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Supporting Information

Pentacenequinone Derivatives: Aggregation-Induced Emission Enhancement, Mechanism and Fluorescent Aggregates for Superamplified Detection of Nitroaromatic Explosives

Sandeep Kaur, § Ankush Gupta, § Vandana Bhalla* and Manoj Kumar

Department of Chemistry, UGC Sponsored-Centre for Advanced Studies-I, Guru Nanak Dev University, Amritsar-143005, Punjab, India

Email Address:[email protected]

S3 General experimental procedures and calculations for quantum yield.

S4 Synthetic scheme of derivatives 5-9.

S5 Absorption spectra of derivatives 5, 6 and 7 showing the variation of absorption intensity

in a H2O/DMSO mixture with different water fractions.

S6 SEM images of 5 showing the nanoaggregates and dynamic light scattering (DLS) results showing the variation in particle size diameter with increasing water content in DMSO solution of 5. (A) 10% (B) 30% and (C) 50% water content in DMSO solution of 5.

S7 Spectra of derivatives 5-7 showing the variation of fluorescence intensity in H2O/DMSO mixture and fluorescence spectra of derivatives 7 showing the variation of fluorescence intensity in H2O/DMSO mixtures.

S8 Dynamic light scattering (DLS) results showing the variation in particle size diameter with increasing water content in DMSO solution of 7 and 6. (A) 10% (B) 30% and (C) 50% water content in DMSO solution of 7.

S9 Spectra of derivative 7 and 6 showing the variation of fluorescence intensity in vs. particle size and SEM images of 6 and 7 showing the formation of aggregates.

S10 Fluorescence spectra of derivative 7 (5 μM) showing the variation of fluorescence intensity in DMSO/Glycerol mixtures and plot showing the variation in fluorescence intensity of derivatives 5-7 in DMSO/glycerol mixtures with different glycerol fractions.

S11 Fluorescence spectra of derivatives 5 and 7 showing the variation of fluorescence intensity with increase in temperature.

S12 Fluorescence anisotropy of derivative 7 in DMSO solution and H2O/DMSO (1:1v/v) mixture.

S13 Absorption spectra of derivatives 8 and 9 in a H2O/THF mixture with different water fractions, SEM images of derivatives 8 and 9 and fluorescence spectra of 9 showing the variation of fluorescence intensity in H2O/THF mixtures with different water fractions.

S1

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2014

S14 Table S1 showing fluorescence lifetimes (τF) of derivative 8-9 recorded at different H2O/THF ratios and table S2 comparative photophysical properties of derivative 8-9.

S15 Change in fluorescence spectra of derivatives 5 and 6 with the addition of PA and Stern- Volmer plot derivatives 5, 6 and 7 in response to PA.

S16 Change in fluorescence spectra of derivatives 8 and 9 with the addition of PA and Stern-Volmer plot in response to PA.

S17 Time resolved fluorescence emission spectra of aggregates of 5-7 with different concentrations of PA.

S18 Time resolved fluorescence emission spectra of aggregates of 8-9 with different concentrations of PA.

S19 Spectral overlap of absorption spectrum of PA and fluorescence spectrum of aggregates of derivatives 5-7.

S20 Spectral overlap of absorption spectrum of PA and fluorescence spectrum of aggregates of derivatives 8-9.S21 Extent of fluorescence quenching of 5-9 observed with various nitro derivatives.

S22 Test strips of derivatives 5-9 for trace detection of PA.

S23 1H NMR spectrum of derivative 5.

S24 Mass spectrum of derivative 5.




S28 13C NMR spectrum of derivative 8.



S31 13C NMR spectrum of derivative 9.


