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 Figure 3. TGA curve of THDT-COF and Pd/THDT-COF.

3.4. FE-SEM & EDX analyses

The morphology was confirmed by FESEM images shown in Figure 4. FESEM image showed

that (Figure 4a) the morphology of the THDT-COF clearly indicate that adopt a structure with

porous nature. But after the incorporation of palladium acetate the morphology of the material

indicate that agglomerated morphology with spherical in shape (Figure 4b). EDX analysis of

THDT-COF and Pd/THDT-COF materials were confirmed existence of this element C, N, O and

Pd entities, shown in Figure

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 (a) (b)

Figure 4. FESEM image of (a) THDT-COF and (b) Pd/THDT-COF.

3.5. Powder XRD analysis

PXRD patterns of the THDT-COF, Pd/THDT-COF are shown in Figure 5. Using the X-ray source

of Cu Kα radiation with wavelength (λ = 1.5406 Å), the X-rays diffraction measurement was used

to determine the crystalline structure. The PXRD pattern shown THDT-COF diffracted an intense

peak with d-spacing 3.36 Å, indicates that THDT-COF is a partial crystalline material. A

comparison of the PXRD patterns of THDT-COF and Pd/THDT-COF revealed that the structure

of THDT-COF was well preserved after the treatment with Pd(OAC)2. In addition, the d-spacing

and diffraction patterns of THDT-COF and Pd/THDT-COF showed a similar pattern, but in the

Pd/THDT-COF new peak was observed in these 2θ values 11.09º, 11.90º indicating that Pd(OAC)2

coordinated with (C=N) imine bond.

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 Figure 5. Powder XRD pattern of THDT-COF and Pd/THDT-COF.

3.6. XPS analysis

The oxidation state of Pd and the strong affinity between Pd(Ⅱ) and nitrogen in imine THDT-COF

were confirmed by XPS, as shown in Figure 6. The two strong binding energy peaks at 336.2 and

341.4 eV was observed, characteristics the Pd3d5/2 and Pd3d3/2 for Pd/THDT-COF, which were

assigned to Pd species is present in +2 oxidation states. In addition, the binding energy of 336.2

eV for the Pd(Ⅱ) species in Pd/THDT-COF shifted negatively by 2.2 eV in comparison with

previously reported literature at 338.4 eV for free Pd(OAC)2. This negative shift indicates the

strong coordination of Pd(OAC)2 with the imine groups of Pd/THDT-COF.

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Figure 6. XPS spectrum of Pd/THdT-COF

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3.7. Catalytic studies of Pd/THDT-COF in Suzuki-Miyaura coupling reaction

Scheme 2. Suzuki-Miyaura coupling reaction between phenylboronic acid and bromo benzene.

First, the catalytic activity of heterogeneous Pd/THDT-COF was analyzed in Suzuki-Miyaura

coupling reaction, here the phenylboronic acid and bromobenzene was used as a model substrate

in the presence of a catalyst for optimization the reaction. Conditions and the results are

summarized in table 1. To test the use of Pd/THDT-COF as a heterogeneous catalyst for Suzuki-

Miyaura coupling reaction, phenylboronic acid was reacted with substituted bromo benzene. With

this initial result, several reaction parameters such as catalyst loading, temperature and reaction

time were screened (table 1). The effect of catalyst loading on reaction conversion was investigated

in H2O:MeOH (1:1) at 80 ºC. It was observed that the conversion was enhanced from 89 to 99%

with increasing the catalyst loading 5 to 10 mg respectively (entries 6-8, table 1). However, with

further rise in catalyst loading no significant change has been observed (entry 9, table 1). Yield of

the product increased from 95 to 99% with increase in temperature from 70 ºC to 80 ºC (entries 7-

8, table 1). To explore the optimum time consuming for the highest yield, the yield of the reaction

was monitored with respect to time. Initially, the rate of reaction was very high and it resulted 46%

conversion in first 1 hour. Prolonging the time of the reaction, the yield increased slowly and

reached to 99% in 5 hours (entry 8, table 1). No improvement in yield was observed when the

reaction was performed for 6 hours (entry 10, table 1 and Figure 7). The Suzuki-Miyaura coupling

reaction was performed in the presence of K2CO3 base, H2O:MeOH (1:1) as a solvent at 80 ºC for

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5 hours, to give 99% of yield (see table 1, entry 8), only selective product of biphenyl was

observed.

