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S1
Supporting Information
Pentacenequinone derivatives for preparation of gold nanoparticles: Facile Synthesis and
Catalytic Application
Kamaldeep Sharma nee Kamaldeep, Sandeep Kaur, Vandana Bhalla,* Manoj Kumar and Ankush Gupta
Department of Chemistry, UGC Centre for Advanced Studies-I, Guru Nanak Dev University,
Amritsar, Punjab -143005- INDIA
S3-S5 Comparison table.
S6 General experimental procedures.
S7 Synthesis of gold nanoparticles and catalysis of p-nitroaniline.
S8 Absorption spectra of derivative 3 showing the variation of absorption intensity in a
H2O/THF mixture with different water fractions and pictorial representation of derivative
3.
S9 Dependence of I/Io ratios of derivative 3 on the solvent composition of the H2O/THF
mixture and SEM images of aggregates of derivative 3 in 60%, 80% and 90% H2O/THF
mixture.
S10 SEM images of aggregates of derivatives 4 and 6 in 60% and 90% H2O/THF mixture.
S11 UV-vis spectra of compound 3 upon additions of various metal ions as their perchlorate
and chloride salt in H2O/THF.
S12 Competitive and selectivity graph of derivative 3 to various metal ions and UV-vis spectra
of compound 3 upon various additions of Au3+
ions in H2O/THF.
S13 Graphical representation of rate of formation of gold nanoparticles
S14 Stern-Volmer plot of aggregates of derivative 3.
S15 Fluorescence spectra of derivative 3 upon additions of various metal ions as their
perchlorate and chloride salt in H2O/THF.
S16 Overlay 1H NMR spectra of 3 and gold nanoparticles of 3 after filteration with THF.
S17 Fourier transforms infrared absorption spectra for compound 3 and gold after filteration
with THF.
S18 UV-vis spectra of compound 3 upon various additions of Au3+
ions in THF and Polarised
optical microscope (POM) image of derivative 3.
S19 XRD diffraction patterns of gold nanoparticles of derivative 3 and UV-vis spectra of 4-
Bromobenzonitrile (10 μM) upon various additions of Au3+
ions in H2O/THF.
S20 SEM image of gold nanoparticles of 4-Bromobenzonitrile.
S21 Absorbance and Fluorescence spectra of compound 4 showing the variation of absorbance
and fluorescence intensity in H2O/THF mixture from 0 to 90%.
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2014
S2
S22 Absorbance and Fluorescence spectra of compound 6 showing the variation of absorbance
and fluorescence intensity in H2O/THF mixture from 0 to 90%.
S23 Absorbance and Fluorescence spectra of 4 upon addition of Au3+
ions in H2O/THF (9/1).
S24 Absorbance and Fluorescence spectra of 6 upon addition of Au3+
ions in H2O/THF (9/1).
S25 XRD diffraction patterns of gold nanoparticles of derivatives 4 and 6.
S26 Transmission electron microscope (TEM) images and size distribution of gold
nanoparticles of derivatives 3, 4, and 6.
S27 Graphical representation of Time vs. absorbance plot and regression plot for the reduction
of p-nitroaniline catalyzed by gold nanoparticles of derivatives 3, 4 and 6. S28
UV-vis spectra for the reduction of p-nitroaniline by adding NaBH4 aqueous solution using
gold nanoparticles of derivatives 4 and 6 as catalysts.
S29 1H NMR of spectrum of p-phenylenediamine.
S30 1H NMR of spectrum of derivative 3.
S31 Mass spectrum of compound 3.
S32 1H NMR of spectrum of derivative 4.
S33 13
C NMR of spectrum of derivative 4.
S34 Mass spectrum of compound 4.
S35 1H NMR of spectrum of derivative 5.
S36 13
C NMR of spectrum of derivative 5.
S37 Mass spectrum of compound 5.
S38 1H NMR of spectrum of derivative 6.
S39 13
C NMR of spectrum of derivative 6.
