An efficient naphthalimide based fluorescent dyad (ANPI) for F- and Hg2+ mimicking OR, XNOR and INHIBIT logic functions

Article abstract of DOI:10.1039/c1nj20058e

A fluorescent bischromophoric dyad combining anthracene and naphthalic anhydride units has been synthesized and characterized. The dyad shows a FRET mediated emission signal at ～535 nm when excited at λ_ex. = 380/360 nm, with efficient energy transfer efficiency (E_T = 93%) and quantum yield (Φ = 0.155). Upon interaction with F^- and Hg ²⁺ ions selectively, a diminished (switched-Off) FRET signal is observed and the naked-eye sensitive color of the solution changed to dark red with enhanced emission corresponding to an anthracene moiety (switched-On). Job's plot analysis revealed a 1:1 stoichiometry between dyad and F ^-/AcO^- and Hg²⁺ ions. The output fluorescence signals exhibited by dyad on chemical inputs of F^-, AcO^- and Hg²⁺ ions mimicked OR, XNOR and INHIBIT logic functions. A ¹H NMR titration experiment suggested deprotonation of -NH proton and "Y-type or tweezer-like" H-bonding interaction in the presence of F^- and AcO^-, respectively, involving -NH, -CHN- and anthracene ring protons.

Full text of DOI:10.1039/c1nj20058e

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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Electronic Supplementary Information
-
2+
An efficient naphthalimide based fluorescent dyad (ANPI) for F and Hg mimicking OR,
XNOR and INHIBIT logic functions
Mohammad Shahid, Priyanka Srivastava and Arvind Misra*
Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi – 221 005.
INDIA.
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Figure S1: H NMR spectrum of 7 in DMSO-d .
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1
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Figure S2: C NMR spectrum of 7 in CDCl .
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Figure S3: FT-IR spectrum of 7.
Figure S4: ESI-MS spectrum of 7.
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Figure S5: H NMR spectrum of 9 in CDCl .
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Figure S6: Fluorescence titration spectra of 7 with AcO anion in DMSO solution at λ
=
ex.
4
50nm.
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Figure S7: Job’ plot (a) and Benesi-Hildebrand plot (b) of dyad 7 for F anion at excitation 450
nm.
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Figure S8: H NMR titration spectra of 7 with F anion in DMSO-d .
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Figure S9: H NMR spectrum of 7 upon addition of 0.5 equiv of F anion in DMSO-d .
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Figure S10: H NMR spectrum of 7 upon addition of 1.5 equiv of F anion in DMSO-d .
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1
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Figure S11: H NMR spectrum of 7 upon addition of 2.5 equiv of F anion in DMSO-d .
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Figure S12: H NMR spectrum of 7 upon addition of 3.5 equiv of F anion in DMSO-d .
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Figure S13: H NMR spectrum of 7 upon addition of 0.5 equiv of AcO anion in DMSO-d .
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Figure S14: H NMR spectrum of 7 upon addition of 1.5 equiv of AcO anion in DMSO-d .
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Figure S15: H NMR spectrum of 7 upon addition of 2.5 equiv of AcO anion in DMSO-d .
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Figure S16: H NMR spectrum of 7 upon addition of 5.0 equiv of AcO anion in DMSO-d .
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Figure S17: Change in fluorescence spectra of 7 upon addition of various metal ions as their
nitrate salts (10 equiv) in ACN solution.
Figure S18: Fluorescence spectra of 8 upon addition of tested (a) metal ions (20 equiv) and (b)
anions in ACN solution.
Figure S19: Fluorescence spectra of 9 upon addition of various ions (20 equiv) in ACN solution.
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+
-
Figure S20: Fluorescence emission spectra of 7.Hg complex upon addition of Br ion (0 – 20
equiv) in ACN.
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Figure S1: H NMR spectrum of 7 in DMSO-d .
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1
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Figure S2: C NMR spectrum of 7 in CDCl .
3
.
3

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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Figure S3: FT-IR spectrum of 7.
Figure S4: ESI-MS spectrum of 7.
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Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2011
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Figure S5: H NMR spectrum of 9 in CDCl .
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This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2011
400
300
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0
500
550
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700
Wavelength (nm)
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Figure S6: Fluorescence titration spectra of 7 with AcO anion in DMSO solution at λex. = 450
nm.
4
3
1
5
0
5
0
0.36
0.24
y = 0.5384x + 0.056
2
(b)
R = 0.9961
(
a)

I
1
/  I
.12
0
0.00
0
1
2
0.0
0.5
7 ] / [ 7 + F ]
1.0
-
-
1
/ [ F ]
[
-
Figure S7: (a) Job’ plot and (b) Benesi-Hildebrand plots of dyad 7 for F anion upon excitation at
50 nm.
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Electronic Supplementary Material (ESI) for New Journal of Chemistry
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Figure S8: H NMR titration spectra of 7 with the F anion in DMSO-d .
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7

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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-
Figure S9: H NMR spectrum of 7 upon addition of 0.5 equiv of F anion in DMSO-d .
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8

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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-
Figure S10: H NMR spectrum of 7 upon addition of 1.5 equiv of F anion in DMSO-d .
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9

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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-
Figure S11: H NMR spectrum of 7 upon addition of 2.5 equiv of F anion in DMSO-d .
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1
0

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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1
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Figure S12: H NMR spectrum of 7 upon addition of 3.5 equiv of F anion in DMSO-d .
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1
1

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-
Figure S13: H NMR spectrum of 7 upon addition of 0.5 equiv of AcO anion in DMSO-d .
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1
2

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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-
Figure S14: H NMR spectrum of 7 upon addition of 1.5 equiv of AcO anion in DMSO-d .
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1
3

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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-
Figure S15: H NMR spectrum of 7 upon addition of 2.5 equiv of AcO anion in DMSO-d .
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1
4

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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-
Figure S16: H NMR spectrum of 7 upon addition of 5.0 equiv of AcO anion in DMSO-d .
6
1
5

Electronic Supplementary Material (ESI) for New Journal of Chemistry
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2
1
25
50
+
+
2+
7
+ Na , K , Mg
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+
+
2+
Ca , Ag , Cd
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+
2+
2+
Ni , Co , Pb
2+
Cu
7
5
0
2+
Hg
4
00
480
560
640
Wavelength (nm)
Figure S17: Change in fluorescence spectra of 7 upon addition of various metal ions as their
nitrate salts (10 equiv) in ACN solution.
510
340
170
0
510
340
170
0
(
a)
(
b)
-
-
8
, Cl , Br
8
+
-
-
I , SCN
M ions
-
AcO
-
F
480
560
Wavelength (nm)
640
480
560
Wavelength (nm)
640
Figure S18: Fluorescence spectra of 8 upon addition of tested (a) metal ions (20 equiv) and (b)
anions in ACN solution.
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1
0
8
6
4
2
0
-
-
9, Cl , Br
-
-
AcO , SCN
-
-
2+
I , F , Hg
4
80
560
640
Wavelength (nm)
Figure S19: Fluorescence spectra of 9 upon addition of various ions (20 equiv) in ACN solution.
2
10
40
7
2+
Hg
-
Br
1
70
0
400
480
560
640
Wavelength (nm)
2
+
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Figure S20: Fluorescence emission spectra of 7.Hg complex upon addition of Br ion (0 – 20
equiv) in ACN.
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