S2

Experimental

General information

All reagents were purchased from Aldrich and were used without further purification. The

UV/vis and fluorescence spectra were recorded with Shimdzu UV-2450 spectrophotometer and

Shimadzu RF-5301(PC) spectrofluorophotometer, respectively. The SEM images were recorded

from Scanning Electron Microscope (SEM)-ZeissEV040. The time-resolved fluorescence spectra

were recorded with a HORIBA time-resolved fluorescence spectrometer. Elemental analysis (C,

H, N) was performed on a Flash EA 1112 CHNS-O analyzer (Thermo Electron Corp.). 1H NMR

were 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.

Calculations for quantum yield1:

Fluorescence quantum yield was determined using optically matching solutions of

diphenylanthracene (Фfr = 0.9 in cyclohexane) as standard at an excitation wavelength of 352 nm

and quantum yield is calculated using the equation:

Фfs = Фfr

Фfs and Фfr are the radiative quantum yields of sample and the reference respectively, As and Ar

are the absorbance of the sample and the reference respectively, Ds and Dr the respective areas of

emission for sample and reference. Ls and Lr are the lengths of the absorption cells of sample

and reference respectively. Ns and Nr are the refractive indices of the sample and reference

solutions (pure solvents were assumed respectively).

1 Demas, J. N.; Grosby, G. A. J. Phys. Chem. 1971, 75, 991-1024.

S3

1-10-ArLr Ns2 Ds

1-10-AsLs Nr2 Dr

Synthetic scheme of derivative5-9

S4

Scheme 2. Pentacenequinone based derivatives 8 and 9.

O

OO

O

B O

O

Pd(PPh3)4, 2M K2CO31,4-dioxane, 90-100 oC

Br

Br

2

Pd(PPh3)4, 2M K2CO31,4-dioxane, 90-100 oC

B O

O

C6H13O

O

O

4c

4b

8

9

OC6H13

OC6H13

O

O

R7

R8

R5

R6

R5=R6=R7=R8=

N

R7=R8= H; R5=R6 = N

R6=R7=R8= H; R5 =

N

O

O

R3

R4

R1

R2

R1=R2=R3=R4= Br

R3=R4= H; R1=R2= Br

R2=R3=R4= H; R1 = Br

N

B O

O

PdCl2(PPh3)2, 2M K2CO31,4-dioxane, 90-100 oC

5;

6;

7;

4a

1;

3;

2;

Scheme 1. Pentacenequinone based derivatives 5-7.

S5

Water Fraction (%)

Fig. S3 Absorption spectra of derivative 7 (10 μM) showing the variation of absorption intensity in a H2O/DMSO mixture with different water fractions.

Abs

orba

nce

0

0.1

0.2

0.3

0.4

0.5

300 350 400 450 500

Level-off tail

9070 50 30 10 0

Water Fraction (%)

Wavelength (nm)


Abs

orba

nce

Wavelength (nm)

00.20.40.60.8

11.21.41.61.8

300 350 400 450 500

Level-off tail

Water Fraction (%)

9070 50 3010 0


Level-off tail

9070 50 30 10 0

Abs

orba

nce

Wavelength (nm)

0

0.1

0.2

0.3

0.4

300 350 400 450 500

S6

(B)

Fig. S4A SEM images of derivative 5 in H2O/DMSO (1:1, v/v) solvent mixture. (Scale bar 200 nm)

0

20

40

60

80

100

1 10 100 1000 10000

Inte

nsity

(P

erce

nt)

Size (d.nm)

Statistics Graph (2 measurements)

0

10

20

30

40

50

60

1 10 100 1000 10000

Inte

nsity

(P

erce

nt)

Size (d.nm)


0

10

20

30

40

50

60

1 10 100 1000 10000

Inte

nsity

(Per

cent

)

Size (d.nm)


Fig. S4B: Dynamic light scattering (DLS) results showing the variation in particle size diameter with increasing water content in DMSO solution of 5. (A) 10% (B) 30% and (C) 50% water content in DMSO solution of 5.

