Nanoaggregates of Pentacenequinone Derivative as Reactors ...

S1

Supporting Information

Nanoaggregates of Pentacenequinone Derivative as Reactors for

Preparation of Palladium Nanoparticles

Vandana Bhalla,* Ankush Gupta and Manoj Kumar

Department of Chemistry, UGC Centre for Advanced Studies, Guru Nanak Dev University, Amritsar,

Punjab -143005- INDIA

Page No. Contents

S2 General experimental procedures and synthetic scheme of compound 3

S3 Synthesis of compound 3

S4 Absorption spectra of compound 3 showing the variation of absorption

intensity in a H2O/THF mixture with different water fractions.

S5 Dependence of I/I0 ratios of 3 on the solvent composition of the THF/water mixture.

S6 Fluorescence spectra of compound 3 in DMSO with different conc. of 3.

S7 Fluorescence spectra of compound 3 showing the variation of fluorescence intensity

in different glycerol fractions and effect of temperature on peak intensity of 3.

S8 Absorption spectra of 3 with different metal ion and table for particle size distribution

at different molar ratio of PdCl2 /aggregates of 3

S9 TEM images of palladium nanoparticles with different molar ratio of PdCl2

/aggregates of 3 and their respective particle size distribution histograms.

S10 XRD patterns of Palladium nanoparticles and SEM-EDX spectrum of palldium

nanoparticles.

S11 Stern-Volmer plot of 3 with Pd2+

ions.

S12 Absorption spectra of 3 with Pd2+

ions in THF.

S13 Competitive and selectivity graph

S14 Fluorescence spectra of compound 4 with Pd2+

ions and fluorescence quenching of

compound 3 on test strips for the visual detection of small amount of Pd2+

ions.

S15 Fluorescence spectra of compound 3 with different metal ion as their chloride salts

S16 1H NMR of spectrum of 3.

S17 13

C NMR of compound 3.

S18 Mass spectrum of compound 3.

S19 Comparison tables

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

S2

General experimental procedures:

All reagents were purchased from Aldrich and were used without further purification. THF was dried

over sodium and benzophenone and kept over molecular sieves overnight before use. UV-vis spectra

were recorded on a SHIMADZU UV-2450 spectrophotometer, with a quartz cuvette (path length, 1

cm). The cell holder was thermostatted at 25oC. The fluorescence spectra were recorded with a

SHIMADZU 5301 PC spectrofluorimeter. The TEM mages was recorded from Transmission Electron

Microscope (TEM) - JEOL 2100F. The confocal images were taken from Laser Confocal Microscope

with Fluorescence Correlation Spectroscopy (FCS) - Olympus FluoView FV1000. 1H was recorded on a

JOEL-FT NMR–AL 300 MHz spectrophotometer using CDCl3 as solvent and tetramethylsilane SiMe4

as internal standards. Data are reported as follows: chemical shifts in ppm (δ), multiplicity (s = singlet,

d = doublet, br = broad singlet m = multiplet), coupling constants J (Hz), integration, and interpretation.

Silica gel 60 (60–120 mesh) was used for column chromatography.

Scheme S1: Synthetic scheme of pentacenequinone derivative 3.

N

BO

O

O

O

O

O

Br

Br

(i) PdCl2(PPh3)2, 2M K2CO3, 1,4-Dioxane, 90 - 100 oC

(i)

1

2N

N

3


S3

Synthesis of compound 3. To a solution of 1 (0.5 g, 1.07 mmol) and 2 (0.484 g, 2.36 mmol) in 1,4-

dioxane were added K2CO3 (0.59 g, 4.28 mmol), distilled H2O (2.1 mL), and [Pd(Cl)2(PPh3)2] (0.165 g,

0.24 mmol) under N2, and the reaction mixture was refluxed overnight. The dioxane was then removed

under vacuum, and the residue so obtained was treated with water, extracted with dichloromethane, and

dried over anhydrous Na2SO4. The organic layer was evaporated, and compound was purified by

column chromatography using (97:3 CHCl3:MeOH) as an eluent to give compound 3 in 55% yield as

yellow solid; mp: >2600C;

1H NMR (300 MHz, CDCl3): δ = 7.50 [d, 2H, J =6, ArH], 7.72-7.74 [m ,

2H, ArH], 8.13-8.16 [m, 4H, ArH], 8.20 [s, 2H, ArH], 8.61 [br, 2H, ArH], 8.97 [s, 2H, ArH], 9.03 [s,

4H, ArH]; 13

C NMR (75.45 MHz, 1,1,2,2-tetrachloroethane-d2): 123.42, 129.76, 129.99, 130.08,

130.30, 130.43, 131.53, 132.12, 134.77, 135.55, 137.32, 138.89, 148.92, 150.22, 182.70; TOF MS

ES+: 463.64 (M+1)+; Elemental analysis: Calcd. for C32H18N2O2: C 83.10; H 3.92; N 6.06; O 6.92;

Found: C 83.05 %; H 3.32 %, N 6.00 %.

