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Electronic Supplementary Information

Pd confined hierarchically conjugated covalent organic polymer for hydrogenation of nitroaromatics: Catalysis, kinetics, thermodynamics and mechanism

Deepika Yadav and Satish Kumar Awasthi*

*Department of Chemistry, University of Delhi, Delhi-7, India.

Table of ContentsMaterials and Instrumentation S2

Figure S1. Solubility of CCTP in various solvents. S2

Figure S2. PXRD patterns of CCTP after successive treatments in H2O, MeOH, DMSO, and CH3CN for 2 days.

S3

Figure S3. EDX pattern of Pd@CCTP. S3

Figure S4. XPS Complete survey spectrum of Pd@CCTP. S4

Figure S5. (a) FE-SEM and (b) TEM image of reused Pd@CCTP. S4

Figure S6. TGA curves of CCTP and Pd@CCTP. S5

Figure S7. UV-vis spectra of the reduction of 4-NP to 4-AP: (a) with NaBH4 but without Pd@CCTP, (b) With catalyst but without NaBH4.

S5

Figure S8. The corresponding plot of at/ao vs Time for reduction of 4-NP to 4-AP as controlled experiments where CCTP or Pd@CCTP was used as catalyst.

S6

Figure S9. CHNS analysis results. S6

Table S1. Reusability of Pd@CCTP. S6

Calculation of TON and TOF for Pd@CCTP catalyst. S7

Table S2. Optimization table for Pd@CCTP catalyzed Sonogashira coupling reaction.

S7

Table S3. Catalytic Performance of Pd@CCTP in the Sonogashira Coupling Reactions.

S8

1H and 13C NMR chemical shifts for 2a-2h. S91H and 13C NMR spectra of 2a-2h. S10-S171H and 13C NMR chemical shift for 3a-3e S18-S19

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2020

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Materials All the reagents, starting materials and organic substrates for hydrogenation were

purchased from Sigma-aldrich/Spectrochem Pvt. Ltd. and used as picked up. Double distilled

water was used from USIC, University of Delhi by a Milli-Q pore water purification system.

Instrumentation IR experiments were carried out in the range of 400-4000 cm-1 (Thermo

Scientific; Model: INCOLET iS50) spectrometer. PXRD experiments were performed using D8

DISCOVER X-ray diffractometer. N2 adsorption-desorption isotherm and Pore size distribution

was measured by Quantachrome Instruments; Model: ASI-CT-11. Thermo Gravimetric Analysis

dataset was obtained through Perkin Elmer, Model: TG/DTA. UV/VIS and UV-DRS

experiments were performed using Schimadzu instrument, Model: UV-2600. X-Ray

photoelectron spectroscopy (XPS) results were obtained using OMICRON Multi probe Surface

Analysis System in UHV. TEM images were obtained using FEI, Germany equipped with digital

imaging and Field Emission Scanning Electron Microscope (FESEM) Model: ZEISS Gemini

SEM-500 were used to study the sur-face morphological pattern of Pd@CCTP. 13C CP-MAS, 1H

and 13C NMR data was obtained through JEOLECX400 spectrophotometer.

Figure S1. Solubility of CCTP in various solvents (a) H2O, (b) MeOH, (c) DMSO and (d) MeCN.

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Figure S2. PXRD patterns of CCTP after successive treatments in H2O, MeOH, DMSO, and

CH3CN for 2 days.

Figure S3. EDX pattern of Pd@CCTP.

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Figure S4. XPS complete survey spectrum of Pd@CCTP showing its elemental composition.

500 nm

(b)

1 μm

(a)

Figure S5. (a) FE-SEM and (b) TEM images of reused Pd@CCTP.

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Figure S6. TGA curves of CCTP and Pd@CCTP.

(a) (b) (c)

Figure S7. UV-Vis absorption spectra of (a) p-Nitrophenol, p-Aminophenol and p-

Nitrophenoxide, (b) 2,4-dinitrophenol, 2,4-dinitrophenol in NaBH4 and 2,4-diaminphenol, (c)

Picric Acid in NaBH4 and reduced picric acid.

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Figure S8. The corresponding plot of at/ao vs Time for reduction of 4-NP to 4-AP as controlled

experiments where CCTP or Pd@CCTP was used as catalyst.

