Supporting Information
Triphenylene based Zinc Ensemble as
Oxidation Inhibitor
Vandana Bhalla*, Harshveer Arora, Abhimanew Dhir, Manoj Kumar*
Department of Chemistry, UGC Centre for Advanced Studies.
Guru Nanak Dev University, Amritsar, INDIA- 143005
Page No. Contents
S3 General experimental procedures and synthesis of compound 1c.
S4 Synthesis of compound 3 and calculations for fluorescence quantum yield.
S5 Calculation of Anti-oxidation activity.
S6 Absorption spectrum of 3 on addition of Zn2+
ions in THF.
S7 Selectivity and competitive selectivity of derivative 3 toward Zn
2+ ions in the
presence of other cations.
S8 Bar graph representing fluorescence behavior of Zn-3 in presence of various anions
S9 1H NMR of Compound 1c.
S10 13
C NMR of compound 1c
S11 Mass Spectrum of Compound 1c
S12 1H NMR of Compound 3
S13 13
C NMR of Compound 3.
S14 Mass Spectrum of Compound 3.
S15-16 SPECFIT data of 3 zinc complex.
S17 Fluorescence emission spectra of 4 on addition of H2O2 in presence Zn-3 in THF:H2O
(9.5:5).
S18 Fluorescence emission spectra of 4 on addition of H2O2 in presence PG in THF:H2O
(9.5:5).
S1
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S19 Fluorescence emission spectra of 4 on addition of H2O2 in presence BHT in THF:H2O
(9.5:5).
S20 Fluorescence emission spectra of 4 on addition of H2O2 in presence BHA in THF:H2O
(9.5:5).
S21 Fluorescence emission spectra of 4 on addition of H2O2 in presence TP in THF:H2O (9.5:5).
S22 Fluorescence emission spectra of 4 on addition of H2O2 in presence SA in THF:H2O (9.5:5).
S23 IR spectrum of 3.
S24 IR spectrum of 3 + Zn2+
.
S25 Mass spectrum of 3. Zn2+
complex.
S26 HPLC data of compound 3
S27-28 Comparison of receptor 3 with other reported compounds in literature.
S2
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General Information.
All reagents were purchased from Aldrich and were used without further purification. THF (AR
grade) was used to perform analytical studies. All the UV-Vis spectra were recorded on
SHIMADZU UV- 2450 spectrophotometer. All the fluorescence spectra were recorded on
SHIMADZU RF 5301 PC spectrofluorometer. 1H and
13C NMR spectra were recorded on JEOL-
FT NMR-AL 300 MHz spectrophotometer using CDCl3 as solvent and TMS 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 (Hz), integration, and
interpretation. Silica Gel 60 (60-120 mesh) was used for column chromatography.
Synthesis of compound 1c
To the mixture of boronic ester 1b (700 mg, 3.20 mmol) and PdCl2(PPh3)2 (75 mg,0.11) in 1,4-
dioxane was added suspension of 2,3,6,7,10,11-hexabromotriphenylene 1a (300 mg, 0.42 mmol)
in aqueous solution of K2CO3 ( 707 mg, 5.12 mmol).The mixture was refluxed overnight at 90oC
under nitrogen and allowed to cool at room temperature. On addition of water to the reaction
mixture, brown solid precipitated out which was filtered, dried and then purified by column
chromatography (95:5::CHCl3:MeOH) to give the product 1c in 70% yield. 1H NMR (300 MHz,
DMSO): δ (ppm) = 5.06 (s, 12H, NH2), 6.49 (d, 12H, ArH, J = 7.2 MHz), 6.98 (d, 12H, ArH, J =
7.2 MHz), 8.48 (s, 6H, ArH): 13
C (75 MHz, DMSO): δ (ppm) = 113.61 (ArC), 124.32 (ArC),
127.38 (ArC), 128.86 (ArC), 130.26 (ArC), 139.76 (ArC), and 147.27 (ArC). ESI-Ms- 775
(M+1)+. Elemental analysis Calcd for C54H42N6: C, 83.69 %; H, 5.46 %; N, 10. 84, Found: C,
83.80 %; H, 5.53 %; N, 10.98 %.
