Electronic Supplementary Information · S1 Electronic Supplementary Information Sulfonamide...

S1

Electronic Supplementary Information

Sulfonamide carbazole receptors for anion recognition

Ángel L. Fuentes de Arriba,a María G. Turiel,a Luis Simón,a,b Francisca Sanz,c Juan F. Boyero,d Francisco M. Muñiz,e Joaquín R. Morána and Victoria Alcázar*f

a Departamento de Química Orgánica, Universidad de Salamanca, Plaza de los Caídos 1-5, E-37008 Salamanca, Spain. b Departamento de Ingeniería Química, Universidad de Salamanca, Plaza de los Caídos 1-5, E-37008 Salamanca, Spain.

c Servicio de Rayos X, Universidad de Salamanca, Plaza de los Caídos 1-5, E-37008 Salamanca, Spain. d Departamento de Química Analítica, Universidad de Salamanca, Plaza de los Caídos 1-5, E-37008 Salamanca, Spain.

e Instituto de Cerámica y Vidrio, CSIC, Kelsen 5, E-28049 Madrid, Spain. f Departamento de Ingeniería Química Industrial y Medio Ambiente, Universidad Politécnica de Madrid, José Gutiérrez Abascal 2, E-28006 Madrid, Spain.

Fax: +34 915618618; Tel: +34 913363203. Email: [email protected]

TABLE OF CONTENTS:

1. General Information. S2

2. General procedures for NMR and fluorescence titrations. S3

3. Copies of 1H and 13C NMR, MS and IR spectra of the new compounds (Fig. S1-S12). S6

4. Selected binding curves with halides (Fig. S13-S19). S18

5. Competitive titration (Fig. S20). S48

6. 1H NMR titrations with halides in DMSO-d6 (Fig. S21-S24). S51

7. Selected binding curves with oxoanions (Fig. S25-S26). S56

8. ORTEP diagrams and X-ray crystal structure data (Fig. S27-S32). S61

9. Modellization studies (Fig. S33-S35). S65

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011

S2

1. General Information.

1H NMR (200 MHz) and 13C NMR (50 MHz) spectra were recorded at room temperature on a Varian

Mod. Mercury VS 2000 and Bruker model WP-200-SY. Chemical shifts (δ) are given in ppm with the

solvent signal as internal standard unless otherwise stated (CHCl3, 7.26 ppm for 1H NMR, CDCl3, 77.0

ppm for 13C NMR; CH3OH, 3.31 ppm for 1H NMR, CD3OD, 49.0 ppm for 13C NMR). Coupling

constants (J) are reported in Hz. The following abbreviations were used to explain the multiplicities: s,

singlet; d, doublet; t, triplet; q, quartet; m, multiplet.

Melting points were determined using a Leica Galen III microscope and are uncorrected. IR spectra

were recorded as films (nujol) with a Nicolet IR100 spectrometer. Mass spectra were recorded with an

Applied Biosystems QSTAR XL. Fluorescence spectra were collected at 293 K using a Shimadzu RF-

5000 and RF-5301PC series spectrophotometers.

Suitable single crystals of the compounds and complexes were mounted on glass fibre for data

collection on a Bruker Kappa APEX II CCD diffractometer. Data were collected at 298 K using Cu Kα

radiation (λ = 1.54178 Å) and ω scan technique, and were corrected for Lorentz and polarization effects.

Structure solution, refinement and data output were carried out with the SHELXTLTM program package.

The structures were solved by direct methods combined with difference Fourier synthesis and refined by

full-matrix least-squares procedures, with anisotropic thermal parameters in the last cycles of refinement

for all non-hydrogen atoms. H atoms of sp3 hybridized carbons were located directly in a difference

Fourier map and freely refined. The rest of the hydrogen atoms were positioned geometrically.

Crystallographic data (excluding structure factors) for the structures reported in this paper have been

deposited at the Cambridge Crystallographic Data Centre as supplementary material nº: CCDC 83281-

83285.

All reagents were obtained from commercial suppliers and used without further purification. Solvents of

technical quality were distilled prior to use. Analytical thin layer chromatography was performed using

pre-coated aluminium-backed plates and visualized by UV. For column chromatography silica gel (70-

200 m) was used.