Synthesis of Palladium Nanoparticles. To a 3 ml solution of compound 3 (1 mM) was added PdCl2

(10 µL of 0.1 M) in DMSO/H2O (1:1, v/v). The reaction was stirred at room temperature for 2 min and

formation of nanoparticles take place. These nanoparticles solution was used as such in the catalytic

experiment.

Reduction Procedure. 20 mg NaBH4 was added to 10 ml solution of 4-nitrophenol (1 mM) with 10 μL

of palladium nanoparticle prepared in above procedure. The reaction was carried out in ultra pure water.

These were then stirred for 4 h.


S4

level-off tail

0

0.5

1

1.5

2

2.5

3

270 300 330 360 390 420 450 480

Wavelength (nm)

Ab

sorb

an

ce

Water Fraction (%)

90

70

50

30

10

0

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.1

440 470 500

Wavelength (nm)

Ab

sorb

an

ce

Fig. S1 Absorption spectra of compound 3 (50 μM) showing the variation of absorption intensity in

a H2O/THF mixture with different water fractions. Inset: enlarge UV spectra of compound 3 (50

μM) with the addition of H2O/THF mixture in the range of 440-500 nm showing level-off long

wavelength tail.


S5

Fig. S2 Dependence of I/I0 ratios of 3 on the solvent composition of the THF/water mixture.

0

15

30

45

60

75

90

0 15 30 45 60 75 90Water Fractions (%)

Inte

nsi

ty


S6

Fig. S3 Fluorescence spectra of compound 3 in DMSO showing the variation of fluorescence

intensity in different concentration of 3.

0

20

40

60

80

100

120

140

400 450 500 550 600

Wavelength (nm)

Inte

nsity

Concentration (M)

1x10-4

1x10-5

5x10-6

1x10-6

1X10-


S7

Fig. S4 Fluorescence spectra of compound 3 (5 µM) showing the variation of fluorescence

intensity in DMSO/glycerol mixtures with different glycerol fractions

0

200

400

600

800

400 450 500 550 600

Glycerol Fraction (%) 90

70

50

30

0

Inte

nsi

ty

Wavelength (nm)

0

100

200

300

400

500

600

700

440 480 520 560 600

Wavelength (nm)

Temperature (°C)

30

75 In

ten

sity

Fig. S5 Fluorescence spectra of compound 3 (5 µM) showing the effect of temperature on peak

intensity of 3 in DMSO/ H2O mixture (1/1, v/v).


S8

Table S1. Particle size distribution at different Molar ratio of PdCl2 /aggregates of 3

Entry Molar ratio of pd2+

ions/

aggregates of 3

Morphology of

palladium nanoparticle

Particle size distribution

1 10 Well defined, Fig.S7A 1 nm 15.7 %

2 nm 21.05 %

2.5 nm 52.8 %

3 nm 10.5 %

2 30 Agglomerated, Fig.S7B 2.5 nm 5.5 %

3 nm 22.2 %

3.5 nm 44.4 %

4 nm 27.7 %

3 40 Agglomerated, Fig.S7C

2.5 nm 13 %

3 nm 30.5 %

3.5 nm 43.5 %

4 nm 13 v

4 50 Agglomerated, Fig.S7D 2.5 nm 12.9 %

3 nm 19.3 %

3.5 nm 32.2 %

4 nm 45.1 %

4.5 nm 22.5 %

Fig. S6 UV-vis spectra of Compound 3 (10.0 μM) upon additions of 500 µM of various metal ions in DMSO:H20

(1:1), buffered with HEPES, pH = 7.0.

( 3, Mg2+

, Cd2+

, Hg2+

, Ni2+

,

Zn2+

, Cu2+

, Pb2+

, Ba2+

, Co2+

,

Na+, K

+, and Li

+)

Ab

sorb

an

ce

Wavelength (nm)

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

200 300 400 500 600


S9

Fig. S7 TEM images of palladium nanoparticles with different molar ratio of PdCl2 to aggregates of

compound 3; molar ratio (A) 10 (B) 30 (C) 40 (D) 50. On right side of these images their respective particle

size distribution histogram.

5 nm

0

10

20

30

40

50

60

1 2 2.5 3

Particle size (nm)

Fre

quen

cy

(%)

(A)

5 nm

0

10

20

30

40

50

2.5 3 3.5 4

Particle size (nm)

Fre

quen

cy

(%)

(B)

5 nm

0

10

20

30

40

50

2.5 3 3.5 4

Particle size (nm)

Fre

quen

cy

(%)

(C)

5 nm

0

10

20

30

40

50

2.5 3 3.5 4 4.5

Particle size (nm)

Fre

quen

cy

(%)

(D)


S10

Fig. S8 (A) XRD patterns of Palladium nanoparticles and (B) SEM-EDX spectrum of nanoaggregates of 3 in

presence of palladium chloride show the presence of palladium nanoparticles

2-theta (deg)

Inte

nsi

ty

(A) 39.9°

46.3°

67.1° 81.1° 85.7°

(B)


S11

Fig. S9 Variation of fluorescence of nanoaggregates of compound 3 (1 μM) at 481 nm in DMSO/H2O

(1:1, v/v) buffered with HEPES, pH =7.0, λex=310 nm in the presence of different concentrations of

Pd2+

ions (Io /I; Io=initial fluorescence intensity at 481 nm; I= fluorescence intensity after the

addition of Pd2+

ions at 481 nm).