S40 Mass spectrum of compound 6.
S41 Comparison table
S3
Reaction time for the reduction of p-
nitroaniline to p-phenylenediamine
Journal
5min. Present manuscript
30 min. Chem. Sci., 2013, 4, 3667.
59 min. Ind. Eng. Chem. Res., 2013, 52, 556.
25 min. CrystEngComm, 2012, 14, 7600
70 min. J. Phys. Chem. C, 2012, 116, 23757
17 min. Langmuir, 2011, 27, 3906
56 min. J. Phys. Chem. C, 2009, 113, 17730
20 min. J. Phys. Chem. C, 2009, 113, 5157
86 min. J. Phys. Chem. C, 2009, 113, 5150
Table S1: Comparison of present method over other reported procedure in literature for the reduction of p-
nitroaniline to p-phenylenediamine by gold nanoparticles of derivative 3.
S4
Method of
formation of gold
nanoparticles
Size of gold
nanoparticles
Reaction time to
prepare gold
nanoparticles
Reducing agent
or surfactants
Reaction temp.
(in oC) Journals
Wet chemical
method 5-10 nm 2 min. No Room temp. Present manuscript
Ultrasound
assisted interfacial
method
143.9 ± 17.5-
249.1 ± 31.3 nm 120 sec.
2-ethoxyaniline
(EOA) 45 Chem. Commun., 2013, 49, 987
Chemical method 12 nm 10 min. NaBH4 0 J. Mater. Chem.C,2013, 1, 902.
Chemical method 20 nm 2 min Glycerol Room temp.
Advances in Nanoparticles,
2013, 2, 78
Chemical method 6-17.5 nm - NaBH4 - Chem. Commun., 2013, 49,
3218
Seed-mediated
growth method
63.6 nm
60 min NaBH4 30
J. Phys. Chem. C 2012, 116,
23757
Chemical method 20-50 nm 90 min Sodium citrate 80-85 Nanoscale Research Letters
2012, 7, 420
Seed-mediated
method 56.4 ± 1.4 nm
2 h NaBH4 Ice cold
solution
Phys. Chem. Chem. Phys.,
2012, 14, 9343
Chemical method 50-200 nm 15 min. Citrate ~100 Langmuir, 2010, 26, 3585
Chemical method ~20 nm 30 min
Tripotassium
citrate ~100
J. Phys. Chem. B 2006, 110,
17813
Wet Chemical
method
Large size
(Hundred
nanometers)
Several hours
No Room temp. Chem. Commun. 2004, 1182
Wet chemical
method Micrometer
sized Several minutes No Room temp Angew. Chem. Int. Ed. 2004,
43, 6360
Wet Chemical
method
4-33 nm 30-150 min. - 80 Macromol. Rapid Commun.
2003, 24, 1024
Wet Chemical
method
5-20 nm
- No Room temp Chem. Mater. 1999, 11, 3268
Table S2: Comparison of present method for the preparation of gold nanoparticles over other reported procedure in literature.
S5
Paper Journal System Detection Limit
Present Manuscript
Fluorescent Aggregates
H2O/THF (6/4 v/v) 100 nM
Analyst, 2013, 138, 3638
Non aggregated form
CH3CN–HEPES buffer (1/1 v/v) 0.6 ppm
Org. Lett. 2012, 14, 5062
Non aggregated form
(0.25% DMSO in HEPES) 0.4 µM
Chem. Commun. 2012, 48, 744
Non aggregated form
EtOH/ PBS buffer ( 1/1 v/v) 320 nM
Chem. Commun. 2011, 47, 4703
Non aggregated form
(0.3% DMF in PBS HEPES) 290 nM
Org. Lett. 2010, 12, 932
Non aggregated form
(Ethanol) 64 ppb
Org. Lett. 2010, 12, 401
Non aggregated form
CH3CN/PBS buffer (1/1 v/v) 0.4 ppm
Chem. Commun. 2009, 7218
Non aggregated form
EtOH–HEPES and DMSO–HEPES
buffer
(1/1 v/v)
100 ppb
Table S3: Comparison of detection limit reported in the present manuscript for detection of gold ions with other reported
detection limits in the literature.
