Post on 11-Jul-2020
A dipodal molecular probe for naked eye detection of trivalent cations (Al3+, Fe3+and Cr3+) in aqueous medium and its applications in real sample analysis and molecular logic gate
Rukmani Chandra, Amit Kumar Manna, Kalyani Rout, Jahangir Mondal,
and Goutam K. Patra*
Department of Chemistry, Guru GhasidasVishwavidyalaya, Bilaspur (C.G)
Table of Contents
Sl.No. Content Figure No.1 Mass spectra of L S12 IR spectra of L S23 1H NMR spectra of L S34 Geometry optimized diagram of the molecule (a) L + Fe3+,
(b) L+ Al3+ and (c) L + Cr3+S4
5 The contour diagrams of selected HOMO and LUMO orbitals of (a) L + Fe3+, (b) L+ Al3+ and (c) L + Cr3+
S5
6 The change in the absorbance intensity of L after addition of 1 equiv. of each of the metal ions in CH3CN:H2O (1:1, v/v) at 418 nm
S6
7 Absorbance spectra of L in different solvents S78 Job’s plot for of Al3+,Fe3+ and Cr3+ S89 ESI-mass spectra of L-Al3+,L-Fe3+ and L+ Cr3+ S910 Binding constants of (a) L-Al3+, (b) L-Fe3+ and (c) L-Cr3+
complexesS10
11 Detection limits forAl3+,Fe3+ and Cr3+ S1112 Competitive selectivity of L towards Fe3+ in the presence
of other metal ions(1 equiv.) (a) asorbance spectra, (b) bar diagram taking absorption intensity at 422 nm in CH3CN/H2O (1/1,v/v) solution.
S12
13 Competitive selectivity of L towards Cr3+ in the presence of other metal ions (1 equiv.) (a) absorbance spectra, (b) bar diagram taking absorption intensity at 416 nm in CH3CN/H2O (1/1,v/v) solution.
S13
14 Detection limit of L′ S1415 Stability constant of L' S1516 Time evolution of Al3+,Fe3+ and Cr3+ S1617 Selected optimized bond distances (Å) and angles (°) of L Table S1
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2018
Fig. S1.ESI-MS spectra of L.
Fig. S2. FTIR spectra of L.
Fig. S3. 1H NMR spectra of L
(a)
(b)
(c)
Fig. S4. Geometry optimized diagram of the molecule (a) L + Fe3+, (b) L+ Al3+ and (c) L + Cr3+
Fig. S5. The contour diagrams of selected HOMO and LUMO orbitals of (a) L + Fe3+, (b) L+ Al3+ and (c) L + Cr3+.
Fig. S6. Absorption spectra of L in different solvents.
Fig. S7. The change in the absorbance intensity of L after addition of 1 equiv. of each of the
metal ions in CH3CN:H2O (1:1, v/v) at 418 nm.
.
0.0 0.2 0.4 0.6 0.8 1.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Al3+at 422 nm Fe3+ at 422 nm Cr3+at 416 nm
Abso
rban
ce
Mole fraction of metalsFig. S8. Job plot for the binding of Lwith Al3+, Fe3+ and Cr3+.
(a)
(b)
(c)
Fig. S9. ESI-MS spectra of (a) L-Al3+,(b) L-Fe3+ and (c) L+ Cr3+
Fig. S10. Binding constants of (a) L-Al3+, (b) L-Fe3+ and (c) L-Cr3+ complexes.
1.0 1 .5 2 .0 2 .5 3 .0 3 .5 4 .0
0 .2
0 .4
0 .6
0 .8
1 .0
1 .2
A4
22
/ A
38
0
[A l3+ ] / (M )
E q u a t io n y = a + bA d j. R -S q u a 0 .9 9 1 1 5
V a lu e S ta n d a rd E r rB In te rc e p t -0 .1 0 8 8 0 .0 2 1 7B S lo p e 0 .3 0 3 7 0 .0 0 7 9 6
(a)
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.50.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
A 422 /
A 380
[Fe3+] / M)
Equation y = a + bAdj. R-Squ 0.99679
Value Standard ErB Intercept -0.250 0.01922B Slope 0.3750 0.00569
(b)
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.00.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
A 416
/ A 3
80
[Cr3+] / M
Equation y = a + bAdj. R-Squa 0.99391
Value Standard ErrB Intercept 0.1436 0.00538B Slope 0.0885 0.002
DL = 0.25 M
(c)
Fig. S11.Detection limits for (a)Al3+, (b) Fe3+ and (c) Cr3+
Fig. S12. Competitive selectivity of L towards Fe3+ in the presence of other metal ions (5
equiv.) (a) absorbance spectra, (b) bar diagram taking absorption intensity at 422 nm in
CH3CN/H2O (1/1,v/v) solution.