200 nm

10% H2O-DMSO mixture of derivative 5

30% H2O- DMSO mixture of derivative 5

50% H2O-DMSO mixture of derivative 5

200 nm 200 nm

S7

Fig. S5 Spectra of derivatives 5-7 showing the variation of fluorescence intensity in H2O/DMSO mixture.

Water fraction (%)

I/Io

765

Fig. S6 Fluorescence spectra of derivative 7 (10 μM) showing the variation of fluorescence intensity in H2O/DMSO mixtures. λex.=322 nm.

Water Fraction (%)50403020 10 0

Wavelength (nm)

Inte

nsity

S8

Fig. S7A: Dynamic light scattering (DLS) results showing the variation in particle size diameter with increasing water content in DMSO solution of 7. (A) 10% (B) 30% and (C) 50% water content in DMSO solution of 7.

Fig. S7B: Dynamic light scattering (DLS) results showing the variation in particle size diameter with increasing water content in DMSO solution of 6. (A) 10% (B) 30% and (C) 50% water content in DMSO solution of 6.

0

10

20

30

40

50

60

1 10 100 1000 10000

Inte

nsity

(Per

cent

)

Size (d.nm)

Statistics Graph (2 measurements)50% H2O-DMSO mixture of derivative 7

0

10

20

30

40

50

60

1 10 100 1000 10000

Inte

nsity

(P

erce

nt)

Size (d.nm)


0

10

20

30

1 10 100 1000 10000

Inte

nsity

(P

erce

nt)

Size (d.nm)


0

20

40

60

80

1 10 100 1000 10000

Inte

nsity

(P

erce

nt)

Size (d.nm)


0

20

40

60

80

100

1 10 100 1000 10000

Inte

nsity

(P

erce

nt)

Size (d.nm)


0

20

40

60

80

1 10 100 1000 10000

Inte

nsity

(P

erce

nt)

Size (d.nm)


S9

Fig. S8A Spectra of derivative 7 showing the variation of fluorescence intensity in vs. particle size.

.

Inte

nsity

Particle size (nm)

460

465

470

475

480

485

490

495

300 400 500 600 700 800

Fig. S8B Spectra of derivative 6 showing the variation of fluorescence intensity in vs. particle size.

Inte

nsity

Particle size (nm)

465

470

475

480

485

490

160 260 360 460 560

200 nm

2 µm2 µm2 µm

Fig. S9 SEM images of (A) 6 and (B) 7 showing the formation of aggregates. Scale bar (A) 200 nm and (B) 2 µm.

(A)

200 nm

(B)

2 µm

S10

0

2

4

6

8

10

12

0 20 40 60 80 100

321

I/Io

Glycerol Fraction (vol %)

765

Fig. S11 Plot showing the variation in fluorescence intensity of derivatives 5-7 in DMSO/glycerol mixtures with different glycerol fractions.

Fig. S10 Fluorescence spectra of derivative 7 (10 μM) showing the variation of fluorescence intensity in DMSO/Glycerol mixtures. λex.=322 nm.

Glycerol Fraction (%)

90 70 50 30 0

Inte

nsity

Wavelength (nm)

S11

Fig. S13 Fluorescence spectra of derivative 7 (10 μM) showing the variation of fluorescence intensity with increase in temperature in H2O/DMSO mixture (1:1, v/v). λex.=322 nm.

Temp (in oC)

25

75

Inte

nsity

Wavelength (nm)

Fig. S12 Fluorescence spectra of derivative 5 (10 µM) showing the variation of fluorescence intensity with increase in temperature in H2O/DMSO mixture (1:1, v/v). λex.=310 nm.