S6
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 250
C. The fluorescence spectra were recorded
with a SHIMADZU 5301 PC spectrofluorimeter. Scanning electron microscope (SEM) images
were obtained with a field-emission scanning electron microscope (SEM CARL ZEISS SUPRA
55). Polarized optical microscope (POM) images were recorded on NIKON ECLIPSE LV100
POL. Elemental analysis (C, H, N) was performed on a Flash EA 1112 CHNS-O analyzer (Thermo
Electron Corp.). 1H was recorded on a JEOL-FT NMR–AL 300 MHz spectrophotometer using
CDCl3 as solvent and tetramethylsilane SiMe4 as internal standards. UV-vis studies were
performed in THF and H2O/THF mixture. 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 (60–120 mesh) was used for column chromatography.
S7
Synthesis of Gold Nanoparticles. To a 3 ml solution of compound 3, 4, and 6 (0.2 mM) was
added 0.1 M AuCl3 (15 μL for 3, 45 μL for 4, 30 μL for 6) in H2O/THF (6:4, v/v). The reaction
was stirred at room temperature for 2 min and formations of nanoparticles take place. These
nanoparticles solution was used as such in the catalytic experiment.
Catalysis of p-nitroaniline. 300 µL of 1 mM p-nitroaniline, 300 µL of 10 mM NaBH4 and 5 µL
(2.5 nmol) of gold nanoparticles of derivative 3, 4, and 6 were mixed. After that, different volumes
of deionized water were added to the reaction mixture to nullify the dilution effect. After stirring
the reaction mixture, a colour change of the reaction mixture from yellow to colourless was
observed which indicate the reduction of p-nitroaniline to p-phenylenediamine. The reduction of
p-nitroaniline takes 5 min. in case of derivative 3, 24 min. in case of 4 and 18 min. in case of
derivative 6. The formation of the reduced product p-phenylenediamine was confirmed from the
1H-NMR spectra (in CDCl3) of the product (see pS29). The reduction of p-nitroaniline was also
carried out in excess. After the complete reduction, the product was purified by column
chromatography and found to be in 98% yield. 1H NMR (400 MHz, CDCl3): δ = 3.29 [s, 4H, NH2],
6.57 (s, 4H, ArH].
S8
Fig. S2 Schematic view of intermolecular charge transfer (ICT) state of derivative 3 with their head to tail
alignment.
Ab
so
rban
ce
Water fraction (%)
90
80
70
60
50
40
30
20
10
0
Wavelength (nm)
Wavelength (nm)
Ab
so
rban
ce
Level off tail
423 nm
Fig. S1 Absorption spectra of derivative 3 (10 μM) showing the variation of absorption intensity in H2O/THF
mixture with different fractions of H2O. Inset: enlarge UV-vis spectra of derivative 3 (10 μM) with the addition
of H2O/THF mixture in the range of 400-600 nm showing level-off long wavelength tail.
S9
Fig. S3A Dependence of I/Io ratios of derivative 3 on the solvent composition of the H2O/THF mixture.
Water Fractions (%)
Inte
nsit
y
(A)
(B)
Fig. S3B SEM images of aggregates of derivative 3 in (a) 60% H2O/THF mixture (b) 80% H2O/THF mixture (c) 90%
H2O/THF mixture. Scale bar (a), (b) and (c) 20 µm.
(b)
20 µm
(c) (a)
S10
10 µm 1 µm
(a)
Fig. S4A SEM images of aggregates of derivative 4 (a) in 60% H2O/THF mixture (b) in 90% H2O/THF mixture. Scale bar
(a) 1µm (b) 10 µm.