S3

2. General Procedure for NMR and fluorescence titrations.

Measurement of binding constants by 1H NMR titrations. A typical procedure for NMR titrations is

described. A solution of receptor 2 (2 mM, 2 mL) in CDCl3 was prepared and a volume of 500L was

added to a standard NMR tube. The 1H NMR spectrum of this sample was then collected at 298 K. A

solution of the tetrabutylammonium salt (0.01 M) was prepared by dissolving the exact amount of the

salt in the remaining solution (1.5 mL) of receptor 2. Aliquots of this solution were then added to the

NMR tube, mixing well after each addition and recording the corresponding 1H NMR spectra. Nine

additions were made of the following volumes: 40L, 40L, 40L, 40L, 40L, 100 L, 100 L,

200 L and 200 L. The concentration of receptor 2 was kept constant during the titration as the anion

solution also contained receptor 2 at its initial concentration. The downfield movements of sulfonamide

NH signals or the upfield shifts of the aromatic protons with respect to TMS were analyzed. These

proton signals ( ppm) were plotted against the ratio of concentrations [Guest]/[Host] and Ka values

were calculated using a Monte Carlo nonlinear curve-fitting method.

The following example illustrates the procedure:

1H NMR Titration of the tetrabutylammonium salt of perchlorate with compound 2.

Concentration of solutions [H] = 2.45 mM and [G] = 0.0123 M

The chemical shift of the H-4´ aromatic proton was followed throughout the titration.

ppm

sat ppm

Sample nº Guest added

(L) Chemical shift

(ppm) [G]/[H]

1 0 7.9515 0 2 40 7.8659 0.373 3 40 7.7961 0.693 4 40 7.7568 0.972 5 40 7.7408 1.101 6 40 7.7321 1.219 7 100 7.7112 1.436 8 100 7.6915 2.034 9 200 7.6831 2.352

10 200 7.6783 2.609


S4

Measurement of binding constants by fluorescence titrations. A typical procedure for fluorescence

titrations is described. A sample of receptor 2 (2 mL, concentrations 1, 5 or 10 M) in

spectrophotometric grade chloroform was transferred to a cuvette and placed into the fluorometer.

The sample was excited at 304 nm and the fluorescence emission intensity was measured at 377 nm

using a spectrofluorometer (slit width = 5 nm). Fluorescence titrations were carried out by addition of

aliquots of a solution of the anion guest (as the TBA or TEA salt). The samples were magnetically

stirred after each addition before recording the new spectra. The stock anion solution was prepared by

dissolving the proper amount of the guest in a receptor solution that has the same concentration as the

initial receptor sample. The concentration of the guest was calculated to be 10 times the concentration of

the receptor and the quenching of the fluorescence signal upon complex formation was analyzed. The

fluorescence intensity was plotted against the ratio of concentrations [Guest]/[Host] and Ka values were

calculated using a Monte Carlo nonlinear curve-fitting method.

The following example illustrates the procedure:

aromatic H-4´ chemical shift

[H] = 2.45×10-3M

Ka = 2.4×103 M-1


S5

Fluorescence titration of the tetrabutylammonium salt of iodide with compound 2.

Concentration of solutions [H] = 1.06×10-5 M and [G] = 1.03×10-4 M

F

Fsat =

Sample nº Guest added

(L) Fluorescence

intensity [G]/[H]

1 0 592 0 2 40 549 0.2 3 40 498 0.4 4 40 465 0.6 5 40 430 0.8 6 40 408 1 7 40 386 1.2 8 40 373 2.4 9 40 360 1.6

10 40 352 1.8 11 40 345 2 12 100 335 2.5 13 100 326 3 14 200 316 4 15 200 310 5

[H] = 1.06×10-5 M

Ka = 4.2×105 M-1


S6

3. Copies of 1H and 13C NMR, MS and IR spectra of the new compounds (Fig. S1-S12). Figure S1. 1H NMR (200MHz, CD3OD) spectrum of compound 4.

HN

t-Bu t-Bu

HO3S SO3H

4


S7

Figure S2. 13C NMR (50MHz, CD3OD) spectrum of compound 4.

HN

t-Bu t-Bu

HO3S SO3H

4


S8

Figure S3. MS spectrum of the compound 4.

HN

t-Bu t-Bu

HO3S SO3H

4


S9

Figure S4. IR spectrum of compound 4.