S3
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Synthesis of compound 3
To the stirred solution of compound 1c (50 mg, 0.07 mmol) in 5ml dry THF was added quinoline
carboxaldehyde 2 (73 mg, 0.47 mmol). The reaction was then stirred overnight at room
temperature. A yellow solid precipitated out which was filtered, and washed with THF. The
crude product was recrystallized form CHCl3: MeOH mixture to give the pure product 3 in 75%
yield. 1H NMR (300 MHz, CDCl3): δ (ppm) = 7.45 (m, 12H, ArH ), 7.59 (t, 6H, ArH ), 7.75 (t,
6H, ArH), 7.35 (d, 12H, ArH, J=8.4 MHz), 7.86 (d, 6H, ArH, J= 8.1), 8.16 (d, 6H, ArH, J =
8.7), 8.24 (d, 6H, ArH, J = 8.7), 8.38 (d, 6H, ArH, J = 8.4), 8.85 [s, 6H (ArH), 6H (N=CH)]. 13
C
(75 MHz, DMSO): δ (ppm) =118.74 (ArC), 121.12 (ArC), 121.24 (ArC), 125.47 (ArC), 127.67
(ArC), 127.71 (ArC), 128.91 (ArC), 129.17 (ArC), 129.77 (ArC), 129.82 (ArC), 129.87 (ArC),
130.45 (ArC), 131.07 (ArC), 131.12 (ArC), 136.55 (ArC), 148.02 (ArC) and 154.94 (ArC).
MALDI-TOF Ms-1609.2 (M+). Elemental analysis Calcd for C114H72N12: C, 85.05 % ; H, 4.51
%; N, 10.44 % ; Found: C, 85.25 % ; H, 4.39 % ; N, 10.48 %.
Calculation of Fluorescence Quantum Yield:
The fluorescence quantum yield for 3 was determined at room temperature in analytical
grade H2O:THF (9.5:5) using optically matching solutions of 9,10 diphenyl anthracene (f)
= 0.95 in ethanol as the standard at an excitation wavelength of 350 nm respectively from a
xenon lamp of the spectrofluorophotometer and the quantum yield was calculated by using
Equation (1), in which (fs) is the radiative quantum yield of the sample, (fr) the radiative
quantum yield of reference, As and Ar are the absorbance of the sample and the reference,
respectively, Ds and Dr the areas of emission for the sample and reference, L s and Lr are the
lengths of the absorption cells, and Ns and Nr are the refractive indices of the sample and
reference solutions (pure solvents were assumed).
S4
Truth Table 2
Equation 1
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Calculation of Antioxidation activity:
The suppression ratio for OOH- was calculated from the following expression:
Oxidation (O) (%) = I0 −Ii / I0-IC × 100
Where Ii = the fluorescence intensity of β-hydroxy naphthaldehyde in the presence of the Zn-
3 + H2O2 or in the presence of the PG + H2O2 .
I0 = fluorescence intensity of β-hydroxy naphthaldehyde in absence of any analyte.
IC = fluorescence intensity of β-hydroxy naphthaldehyde in the presence of H2O2.
Anti-oxidation activity A = (100- O) %.
S5
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S6
0
0.5
1
1.5
2
2.5
3
3.5
225 325 425 525
Wavelength (nm)
Ab
s.
Figure S1. Absorption spectrum of 3 (10 μM) on
addition of Zn2+ (200 equiv.) ions in THF.
3 + Zn2+
ions
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S7
Figure S2: Selectivity (blue bars) and competitive selectivity
(red bars) of derivative 3 (5 μM) toward Zn2+ ions in the
presence of other cations.
Zn2
Fe3+
Fe2+
Cu2+
Hg2+
Ni2+
Cd2+
Pb2+
Mn2+
Co2+
Li2+
Na+
Mg2+
K+
Ca2+
Ba2+
I-I 0
/I0 X
100
Metal ions
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S8
0
10
20
30
40
50
60
70
80
90
100
1 2 3 4 5 6 7 8 9 10 11 F- CN- OAc- Cl- Br- I- EDTA-4 HSO4- NO3
- H2PO4- ClO4
-
I-I 0
/I0 X
100
Figure S3: Bar graph representing fluorescence
behaviour of Zn-3 in presence of various anions.