(b)
200 nm
(a)
Fig. S4B SEM images of aggregates of derivative 6 (a) in 60% H2O/THF mixture (b) in 90% H2O/THF mixture. Scale bar
(a) and (b) 200 nm.
(b)
200 nm
S11
Fig. S6 UV-vis spectra of derivative 3 (10 μM) upon additions of 500 μM of various metal ions as their
chloride salt in H2O/THF (6/4), buffered with HEPES, pH = 7.0.
Ab
so
rban
ce
3
Al3+
Hg2+
Na+
Pd2+
Cu2+
Ca2+
Ni2+
Zn2+
K+
Co2+
Cr3+
Au3+
Wavelength (nm)
Fig. S5 UV-vis spectra of derivative 3 (10 μM) upon additions of 500 μM of various metal ions as their perchlorate
salt in H2O/THF (6/4), buffered with HEPES, pH = 7.0.
Ab
so
rban
ce
Wavelength (nm)
3
K+
Li+
Hg2+
Co2+
Ag+
Pb2+
Cu2+
Cd2+
Ni2+
Na+
Zn2+
Au3+
Ba2+
Fe3+
S12
Fig. S8 UV-vis spectra of derivative 3 (10 μM) upon various additions of Au3+
ions in H2O/THF (6/4). Inset:
enlarge UV spectra of compound 3 (10 μM) in the range of 400-700 nm.
Wavelength (nm)
Ab
so
rban
ce
Au3+
(equiv.)
50
0
Appearance of band at 562 nm indicates
the formation of gold nanoparticles
Ab
so
rban
ce
Wavelength (nm)
562 nm
Fig. S7 Fluorescence response of derivative 3 (10 μM) to various cations (500 μM) in H2O/THF (6/4); buffered
with HEPES, pH = 7.0; λex = 310 nm. Bars represent the emission intensity ratio (Io – I)/Io ×100 (Io = initial
fluorescence intensity at 476 nm; I = final fluorescence intensity at 476 nm after the addition of Au3+
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 Au3+
(500 μM) to the above solution.
Au3+
Fe3+
Hg2+
Co2+
Ni2+
Cd2+
Pd2+
Pb2+
Zn2+
Cu2+
Ba2+
Ag+ Li
+ Na
+ K
+
(Io-I
)/I o
x10
0 (A)
(B)
S13
The first order1 rate constant for the formation of gold nanoparticles was calculated from the
changes of intensity of absorbance of aggregates of derivative 3 in the presence of Au3+
ions at
different time interval2.
From the time vs. absorbance plot at fixed wavelength 562 nm by using first order rate equation
we get the rate constant = k = slope×2.303 = 1.43×10-3
Sec-1
.
1 Luty-Błocho, M.; Pacławski, K.; Wojnicki, M.; Fitzner, K. Inorganica Chimica Acta 2013, 395
189–196.
2 Goswami, S.; Das, S.; Aich, K.; Sarkar, D.; Mondal, T. K.; Quah, C. K.; Fun, H-K. Dalton Trans. 2013,
42, 15113–15119.
(A)
Fig. S9 Graphical representation of the rate of formation of gold nanoparticles of derivative 3. (A) Time
(min.) vs. absorbance plot at 562 nm (B) regression plot of A.
Ab
so
rban
ce
Time (min.)
(B)
Regression Statistics
Multiple R 0.992481
R Square 0.985019
Intercept 0.103885
Slope 0.003745
S14
Fig. S10 Variation of fluorescence intensity of aggregates of derivative 3 (10 μM) at 476 nm in H2O/THF (6:4, v/v)
buffered with HEPES, pH =7.0, λex. = 310 nm in the presence of different concentrations of Au3+
ions (Io/I; Io = initial
fluorescence intensity at 476 nm; I= fluorescence intensity after the addition of Au3+
ions at 476 nm). Inset shows the
linear Stern-Volmer plot at lower concentration of Au3+
ions.