Table 1. Suzuki-Miyaura coupling reaction of phenylboronic acid with bromo benzene promoted

by catalyst Pd/THDT-COF

Entrya Catalyst Time Solvent T Yield(%)b

(mg) (h) (ºC)
1 7.5 2 H2O 25 22
2 10 5 H2O 70 58.4
3 10 6 H2O 80 64.9
4 15 5 H2O 70 72.5
5 10 5 MeOH 80 92.3
6 5 5 H2O:MeOH (1:1) 80 89
7 7.5 5 H2O:MeOH (1:1) 70 95
8 10 5 H2O:MeOH (1:1) 80 99
9 12.5 5 H2O:MeOH (1:1) 80 98
10 10 6 H2O:MeOH (1:1) 80 99
11 10 1 H2O:MeOH (1:1) 80 46
12 10 3 H2O:MeOH (1:1) 80 64
13 10 4 H2O:MeOH (1:1) 80 79
a
Reaction condition: bromobenzene (1 mmol), phenylboronic acid
(1.2 mmol), base (1.2 mmol), solvent (4 mL), bIsolated yield based
on bromobenzene

The reaction was optimized with various organic and inorganic bases such as K2CO3, CH3COONa,

NEt3, Na2CO3, NaOH (Table 2, entries 3-7) used for this coupling reaction.

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Figure 7. Plot of biphenyl yield vs. time for Suzuki-Miyaura coupling reaction of phenylboronic

acid and bromo benzene with Pd/THDT-COF.

But K2CO3 gave excellent yield and 99% conversions (Table 2, entry 3). Other bases gave a

moderate amount of yield (Table 2, entries 4-7).

The concentration of base plays a crucial role in these Pd/THDT-COF catalysed Suzuki-Miyaura

coupling reaction. When an amount of base was reduced to 1 mmol, the yield (Table 2, entry 8)

was reduced to 92%. In addition to that no product was obtained (see Table 2, entries 1 and 2)

either in the presence of THDT-COF and base or THDT-COF alone. In these reactions clearly

demonstrated that the Pd/THDT-COF was playing an important role in the Suzuki-Miyaura

coupling reaction. Therefore, Suzuki-Miyaura coupling reaction was performed at the optimum

reaction condition: phenylboronic acid (1.2 mmol), bromo benzene (1 mmol), K2CO3 and catalyst

Pd/THDT-COF (10 mg) in H2O:MeOH (1:1) at 80 ºC for 5 hours. The catalyst was separated from

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the solution by filtration. The filtrate was evaporated to obtain the crude product which purified

by column chromatography using mixed solvent petroleum ether/ethyl acetate.

Table 2. Optimisation of Suzuki-Miyaura coupling reaction conditions

aEntry Catalyst Solvent Base Yield

(%)b
1 THDT-COF H2O:MeOH (1:1) K2CO3 -
2 THDT-COF H2O:MeOH (1:1) - -
3 Pd/THDT-COF H2O:MeOH (1:1) K2CO3 99
4 Pd/THDT-COF H2O:MeOH (1:1) NaOH 81
5 Pd/THDT-COF H2O:MeOH (1:1) Et3N 79
6 Pd/THDT-COF H2O:MeOH (1:1) Na2CO3 71
7 Pd/THDT-COF H2O:MeOH (1:1) CH3COONa 40
c
8 Pd/THDT-COF H2O:MeOH (1:1) K2CO3 92
a
Reaction condition: bromo benzene (1 mmol), boronic acid (1.2 mmol),
base (1.2 mmol), MeOH (2 mL), H2O (2 mL), catalyst (10 mg), 5 h, 80ºC.
b
Isolated yield based on bromo benzene. cyield of the reaction carried out
(1.0 mmol) of base.

Later on, the formation of desired product was confirmed by NMR spectroscopy (Figure ). The

reaction was studied wide range of substrates containing both electron-withdrawing and donating

groups afforded on bromo benzene, gave the coupled biphenyl products with excellent yield (Table

3).

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Table 3. Suzuki-Miyaura coupling reaction catalyzed by Pd/THDT-COF with various

substituents.

Entrya R R1 Yieldb
(%)
1 H H 99
2 H 4-OMe 90
3 H 4-Me 89
4c H 4-Br 68
5 H 4-NO2 91
6 H 4-COCH3 98
7 H 4-CN 93
8 H 2-Me 84
a
Reaction condition: bromo benzene (1
mmol), boronic acid (1.2 mmol), base (1.2
mmol), MeOH (2 mL), H2O (2 mL),
Pd/THDT-COF (10 mg), 5h, 80ºC, bIsolated
yield based on bromo benzene.
c
phenylboronic acid (2.4 mmol).

4. Conclusions

In conclusion, the palladium acetate incorporated imine-based covalent organic frameworks have

been successfully synthesized by the facile imine-forming condensation reaction. The Pd/THDT-

COF as a highly efficient heterogeneous catalyst for promoting the Suzuki-Miyaura coupling

reaction with a variety of aryl halides and arylboronic acid, to give the excellent yield (upto 99%).

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The reaction employs environmentally friendly water as a part of solvent and the promoter/ ligand/

additives/ inert atmosphere and organic media free protocol.

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