Figure S9. CHNS analysis results of CCTP.

Table S1. Reusability of Pd@CCTP.a

Number of Cycle

1 2 3 4 5 6 7 8 9

Yield (%)

99 98 98 97 97 96 95 95 94

aReaction conditions: Substituted p-nitrophenol (0.5 mmol), NaBH4 (50 mmol), Pd@CCTP (0.97 mol% Pd, 10 mg), H2O (5 mL).

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Calculation of TON and TOF for Pd@CCTP catalyst:

The Pd content of Pd@CCTP was found to be 5.14 wt% by ICP-MS.

Amount of Pd in 1g of the Pd@CCTP catalyst = (5.14 /100) x 1 = 0.0514g

The molecular weight of Pd = 106.42 g/mol

Moles of Pd obtained from the catalyst (1g) = (1 mmol / 0.10642 g) x 0.0514 = 0.483 mmol/g

= 0.000483 mmol/mg

Amount of Pd used in catalysis (10mg) = 10mg x 0.000483 mmol/mg = 0.00483 mmol

Table S2. Optimization table for Pd@CCTP catalyzed Sonogashira coupling reaction.

Solvent Catalyst Base Temp. (oC) Time (h) Yieldb

H2O - K2CO3 100 12 NRc

H2O CCTP K2CO3 150 12 NRc

H2O PdCl2 K2CO3 100 10 55

H2O Pd@CCTP K2CO3 RT 3 97

DMSO Pd@CCTP K2CO3 50 4 82

DMF Pd@CCTP K2CO3 50 4 80

H2O Pd@CCTP NEt3 RT 5 34

H2O Pd@CCTP K3PO4 RT 5 84

H2O Pd@CCTP Cs2CO3 RT 5 88aReaction conditions: Substituted aryl iodide (1.2 mmol), phenylacetylene (1 mmol), catalyst (10 mg), base

(1.5 mmol), solvent (3 mL). bIsolated Yield (%). cNo Reaction.

TON = No. of moles of product per mole of catalyst. TOF = TON/ Reaction Time (h)

IReactionConditions

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Table S3. Catalytic Performance of Pd@CCTP in the Sonogashira Coupling Reactions.a

Product Aryl Iodide Time (h) bYield (%)

3aI

3 97

3bIO2N

3 98

3cINC

3 98

3dIH2N

3 96

3e I

NH

O 3 96

aReaction Conditions: aryl iodide (1.2 mmol), phenylacetylene (1 mmol), Pd@CCTP (10 mg, 0.97 mol% Pd in

Pd@CCTP), base (1.5 mmol), solvent (3 mL). bIsolated yield.

IR R

Pd@CCTPK2CO3, H2O, RT

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1H and 13C NMR chemical shifts for 2a-2h.

2a) 1H-NMR (400 MHz, DMSO-d6) δ 8.30 (s, 1n), 6.41 (dd, J = 24.9, 8.6 Hz, 4n), 4.33 (s, 2n).13C-NMR (101 MHz, DMSO-d6) δ 148.76, 141.17, 116.07, 115.78.

2b) 1H-NMR (400 MHz, DMSO-d6) δ 6.60 (d, J = 8.7 Hz, 2n), 6.47 (d, J = 9.2 Hz, 2n), 4.53 (s, 2n), 3.57 (s, 3n).13C-NMR (101 MHz, DMSO- d6) δ 151.16, 142.82, 115.47, 114.98, 55.78.

2c) 1H-NMR (400 MHz, DMSO-d6) δ 7.34 (d, J = 8.7 Hz, 2n), 6.57 (d, J = 8.7 Hz, 2n), 6.08 (s, 2n).

13C-NMR (101 MHz, DMSO-d6) δ 153.51, 133.97, 121.21, 113.99, 96.11.

2d) 1H-NMR (400 MHz, CDCl3-d) δ 7.35-7.38 (m, 2n), 6.62 (dd, J = 8.5, 1.4 Hz, 2n), 4.23 (s, 2n).

13C-NMR (101 MHz, CDCl3-d) δ 150.74, 133.88, 120.38, 114.52, 99.83.