I o/I
Au3+
ions (10 μM)
Au3+
ions (10 μM)
Io/I
S15
Fig. S11 Fluorescence spectra of derivative 3 (10 μM) upon additions of various metal ions (500 μM) as their
perchlorate salt in H2O/THF (6/4) buffered with HEPES, pH = 7.0.
Inte
nsit
y
Wavelength (nm)
3, Zn2+
, Cu2+
, Ni2+
, Co2+
, Pb2+
,
Cd2+
, Hg2+,
Ba2+
, Ag
+, K
+, Na
+,
Li+
Fe3+
Fig. S12 Fluorescence spectra of derivative 3 (10 μM) upon additions of various metal ions (500 μM) as their chloride
salt in H2O/THF (6/4) buffered with HEPES, pH = 7.0.
Wavelength (nm)
Inte
nsit
y
/n
sity
3, Hg2+
, Co2+
, Cu2+
, Cr3+
, Al3+
,
Ni2+
, Zn2+
, Pd2+
, Ca2+
, K+, Na
+
S16
Compound 3 + AuCl3
After filtered with THF
(Filterate)
Compound
3
Fig. S13: Overlay 1H NMR spectra of derivative 3 and gold nanoparticles of derivative 3 after filteration with THF.
S17
Fig. S14 Fourier transforms infrared absorption spectra of derivative 3.
Wavenumber (cm-1
)
% T
ran
sm
itta
nce
Fig. S15 Fourier transforms infrared absorption spectra of gold nanoparticles of derivative 3 after
filteration with THF.
S18
Fig. S16 UV-vis spectra of derivative 3 (10 μM) upon various additions of Au3+
ions in THF. Inset: enlarge UV
spectra of compound 3 (10 μM) in the range of 400-700 nm.
Wavelength (nm)
Au3+
(equiv.)
50
0
Ab
so
rban
ce
Ab
so
rban
ce
Wavelength (nm)
Fig. S17 Polarized optical micrograph of gold nanoparticles of derivative 3 at room temperature through crossed
polarizing filters.
No absorption band
at 562 nm
S19
Fig. S18 Representative XRD diffraction patterns of gold nanoparticles of derivative 3.
2-theta (deg)
30 40 50 60 70 80
0.0e+000
2.0e+003
4.0e+003
6.0e+003
8.0e+003
30 40 50 60 70 80 -1000
1000
Intensity (cps)
2-theta (deg)
Meas. data:AUNP/Data 1
Intensity (cps)
(111)
(200) (220) (311)
)
In
ten
sity (
cp
s)
Fig. S19 UV-vis spectra of 4-Bromobenzonitrile (10 μM) upon various additions of Au3+
ions in H2O/THF (6/4).
Inset: enlarge UV spectra of 4-Bromobenzonitrile (10 μM) in the range of 400-700 nm.
Ab
so
rban
ce
Wavelength (nm)
Au3+
(equiv.)
50
0
Wavelength (nm)
Ab
so
rban
ce
After 60 min.
540 nm
S20
Fig. S20 SEM image of gold nanoparticles of 4-Bromobenzonitrile showing size of gold nanoparticles. Scale bar 200 nm.
S21
Fig. S21 Absorption spectrum of derivative 4 (10 μM) showing the variation of absorption intensity in
H2O/THF mixture with different fractions of water. Inset: enlarge UV-vis spectra of derivative 4 (10 μM) with
the addition of H2O/THF mixture in the range of 450-600 nm showing level-off long wavelength tail.
Wavelength (nm)
Ab
so
rban
ce
Level off tail
Water fraction (%)
90
80
70
60
50
40
30
20
10
0
Ab
so
rban
ce
Wavelength (nm)
Fig. S22 Fluorescence spectrum of derivative 4 (10 µM) showing the variation of fluorescence intensity in
H2O/THF mixture from 0 to 90% volume fractions of water in THF. λex = 327 nm.