Anions
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S9
1H NMR of Compound 1c
NH2NH2
NH2 NH2
NH2NH2
1c
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S10
13C NMR of compound 1c
NH2NH2
NH2 NH2
NH2NH2
1c
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S11
m/z680 685 690 695 700 705 710 715 720 725 730 735 740 745 750 755 760 765 770 775 780 785 790 795 800 805 810 815
%
0
100
HARSHVEER H-44 28 (0.519) Cm (19:47) TOF MS ES+ 1.45e4775.3
14458
684.31436
682.3518 685.3
731
776.38006
777.32045
803.4443
NH2NH2
NH2 NH2
NH2NH2
1c
Mass Spectrum of Compound 1c
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S12
N
N N
N
NN
N
N
N
N
N
N
3
1H NMR of Compound 3
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S10
S13
N
N N
N
NN
N
N
N
N
N
N
3
13C NMR of Compound 3
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S12
S14
Mass Spectrum of Compound 3
1609 Expanded version of compound 3
N
N N
N
NN
N
N
N
N
N
N
3
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SPECFIT data for calculation of stability constant for 3 zinc complex [PROGRAM] Name = SPECFIT Version = 3.0 [FILE] Name = WITH ZN UPTO 10 EQV FOR BC.FAC Path = C:\Program Files\SPECFIT\DATA\ Date = 11-Aug-11 Time = 9:33:46 PM Ncomp = 2
Nmeas = 11 Nwave = 351 [FACTOR ANALYSIS] Tolerance = 1.000E-09 Max.Factors = 10 Num.Factors = 6 Significant = 2
Eigen Noise = 1.907E-01 Exp't Noise = 1.907E-01 # Eigenvalue Square Sum Residual Prediction 1 3.816E+05 2.494E+04 2.542E+00 Data Vector 2 2.480E+04 1.403E+02 1.907E-01 Data Vector 3 6.522E+01 7.505E+01 1.395E-01 Possibly Data 4 1.845E+01 5.660E+01 1.211E-01 Probably Noise 5 1.488E+01 4.172E+01 1.040E-01 Probably Noise 6 1.101E+01 3.071E+01 8.925E-02 Probably Noise [MODEL] Date = 11-Aug-11 Time = 9:50:39 PM Model = 0 Index = 3 Function = 1 Species = 3 Params = 3
[SPECIES] [COLORED] [FIXED] [SPECTRUM] 1 0 0 True False 0 1 0 False False 3 1 0 True False [SPECIES] [FIXED] [PARAMETER] [ERROR] 1 0 0 True 0.00000E+00 +/- 0.00000E+00 0 1 0 True 0.00000E+00 +/- 0.00000E+00 3 1 0 False 1.32388E+01 +/- 1.83800E-01
[CONVERGENCE] Iterations = 12 Convergence Limit = 1.000E-04 Convergence Found = 2.190E-05 Marquardt Parameter = 0.0 Sum(Y-y)^2 Residuals = 6.43513E+04 Std. Deviation of Fit(Y) = 4.08305E+00 [STATISTICS] Experimental Noise = 1.907E-01
Relative Error Of Fit = 43.3677% Durbin-Watson Factor = 1.1123 Goodness Of Fit, Chi^2 = 4.587E+02 Durbin-Watson Factor (raw data) = None Goodness Of Fit, Chi^2 (raw data) = None
S15
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[COVARIANCE] 2.776E-01
[CORRELATION] 1.000E+00 [END FILE]
S16
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S17
0
50
100
150
200
250
300
350
400
450
340 440 540
Wavelength (nm)
Inte
nsi
ty
H2O2 (1300 μl) + Zn-3
Figure S4. Fluorescence emission spectra of 4 (3
μM) on addition of H2O2 (1300 μl) in presence of
250 μl of 100 μM of Zn-3 in THF:H2O (9.5:5).
