Counterion displacement assay with Biginelli product: Ratiometric Sensor for Hg2+ and Resultant complex as sensor for Cl-

AmanpreetKaur,a HemantSharma,bNarinderSingh,bNavneetKaura*

a Centre for Nanoscience and Nanotechnology (UIEAST), Panjab University, Chandigarh, India, 160014. bDepartment of Chemistry, Indian Institute of Technology Ropar (IIT Ropar), Rupnagar, Panjab, India, 140001. Corresponding Author: + 911722534464 navneetkaur@pu.ac.in Table of Contents  

Figure S1.1H NMR spectrum of Sensor1.

Figure S2.13C NMR spectrum of Sensor1.

Figure S3.IR spectrum of Sensor1.

Figure S4. Mass spectrum of Sensor1.

Figure S5.1H NMR spectrum of Sensor2.

Figure S6.13C NMR spectrum of Sensor2.

Figure S7.IR spectrum of Sensor2.

Figure S8. Mass spectrum of Sensor2.

Figure S9. Partial 1H NMR spectrum of Sensor1 + Hg2+.

Figure S10.PartialIR spectrum of Sensor1 and 1 + Hg2+.

Figure S11.UV-Vis absorption spectra of 1-2 (10 µM)in DMF/H2O (7/3; v/v) solvent system.

Figure S12.Fluorescence spectra of 1-2 (10 µM)in DMF/H2O (7/3; v/v) solvent system(λex=338 nm).

Figure S13. Salt perturbation studies of 1 recorded with 10 µM concentration of sensor in DMF/H2O (7:3, v/v) solvent system with the respective fluorescence spectrum recorded upon addition of 100 equiv. of tetrabutylammonium nitrate under the same concentration of sensor and solvent system.

Figure S14.Job’s plot between sensor1 and Hg(II). The concentration of [HG] was calculated by the equation [HG] = ΔI/Io ×[H].

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Figure S15.pH titration of Sensor 1 (10 µM)in DMF/H2O (1/9; v/v) solvent system (λex=338 nm).

Figure S16.UV-Vis absorption spectra of(1)2.Hg2+ (2.5 µM) in THF/H2O (4:1, v/v) solvent system.

Figure S17.Fluorescence spectrum of (1)2.Hg2+ (2.5 µM) in THF/H2O (4:1, v/v) solvent system (λex=338 nm).

Figure S18. Size distribution of complex (1)2.Hg2+ in DMF/H2O (8:92, v/v) solvent system.

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Figure S1. 1H NMR spectrum of Sensor1.

Figure S2. 13C NMR spectrum of Sensor1.

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Figure S3.IR spectrum of Sensor1.

Figure S4. Mass spectrum of Sensor1.

M+1

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 4

%

0

100 311.11735

248.11129

185.01059

144.0232109.1

212140.0192

126.0136

124.1;63 128.197

169.1204

149.0204

179.0102

209.2341

205.0235

191.0156

227.2288210.1

230

226.2121

247.0113

279.1977

250.1361

255.1258

259.189

280.1247 297.1

218

281.181

387.11072

312.1466

336.2180325.1

135313.1

97

355.1176

338.372

359.263

435.3972

388.1309

414.1215

412.1;136

389.185

415.180

432

4

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Figure S5. 1H NMR spectrum of Sensor2.

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Figure S6. 13C NMR spectrum of Sensor2.

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Figure

Figure

Tra

nsm

ittan

ce

100

%

0

100

104.01062

106.0473

S7. IR spec

S8. Mass sp

0.94

0.95

0.96

0.97

0.98

0.99

1

1.01

500

120 140

155116

137.1539

149.0237

ctrum ofSen

pectrum of

1000

160 180

183.13342

5.161

158.0254

179.0206

191.0476

nsor2.

Sensor 2.

1500Wave

200 220

205.0885

207.0313 230.1

241227.2201

2000number (c

240 260

248.15167

250.11734

2

256.1778

257.1180

2500cm-1)

280 300

279.11185

297.1903

281.1523

282.3242

298.1210

3000

320 340

325.12974

338.3883

326.1762 342.1

452

M+

3500 4

360 380

385.14610

386.11276

387.224

1

4000

400 420

407.11283

16

24

408.1350

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Figure S9. Stacked partial1H NMR spectra of: (A) Sensor 1 and (B-D) upon successive addition of Hg2+ to the solution of Sensor 1.

Figure S10. Stacked partial IR spectra of Sensor1 and 1 + Hg2+.

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Figure S11. UV-Vis absorption spectra of 1-2(10 µM)in DMF/H2O (7/3; v/v) solvent system.

Figure S12. Fluorescence spectra of 1-2 (10 µM)in DMF/H2O (7/3; v/v) solvent system(λex=338 nm).

0

0.2

0.4

0.6

0.8

1

270 300 330 360 390

Ab

sorb

an

ce

Wavelength (nm)

Sensor 1

Sensor 2

0

200

400

600

800

325 375 425 475 525

Flu

ore

sce

nce

Inte

nsi

ty

Wavelength (nm)

Sensor 1

Sensor 2

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Figure S13. Salt perturbation studies of 1recorded with 10 µM concentration of sensor in DMF/H2O (7:3, v/v) solvent system with the respective fluorescence spectrum recorded upon addition of 100 equiv. of tetrabutylammonium nitrate under the same concentration of sensor and solvent system.

Figure S14. Job’s plot between sensor1 and Hg(II). The concentration of [HG] was calculated by the equation [HG] = ΔI/Io ×[H].

0

200

400

600

800

1000

330 380 430 480 530

Flu

ore

sce

nce

Inte

nsi

ty

Wavelength (nm)

Sensor 1Sensor 1 + TBA‐NitrateSensor 2Sensor 2 + TBA‐Nitrate

0

5E‐08

0.0000001

1.5E‐07

0.0000002

2.5E‐07

0.0000003

3.5E‐07

0 0.2 0.4 0.6 0.8 1

[HG]

[H]/[H]+[G]

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Figure S15. pH titration of Sensor1(10 µM)in DMF/H2O (1/9; v/v) solvent system (λex=338 nm).

Figure S16. UV-Vis absorption spectra of(1)2.Hg2+ (2.5 µM) in THF/H2O (4:1, v/v) solvent system.

0

200

400

600

800

1000

300 350 400 450 500 550 600

Flu

ore

sce

nce

Inte

nsi

ty

Wavelength (nm)

10.48 10.16 9.95

9.61 8.8 8.24

7.88 7.39 6.43

6.12 5.61 5.28

4.87 4.42 4.24

3.97 3.55 3.33

2.69 2.06 10.8

10.9 11.6 12.1

0

0.2

0.4

0.6

0.8

1

260 310 360

Ab

sorb

an

ce

Wavelength (nm)

1 + Hg(II)

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Figure S17. Fluorescence spectrum of (1)2.Hg2+ (2.5 µM) in THF/H2O (4:1, v/v) solvent system (λex=338 nm).

Figure S18. Size distribution of complex (1)2.Hg2+ in DMF/H2O (8:92, v/v) solvent system.

 

0

100

200

300

365 415 465 515 565

Flu

ore

sce

nce

Inte

nsi

ty

Wavelength (nm)

1+Hg(II)

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