Wavelength (nm)
Inte
nsit
y
Water fraction (%)
90
80
70
60
50
40
30
20
10
0
S22
Wavelength (nm)
Inte
ns
ity
Water fraction (%) 90 80 70 60 50 40 30 20 10 0
Fig. S24 Fluorescence spectrum of derivative 6 (1x10-4
M) showing the variation of fluorescence intensity
in various H2O/THF mixtures. λex = 322 nm.
Water fraction (%) 90 80 70 60 50 40 30 20 10 0
A
bs
orb
an
ce
Wavelength (nm)
Level-off tail
Fig. S23 Absorption spectrum of derivative 6 (10 μM) showing the variation of absorption
intensity in H2O/THF mixture with different fractions of water.
S23
Fig. S26 Fluorescence spectrum of derivative 4 (10 µM) upon addition of Au3+
ions in H2O/THF (9/1);
buffered with HEPES, pH = 7.0
0 equiv.
150 equiv.
Au3+
Inte
nsit
y
Wavelength (nm)
Wavelength (nm)
Ab
so
rban
ce
Au
3+ (equiv.)
70
0
550 nm
Ab
so
rban
ce
Wavelength (nm)
After 1 hr of titration
After 1/2 hr of titration
Fig. S25 UV-vis spectrum of derivative 4 (10 μM) upon various additions of Au3+
ions in H2O/THF (9/1). Inset:
enlarge UV spectrum of compound 4 (10 μM) in the range of 450-700 nm showing a new absorption band at 550 nm.
S24
Fig. S27. UV-vis spectrum of derivative 6 (10 µM) upon addition of Au3+
ions (10 equiv.) in
H2O/THF (9:1) mixture; buffered with HEPES, pH = 7.0.
Wavelength (nm)
Ab
so
rba
nce
580 nm, formation of gold nanoparticles
Au3+
(equiv.)
10
0
Fig. S28 Fluorescence spectrum of derivative 6 (1 x 10-4
µM) upon addition of Au3+
ions in
H2O/THF (9:1); buffered with HEPES, pH = 7.0. λex = 322 nm
Wavelength (nm)
Inte
ns
ity
Au3+
0 equiv.
10 equiv.
S25
30 40 50 60 70 80
0
1000
2000
3000
30 40 50 60 70 80
-400
-200
0
200
400
Inte
nsity (
cp
s)
2-theta (deg)
Inte
nsity (
cp
s)
2-theta (deg)
(311) (220)
(200)
(111)
Fig. S29 Representative XRD diffraction patterns of gold nanoparticles of derivative 4.
40 50 60 70 80
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
7000
7500
8000
8500
9000
2-theta (deg)
Inte
nsity (
cps)
Fig. S30 Representative XRD diffraction patterns of gold nanoparticles of derivative 6.
(111)
(200)
(220) (311)
S26
Fig. S31 Transmission electron microscope (TEM) images and size distribution of gold nanoparticles of (A)
derivative 3 (B) derivative 4 (C) derivative 6. Scale bar (A) 20 nm (B) 200 nm (C) 20 nm.
Fre
qu
en
cy
(%
)
Particle size (nm)
20 nm
(C)
Fre
qu
en
cy
(%
)
Particle size (nm)
20 nm
(A)
Particle size (nm)
Fre
qu
en
cy
(%
)
200 nm
(B)
S27
Catalytic reduction of p-nitroaniline follows Pseudo-first-order kinetics.3 The apparent rate
constants for the degradation of p-nitroaniline by gold nanoparticles of derivatives 3, 4 and 6 listed
in following table:
(3) Zelentsov, S. V.; Simdyanov, I. V.; Kuznetsov, M. V. High Energy Chemistry 2005, 39, 309-312.
Gold nanoparticles Rate constant
Derivative 3 1.62×10-2 sec-1
Derivative 4 5.64×10-3 sec-1
Derivative 6 5.67×10-3 sec-1
Ab
so
rban
ce
Time (min.)