2e) 1H-NMR (400 MHz, DMSO-d6) δ 7.20 (d, J = 2.3 Hz, 1H), 7.00 (dd, J = 8.7, 2.3 Hz, 1H), 6.77 (q, J = 4.1 Hz, 1H), 5.33 (s, 2H).13C-NMR (101 MHz, DMSO-d6) δ 144.01, 128.57, 128.08, 119.73, 118.11, 116.95.

2f) 1H-NMR (400 MHz, DMSO-d6) δ 6.33 (s, 4n), 4.14 (s, 4n).13C-NMR (101 MHz, DMSO-d6) δ 139.44, 116.00.

2g) 1H-NMR (400 MHz, DMSO-d6) δ 6.51 (d, J = 8.2 Hz, 1n), 5.84 (d, J = 2.2 Hz, 1n), 5.72 (dd, J = 7.8, 2.2 Hz, 1n), 4.40 (s, 4n), 1.85 (s, 3n).13C-NMR (101 MHz, DMSO-d6) δ 147.57, 147.16, 130.67, 109.88, 103.75, 100.86, 16.52.

2h) 1H-NMR (400 MHz, DMSO-d6) δ 6.78 (d, J = 8.0 Hz, 2n), 6.44 (d, J = 8.4 Hz, 2n), 4.72 (s, 2n), 2.09 (s, 3n).13C-NMR (101 MHz, DMSO-d6) δ 146.74, 129.76, 124.13, 114.60, 20.64.

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1H and 13C NMR spectra.

2a

OH

NH2

OH

NH2

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2b

OHNH2

OHNH2

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2c

OMe

NH2

OMe

NH2

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2d

CN

NH2

CN

NH2

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2e

Cl

NH2Cl

Cl

NH2Cl

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2f

NH2

NH2

NH2

NH2

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2g

NH2NH2

NH2NH2

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2h

NH2

NH2

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1H and 13C NMR chemical shift for 3a-3e

3a. 1,2-diphenylethyne

1H-NMR (400 MHz, CDCl3) δ 7.54 (d, J = 7.8 Hz, 5H), 7.37 (d, J = 6.9 Hz, 5H).13C-NMR (101 MHz, CDCl3) δ 133.77, 132.88, 130.49, 129.54, 123.05.

3b. 1-nitro-4-(phenylethynyl)benzene

NO2

1H-NMR (400 MHz, CDCl3) δ 8.22 (d, J = 8.7 Hz, 2H), 7.66 (d, J = 8.7 Hz, 2H), 7.52-7.57 (m,

2H), 7.39 (dd, J = 4.8, 1.1 Hz, 3H)13C-NMR (101 MHz, CDCl3) δ 147.94, 139.72, 132.81, 125.80, 124.61, 123.07, 95.62, 88.53

3c. 4-(phenylethynyl)benzonitrile

CN

1H-NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.7 Hz, 2H), 7.59-7.62 (dd, 2H), 7.53 (d, J = 7.8 Hz,

2H), 7.35 (d, J = 7.3 Hz, 3H).13C-NMR (101 MHz, CDCl3) δ 139.44, 134.09, 133.45, 132.99, 132.74, 130.07, 129.39, 122.71,

119.37, 112.83, 100.77.

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3d. 4-(phenylethynyl)aniline

NH2

1H-NMR (400 MHz, CDCl3) δ 7.40 (d, J = 9.4 Hz, 2H), 7.10 (t, J = 8.2 Hz, 2H), 6.76 (d, J = 7.7

Hz, 2H), 6.60-6.64 (t, J = 8.4 Hz, 2H), 4.12 (s, 2H)13C-NMR (101 MHz, CDCl3) δ 145.31, 136.90, 133.84, 129.59, 120.69, 117.05, 110.47, 95.75,

89.83

3e. N-(4-(phenylethynyl)phenyl)acetamide

HN

O

1H-NMR (400 MHz, CDCl3) δ 9.84 (s, 1H), 7.84 (d, J = 7.3 Hz, 2H), 7.52-7.57 (m, 4H), 7.45-

7.50 (m, 3H), 2.04 (s, 3H)13C-NMR (101 MHz, CDCl3) δ 164.38, 136.91, 133.84, 129.59, 124.81, 120.69, 117.05, 110.47,

95.75, 89.83