Wavelength (nm)

Inte

nsity

Temp (in oC)

25

75

S12

Ani

sotro

py

-4.00E-01

-3.00E-01

-2.00E-01

-1.00E-01

0.00E+00

1.00E-01

2.00E-01

3.00E-01

4.00E-01

5.00E-01

4 4.5 5 5.5 6 6.5 7 7.5 8

Time (ns)

Fig. S14 Fluorescence anisotropy of derivative 7 in DMSO solution

Ani

sotro

py

-4.00E-01

-3.00E-01

-2.00E-01

-1.00E-01

0.00E+00

1.00E-01

2.00E-01

3.00E-01

4.00E-01

5.00E-01

4 5 6 7 8 9 10 11 12

Time (ns)

Fig. S15 Fluorescence anisotropy of derivative 7 in H2O/ DMSO (1:1, V/V) mixture.

S13

Fig. S17 SEM images of derivatives (A) 8 and (B) 9 showing formation of aggregates. Scale bar 200 nm

(A)

200 nm

(B)

200 nm

Inte

nsity

Wavelength (nm)

(a) (b)

90706030 10 0

Water Fraction (%)

Fig. S18 Fluorescence spectra of 9 (10 µM) showing the variation of fluorescence intensity in H2O/THF mixtures with different water fractions. Inset photographs (Under 365 nm UV-light) (a) in pure THF (b) with the addition of 90% water in THF.

(B)

Fig. S16B Absorption spectra of derivative 9 (10 μM) showing the variation of absorption intensity in H2O/THF mixture with different water fractions. (Inset photographs showing formation of new band at 420 nm)

Water Fraction (%)

Wavelength (nm)

0

0.05

0.1

0.15

390 410 430 450

Abs

orba

nce

Wavelength (nm)

Abs

orba

nce

Level-off tail

9070 50 30 10 0

Fig. S16A Absorption spectra of derivative 8 (10 μM) showing the variation of absorption intensity in H2O/THF mixture with different water fractions. (Inset photographs showing formation of new band at 420 nm)

(A)

Abs

orba

nce

Level-off tail

Wavelength (nm)

9070 50 30 10 0

0

0.2

0.4

0.6

350 390 430 470

Wavelength (nm)A

bsor

banc

e

Water Fraction (%)

Level-off tail

S14

Table S2. Comparative photophysical properties of derivative 8-9:

Table S2 a solution in THF. b monoexponential life time in THF. c A1, A2 : fractional amount of molecules in each environment in solution. d

Radiative rate constant in solution (Kf = ΦF/τF). e non-radiative rate constant in solution (knr = (1- ΦF)/τF). f aggregates in H2O/THF with 90 vol% of water. A1, A2: g fractional amount of molecules in each environment in aggregates. h τF1 and τF2: biexponential life time of aggregates in 90 vol% of water in THF. i Radiative rate constant in aggregates (Kf = ΦF/τF). j non-radiative rate constant in aggregates(Knr = (1- ΦF)/τF).

Table S1. Fluorescence lifetimes (τF) of derivative 8-9 recorded at different H2O/THF ratios (decay monitored at the corresponding λmax; excitation at 300 nm)

Derivative H2O/THF ratio λmax (nm) τF1 (ns) τF2(ns)

1

1.5

2

2.5

3

0 5 10 15 20 25 30

S15

Fig. S20 (A) Change in fluorescence spectra of derivative 6 (10 μM) with the addition of PA in H2O/DMSO (1:1) mixture, (B) Stern-Volmer plot in response to PA, inset Fig. shows the Stern-Volmer plot obtained at lower concentration of PA.

Wavelength (nm)

Inte

nsity

(A)

PA

2

4

6

8

10

12

0 8 16 24 32 40 48 56 64

Io/I

PA (in 10 x 10 -6 M)

(B)

1

1.2

1.4

1.6

1.8

2

2.2

0 5 10 15 20 25 30

Io/I

PA (in 10 x 10 -6 M)

0 equiv.

60 equiv.

0 equiv.

62 equiv.

Fig. S19 (A) Change in fluorescence spectra of derivative 5 (10 μM) with the addition of PA in H2O/DMSO (1:1) mixture, inset photograph shows the fluorescence intensity changes upon addition of PA from (a) 0 to (b) 62 equiv. (B) Stern-Volmer plot in response to PA, inset Fig. shows the Stern-Volmer plot obtained at lower concentration of PA.