Pd2+

ions (1 μM)

I o/I

1

2

3

4

5

6

7

8

0 100 200 300 400

I o/I

1

1.125

1.25

1.375

1.5

0 50 100

Pd2+

ions (1 μM)


S12

Fig. S10 UV-vis spectra of Compound 3 (10 μM) upon additions of 20 equivalents of Pd2+

ions

in THF. Inset: enlarge UV spectra of compound 3 (10 μM) in the range of 400-500 nm.

0

1

2

3

200 300 400 500

Pd2+

200 μM

0 μM

Wavelength (nm)

Ab

sorb

an

ce

0

0.1

0.2

0.3

0.4

0.5

400 425 450 475 500

Shows no interaction with

Pd2+

ions


S13

0

15

30

45

60

75

90

1 3 5 7 9 11 13

Series1 Series2A B

Pd2+

Ba2+

Mg2+

Cd2+

Hg2+

Ni2+

Zn2+

Cu2+

Pb2+

Co2+

K+

Na+ Li

+

Fig. S11 Fluorescence response of 3 (1 μM) to various cations (400 µM) in DMSO/water

(1:1) buffered with HEPES, pH = 7.0; λex = 310 nm. Bars represent the emission intensity

ratio (I0 - I/I0) ×100 (I0 = initial fluorescence intensity at 481 nm; I = final fluorescence

intensity at 481 nm after the addition of Pd2+

ions). (A) The sky blue bars represent the

addition of individual metal ions, (B) the brown bars represent the change in the emission that

occurs upon the subsequent addition of Pd2+

(400 µM) to the above solution.

(Io-I

/Io)x

100


S14

Fig. S12 Change in the fluorescence spectra of compound 4 (1 μM) upon various additions of Pd2+

in

DMSO/water (1:1) buffered with HEPES, pH = 7.0; λex=328nm.

Fig. S13 Photographs (under 365 nm UV-light) Fluorescence quenching of compound 3 on test

strips for the visual detection of small amount of Pd2+

ions (A) test strip; Pd2+

ions of different

concentration (B) 10-3

M (C) 10-5

M (D) 10-7

M.

0

50

100

150

200

450 500 550 600 650

Pd2+

0 μM

500 μM

Wavelength (nm)

Inte

nsi

ty


S15

Fig. S14 Change in the fluorescence spectra of compound 3 (1 μM) upon additions of metal ion (500

μM) as their chloride salt in DMSO/water (1:1) buffered with HEPES, pH = 7.0.

Inte

nsi

ty

Wavelength (nm)

( 3, Mg2+

, Hg2+

, Ni2+

, Zn2+

,

Cu2+

, Co2+

, Na+ and K

+)

0

50

100

150

200

250

420 480 540 600


S16

Fig. S15 1H NMR of spectrum of compound 3 in CDCl3

O

O

N

N

CH2Cl2

H2O

TMS


S17

O

O

N

N

Fig. S16 13

C NMR of compound 3 in 1,1,2,2-tetrachloroethane-d2


S18

O

O

N

N

Fig. S17 Mass spectrum of compound 3


S19

Table S2: Comparison of present method over other reported procedure in literature for the preparation of

palladium nanoparticles.

Table S3: Comparison of present probe 3 for Pd2+

ions detection over other reported Pd2+

ion detector

reported in the literature

S.No Reaction time to

prepare Pd

nanoparticles

Journal

1 2 min. Present Manuscript

2 12 h Green Chem., 2012, 14, 586

3 30 min. Phys. Chem. Chem. Phys., 2012, 14, 6026.

4 5 h J. Mater. Chem., 2012, 22, 17604.

5 9 h J. Mater. Chem., 2012, 22, 18314

6 3 h Green Chem., 2012, 14, 1073.

7 48 h Chem. Commun., 2012,48, 8955.

8 3-1 h Chem. Commun., 2012, 48, 2021.

S.No System Utilization of

fluorescent

nanoaggregates

for Pd2+

ions

detection

Test strip for

detection of

trace amount of

Pd2+

ions

Reduction of

Pd2+

to Pd

nanoparticles

Journal

1 Compound 3

Yes Yes Yes Present manuscript

2 Solution phase No No No Chem. Commun., 2011,

47, 9101

4 Solution Phase No No No Chem. Commun., 2012,

48, 2867

5 Solution Phase No No No Org. Lett., 2011, 13,

4922


46, 3964


46, 1079

8 Solution Phase No No No Asian J. Org. Chem.

2012, DOI:

10.1002/ajoc.201200061


http://pubs.rsc.org/en/journals/journal/jm

http://pubs.rsc.org/en/journals/journal/jm

Nanoaggregates of Pentacenequinone Derivative as Reactors ...

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