Regression Statistics
Multiple R 0.986152
R Square 0.972496
Intercept 3.3815
Slope -0.14706
(C) (D)
Fig. S32 Graphical representation of Time vs. absorbance plot and regression plot for the reduction of p-nitroaniline
catalyzed by gold nanoparticles (A) and (B) of derivative 3 (C) and (D) of derivative 4 (E) and (F) of derivative 6.
Regression Statistics
Multiple R 0.996027
R Square 0.99207
Intercept 3.289689
Slope -0.14768
0
0.5
1
1.5
2
2.5
3
3.5
0 5 10 15 20Time (min.)
Ab
so
rba
nc
e
Time (min.)
Ab
so
rban
ce
(E) (F)
Ab
so
rban
ce
Time (min.)
(A) (B)
Regression Statistics
Multiple R 0.997066
R Square 0.994141
Intercept 2.305667
Slope -0.4208
S28
Fig. S33 UV-vis spectrum for the reduction of p-nitroaniline by adding NaBH4 aqueous
solution using gold nanoparticles of derivative 4 as catalysts.
Ab
so
rban
ce
Wavelength (nm)
378 nm
303 nm
234 nm
24 min.
0
0 min.
24 min.
Wavelength (nm)
Ab
so
rba
nce
234 nm
18 min.
0 min.
378 nm
303 nm 0 min. 18 min.
Fig. S34 UV-vis spectrum for the reduction of p-nitroaniline by adding NaBH4 aqueous
solution using gold nanoparticles of derivative 6 as catalysts.
S29
CDCl3
Fig. S35 1H NMR spectra of the reduced product p-Phenylenediamine in CDCl3.
1H NMR of compound of p-phenylenediamine in CDCl3
S30
Fig. S36 1H NMR of spectrum of compound 3 in CDCl3.
1H NMR of compound 3 in CDCl3
TMS
CDCl3 H2O
S31
Fig. S37 Mass spectrum of compound 3.
[M+H]+ [M+H]
Mass spectrum of compound 3
S32
1H NMR of compound 4 in CDCl3
TMS
H2O
CDCl3
Fig. S38 1H NMR spectrum of compound 4 in CDCl3.
S33
13C NMR of compound 4 in CDCl3
Fig. S39 13
C NMR spectrum of compound 4 in CDCl3.
CDCl3
S34
Mass spectrum of compound 4
[M+Na]+
Fig. S40 Mass spectrum of compound 4.
S35
1H NMR spectrum of compound 5
Fig. S41 1H NMR spectrum of compound 5 in CDCl3
TMS
S36
13C NMR spectrum of compound 5
Fig S42 13
C NMR spectrum of compound 5 in CDCl3.
CDCl3
S37
Inte
nsit
y
Fig. S43 Mass spectrum of compound 5
Mass spectrum of compound 5
(M+Na+2)+
S38
TMS
Fig. S44 1H NMR spectrum of compound 6.
CDCl3
Acetone
1H NMR spectrum of compound 6.
H2O
S39
Fig. S45 13
C NMR spectrum of compound 6.
13C NMR spectrum of compound 6
CDCl3
S40
Fig. S46 Mass spectrum of compound 6
Mass spectrum of compound 6
(M+Na)+
S41
Reaction time for the reduction of p-
nitroaniline to p-phenylenediamine
catalyst Journal
5 min. Gold nanoparticles Present manuscript
2.0 hours Fe-Nano-ZSM-5 Ind. Eng. Chem. Res. 2013, 52,
11479
10.0 hours Fe–phenanthroline/C Chem. Commun., 2011, 47,
10972
3.0 hours Iron(II) chloride
tetrahydrate
Tetrahedron Lett. 2008, 49 1828
30 min. Fe2+
ions Journal of Hazardous Materials
2008, 153, 187
Table S4: Comparison of relative efficiency of gold nanoparticles of derivative 3 over reported procedure in
literature for the reduction of p-nitroaniline to p-phenylenediamine by iron metal.