1

2

3

4

5

6

0 10 20 30 40 50 60 70

Io/I

PA (in 10 x10 -6 M)

1

1.2

1.4

1.6

1.8

2

0 5 10 15 20 25 30

Io/I

PA (in 10 x 10 -6 M)

(B) a b

Inte

nsity

Wavelength (nm)

PA(A)

Fig. S21 Stern-Volmer plot in response to PA of derivative 7; inset figure shows the Stern-Volmer plot obtained at lower concentration of PA.

(B)

2

4

6

8

10

12

14

0 10 20 30 40 50 60

I/Io

PA (in 10x10-6 M)

I 0/I

S16

Wavelength (nm)

PA

Inte

nsity

(B)

1

1.1

1.2

1.3

1.4

1.5

1.6

0 5 10 15

Io/I

PA (in 10x10-6 M)

Fig. S23 (A) Change in fluorescence spectra of derivative 9 (10 μM) with the addition of PA in H2O/THF (9:1) mixture, inset photograph shows the fluorescence intensity changes upon addition of PA from (a) 0 to (b) 40 equiv. (B) Stern-Volmer plot in response to PA, inset Fig. shows the Stern-Volmer plot obtained at lower concentration of PA.

1

1.5

2

2.5

3

3.5

4

4.5

5

0 10 20 30 40 50

Io/I

PA (in 10x10-6 M)

(a) (b)

(A)0 equiv.

40 equiv.

Fig. 22 (A) Change in fluorescence spectra of derivative 8 (10 μM) with the addition of PA in H2O/THF (9:1) mixture, inset photograph shows the fluorescence intensity changes upon addition of PA from (a) 0 to (b) 40 equiv. (B) Stern-Volmer plot in response to PA, inset Fig. shows the Stern-Volmer plot obtained at lower concentration of PA.

1

2

3

4

5

6

0 10 20 30 40 50

Io/I

PA (in 10x10-6 M)

1

1.5

2

2.5

3

0 5 10 15 20 25

Io/I

PA (in 10 x 10-6 M)

(B)

Wavelength (nm)

PA

Inte

nsity

(A)0 equiv.

40 equiv.

(a) (b)

S17

Fig. S24 Time resolved fluorescence emission spectra of aggregates of compound 5 with different concentrations of PA and showing the fluorescence lifetime of aggregates of 5 is invariant at different concentration of PA

IRF

0

5

10

15

20

25

30

40

PA (in equiv.)

0

0.5

1

1.5

2

0 10 20 30 40Conc. of PA/equiv.

τ 0/τ

Fig.S25 Time resolved fluorescence emission spectra of aggregates of compound 6 with different concentrations of PA and showing the fluorescence lifetime of aggregates of 6 is invariant at different concentration of PA

1

10

100

1000

10000

0 5 10 15 20 25 30Time (ns)

Cou

nts

Series1

Series2

Series3

Series4

Series5

Series6

Series7

IRF

0

5

10

15

20

30

PA (in equiv.)

0

0.5

1

1.5

2

0 5 10 15 20 25 30

Conc. of PA/equiv.

τ 0/τ


PA (in equiv.)

IRF

0

5

10

15

20

30

0

0.5

1

1.5

2

0 5 10 15 20 25 30Conc. Of PA/equiv.

τ 0/τ

S18

IRF


PA (in equiv.)IRF

0

5

10

15

20

30

0

0.5

1

1.5

2

0 5 10 15 20 25 30 35 40Con. of PA/equiv.

τ 0/τ

τ 0/τ


1

10

100

1000

10000

0 5 10 15 20 25 30Time (ns)

Cou

nts

Series1

Series2

Series3

Series4

Series5

Series6

Series7

IRF

0

10

15

20

25

30

PA (in equiv)

0

0.5

1

1.5

2

0 5 10 15 20 25 30

conc. of PA/equiv.

