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