Fig. S13. Competitive selectivity of L towards Cr3+ in the presence of other metal ions (5
equiv.) (a) absorbance spectra, (b) bar diagram taking absorption intensity at 416 nm in
CH3CN/H2O (1/1,v/v) solution.
Fig. S14. Detection limit for Cu2+
Fig. S15. Stability constant of L′-Cu2+
0 2 4 6 8 10 12
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Fe3+ at 422 nm Al3+ at 422 nm Cr3+ at 416 nm
Abs
orba
nce
Time (min)
Fig. S16.Time evolution for Fe3+, Al3+ and Cr3+
Table S1. Selected optimized bond distances (Å) and angles (°) of L
Bond Length (Å) Bond Angle (°)
C1-C2 1.3916 C2-C1-C3 119.723 C57-C56-C58 116.4854
C1-C3 1.4104 C1-C2-C4 120.5773 C56-C57-C59 123.595
C2-C4 1.4061 C1-C3-C6 119.9209 C56-C57-O65 115.6621
C3-C6 1.4066 C1-C3-N50 117.4539 C59-C57-O65 120.7426
C3-N50 1.428 C6-C3-N50 122.4539 C56-C58-C60 121.8981
C4-C7 1.401 C2-C4-C7 119.5013 C57-C59-C62 118.6709
C4-C10 1.506 C2-C4-C10 120.0315 C58-C60-C62 120.6474
C6-C7 1.3966 C7-C4-C10 120.459 C59-C62-C60 118.7029
C10-C11 1.5059 C3-C6-C7 119.7877 C59-C62-N67 120.6457
C11-C12 1.4038 C4-C7-C6 120.4886 C60-C62-N67 120.6514
C11-C13 1.4034 C4-C10-C11 112.793 C62-N67-C68 122.0461
C12-C14 1.394 C10-C11-C12 120.3152 C62-N67-C69 121.941
C13-C16 1.3943 C10-C11-C13 120.2059 C68-N67-C69 116.0108
C14-C18 1.4085 C12-C11-C13 119.473 N67-C68-C70 111.5412
C16-C18 1.4084 C11-C12-C14 120.5498 C67-C69-C71 111.5894
C18-N53 1.4284 C11-C13-C16 120.5386
C21-C22 1.4114 C12-C14-C18 119.7629
C21-C23 1.4096 C13-C16-C18 119.769
C21-C52 1.465 C14-C18-C16 119.9029
C22-C24 1.3959 C14-C18-N53 117.2902
C22-O30 1.375 C16-C18-N53 122.6447
C23-C25 1.3863 C22-C21-C23 116.5109
C24-C27 1.4162 C22-C21-C52 120.6621
C25-C27 1.4233 C23-C21-C52 122.827
C27-N32 1.4047 C21-C22-C24 123.4485
N32-C33 1.49 C21-C22-O30 115.7105
N32-C34 1.4908 C24-C22-O30 120.8403
C33-C35 1.5281 C21-C23-C25 121.8034
C34-C36 1.5277 C22-C24-C27 118.8337
N50-C51 1.3004 C23-C25-C27 120.7744
C51-C56 1.4634 C24-C27-C25 118.6246
C52-N53 1.3 C24-C27-N32 120.5963
C56-C57 1.4115 C25-C27-N32 120.6017
C56-C58 1.4109 C27-N32-C33 119.8171
C57-C59 1.3948 C27-N32-C34 119.6529
C57-O65 1.3751 C33-N32-C34 114.8051
C58-C60 1.3845 N32-C33-C35 113.9605
C59-C62 1.4189 N32-C34-C36 113.9522
C60-C62 1.4266 C3-N50-C51 121.5536
C62-N67 1.3891 N50-C51-C56 120.231
N67-C68 1.4859 C21-C52-N53 120.1215
N67-C69 1.4866 C18-N53-C52 121.5511
C68-C70 1.5286 C51-C56-C57 120.728
C69-C71 1.5282 C51-C56-C58 122.7865