τ 0/τ

S19

Fig. S30 Spectral overlaps of absorption spectrum of PA and fluorescence spectrum of aggregates of derivative 6.


(C)

Fig. S31 Spectral overlap of absorption spectrum of PA and fluorescence spectrum of aggregates of compound 7.

S20



S21

Fig. S34 Extent of fluorescence quenching of 5-7 (10 μM) observed in H2O/DMSO (1:1) mixture after the addition of 62 equiv. of various nitroderivatives. 1=PA, 2=TNT, 3=DNT, 4=DNB, 5=DNBA, 6=BQ, 7=NM, 8=DMDNB

765

(% Q

uenc

hing

)Nitro derivative

Fig. S35 Extent of fluorescence quenching of 8 and 9 (10 μM) observed in H2O/THF (9:1) mixture after the addition of 40 equiv. of various nitroderivatives. 1=PA, 2=DNT, 3=DNB, 4=BQ, 5=DNBA, 6=TNT, 7=NM, 8=DMDNB

(% Q

uenc

hing

)

Nitro derivatives

89

S22

Fig. S40 Photographs (under 365 nm UV light) of fluorescence quenching of aggregates of derivative 5 on test strips for the visual detection of small amount of PA (a) test strip; PA of different concentration (b) 10-4 M (c) 10-6 M (d) 10-8 M.

(a) (b) (c) (d)(b)

Fig. S36 Photographs (under 365 nm UV light) of derivative 5 on test strips (a) before and (b) after dipping into aqueous solutions of PA.

(a)

Fig. S41 Photographs (under 365 nm UV light) of fluorescence quenching of nanoaggregates of derivative 6 on test strips for the visual detection of small amount of PA (A) test strip; PA of different concentration (b) 10-4 M (c) 10-6

M (d) 10-8 M.

(a) (b) (c) (d)

Fig. S42 Photographs (under 365 nm UV light) of fluorescence quenching of nanoaggregates of derivative 8 on test strips for the visual detection of small amount of PA (A) test strip; PA of different concentration (b) 10-4 M (c) 10-6

M (d) 10-8 M.

(a) (b) (c) (d)

(a) (b) (c) (d)

Fig. S43 Photographs (under 365 nm UV light) of fluorescence quenching of nanoaggregates of derivative 9 on test strips for the visual detection of small amount of PA (A) test strip; PA of different concentration (b) 10-4 M (c) 10-6 M (d) 10-8 M.

Fig. S38 Photographs of derivative 8 on test strips (a) before and (b) after dipping into aqueous solutions of PA.

(a) (b)

(a) (b)



(a) (b)

1H NMR spectrum of derivative 5 in CDCl3

S23

O

O

N

Fig. S44 1H NMR spectrum of derivative 5 in CDCl3

Mass spectrum of derivative 5

S24

Fig. S45 Mass spectrum of derivative 5

m/z100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440

%

0

100Ankush ANK 1PY 68 (1.260) Cm (2:167) 1: TOF MS ES+

1.07e5386.2107225

279.210138

355.29835299.1

7745 356.23616

387.234928

388.26028

O

O

N


S25

O

O

N

N

N

N



S26

O

O

N

N

N

N


S27



TMS

O

O

OC6H13

OC6H13

S28

Fig. S49 13C NMR spectrum of derivative 8 in CDCl3.

13C NMR spectrum of derivative 8 in CDCl3

O

O

OC6H13

OC6H13

CDCl3

S29

Inte

nsity



Mass spectrum of derivative9

O

O

OC6H13

OC6H13

S30

CDCl3



O

O

CDCl3

H20

S31

Fig. S52 13C NMR spectrum of derivative 9 in CDCl3

13C NMR spectrum of derivative 9

O

O CDCl3

S32



O

O

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