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S18
0
50
100
150
200
250
300
340 440 540
wavelength (nm)
Inte
nsi
ty
H2O2 (1025 μl) + PG
Figure S5. Fluorescence emission spectra of 4 (3
μM) on addition of H2O2 (1025 μl) in presence of
250 μl of 100 μM of PG in THF:H2O (9.5:5).
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S19
0
50
100
150
200
250
300
340 440 540
Wavelength (nm)
Inte
nsi
ty
H2O2 (1000 μl) + BHT
Figure S6. Fluorescence emission spectra of 4 (3
μM) on addition of H2O2 (1000 μl) in presence of
250 μl of 100 μM of BHT in THF:H2O (9.5:5).
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S20
0
50
100
150
200
250
300
340 390 440 490 540
Wavelength (nm)
Inte
nsi
ty
H2O2 (1000 μl) + BHA
Figure S7. Fluorescence emission spectra of 4 (3
μM) on addition of H2O2 (1000 μl) in presence of
250 μl of 100 μM of BHA in THF:H2O (9.5:5).
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S21
0
50
100
150
200
250
300
350 400 450 500 550
wavelength (nm)
Inte
nsi
ty
H2O2 (975 μl) + TP
Figure S8. Fluorescence emission spectra of 4 (3 μM)
on addition of H2O2 (950 μl) in presence of 250 μl of
100 μM of TP in THF:H2O (9.5:5).
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S22
0
50
100
150
200
250
300
350
400
335 435 535
Wavelength (nm)
Inte
nsi
ty
H2O2 (950 μl) + SA
Figure S9. Fluorescence emission spectra of 4 (3 μM)
on addition of H2O2 (950 μl) in presence of 250 μl of
100 μM of SA in THF:H2O (9.5:5).
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S23
C=N
IR spectrum of 3
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S24
IR spectrum of 3 + Zn2+
1590, C=N + Zn2+
Expanded version of 3 + Zn2+
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S25
Mass spectrum of 3 + Zn2+
3 + 3 x [Zn2+
(ClO4)-]
+ Na
+
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HPLC data for compound 3
S26
Peak# Ret.Time Area % Single Point Threshold
1 6.770 0.2204 0.792904
2 7.530 99.7796 0.99996
Total 100.000
5.0 6.0 7.0 8.0 9.0 10.0min
0
250
500mAU
246nm,4nm (1.00)
0 10 20 30 40 min
0
100
200
300
400
mAU246nm,4nm (1.00)
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Comparison of receptor 3 with other Zinc receptors reported in the literature.
S.No. References Selectivity/Interference Quantum yield Peroxide
detection with
Zn2+
ensemble
1 Y Mikata, A.
Yamashita, A.
Kawamura, H.
Kinno, Y.
Miyamoto, S.
Tamotsu, Dalton
Trans, 2009, 3800.
Responds to Cd2+
also
0.28
NO
2
X.Y. Chen, J. Shi,
Y. M. Li, F. L.
Wang, X. Wu, Q.
X. Guo, L. Liu,
Org. Lett., 2009,
11, 19, 4426.
Respond to Cd2+
also.
0.556
NO
3
Y. Xu and Y.
Pang. Dalton
Trans., 2011, 40,
1503.
Respond to Hg2+
and
Cu2+
0.052
NO
4
J. F .Zhang, S.
Kim, J. H. Han, S.
J. Lee, T. Pradhan,
Q. Y. Cao, S. J.
Lee, C. Kang, J.
S. Kim, Org. Lett.,
2011, 13, 5294.
Responds to Hg2+
and
Cd2+
also.
*
NO
5
L. E. Mcquade, S.
J. Lippard, Inorg.
Chem. 2010, 49,
9535.
Respond to Cd2+
also.
*
NO
S27
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* No data available
6 F, Sun,; G. Zhang,
D. Zhang, L. Xue,
and H. Jiang, Org.
Lett., 2011, 13,
6378.
Respond to Cd2+
also.
*
NO
7
Receptor 3
Highly selective to
Zn2+
ion and no
interference with other
metal ions.
0.65
YES
S28
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