HN

t-Bu t-Bu

HO3S SO3H

4


S10

Figure S5. 1H NMR (200MHz, CDCl3) spectrum of the receptor 1.

t = 3h

Aldol 3, 4-nitrobenzaldehyde, imidazolidinone 4 and aldol imidazolidinones 5a and 5b

HN

t-Bu t-Bu

S SO

OOO

1

NH HN


S11

Figure S6. 13C NMR (50MHz, CDCl3) spectrum of receptor 1.

HN

t-Bu t-Bu

S SO

OOO

1

NH HN


S12

Figure S7. MS spectrum of receptor 1.

HN

t-Bu t-Bu

S SO

OOO

1

NH HN


S13

Figure S8. IR spectrum of receptor 1.

HN

t-Bu t-Bu

S SO

OOO

1

NH HN


S14

Figure S9. 1H NMR (200MHz, CDCl3) spectrum of receptor 2.

HN

t-Bu t-Bu

S SO

OOO

2

NHF3C HN CF3

CF3 CF3


S15

Figure S10. 13C NMR (50MHz, CDCl3) spectrum of receptor 2.


S16

Figure S11. MS spectrum of receptor 2.

HN

t-Bu t-Bu

S SO

OOO

2

NHF3C HN CF3

CF3 CF3


S17

Figure S12. IR spectrum of receptor 2.

HN

t-Bu t-Bu

S SO

OOO

2

NHF3C HN CF3

CF3 CF3


S18

4. Selected binding curves with halides (Fig. S13-S19).

Figure S13. Comparison of the association constants obtained for the complexes between receptor 2

and two example guests, by evaluation of the chemical shifts of sulfonamide NH and H-4´ aromatic

proton.

Titration with tetrabutylammonium hydrogen sulfate.

Chemical shifts (ppm) [G]/[H]

Sulfonamide NH chemical shifts

[H] = 2.46×10-3 M

Ka = 8.8×104 M-1

HN

t-Bu t-Bu

S SO

OOO

2

NF3C N CF3

CF3 CF3

H H


S19


Aromatic H-4´ chemical shifts

[H] = 2.46×10-3 M

Ka = 8.9×104 M-1


HN

t-Bu t-Bu

S SO

OOO

2

NHF3C HN CF3

CF3 CF3

H H


S20

Titration with tetrabutylammonium perchlorate.


[H] = 2.45×10-3 M

Ka = 2.4×103 M-1

HN

t-Bu t-Bu

S SO

OOO

2

NF3C N CF3

CF3 CF3

H H



S21


Aromatic H-4´chemical shifts

[H] = 2.45×10-3 M

Ka = 2.4×103M-1


HN

t-Bu t-Bu

S SO

OOO

2

NHF3C HN CF3

CF3 CF3

H H


S22

Figure S14. NMR titration curves for the binding of receptor 2 with halides (as their TBA or TEA salts)

with association constants beyond the upper limit of the technique (Ka>104).

Titration with tetrabutylammonium iodide.


TBA iodide


[H] = 2.36×10-3 M

Ka = 1.7×105 M-1


S23

Titration with tetraethylammonium bromide.

TEA bromide


[H] = 2.125×10-3 M

Ka = 5.4×106 M-1



S24

Figure S15. Fluorescence binding isotherm for the titration of receptor 2 (c = 10-5 M) with

tetrabutylammonium iodide in CHCl3 (ex = 304 nm; em = 377 nm; slit width = 5nm).

TBA iodide

[H] = 10-5 M

Ka = 4.2×105 M-1

Fluorescence (a.u.) [G]/[H]


S25

Figure S16: Fluorescence titration of receptor 2 (c = 10-5 M) with tetrabutylammonium iodide in CHCl3

(ex = 304 nm; em = 377 nm; slit width = 5nm).

wavelength compound 2 0.2 equiv.

TBAI 0.4 equiv.

TBAI0.6 equiv.

TBAI0.8 equiv.

TBAI1.0 equiv.

TBAI 1.2 equiv.

TBAI

300 1 1 2 1 3 1 2

301 3 1 2 0 1 0 3

302 0 2 1 2 0 2 1

303 2 2 3 2 1 1 1

304 1 1 1 1 2 1 1

305 2 5 3 1 1 4 2

306 2 3 4 5 4 6 3

307 12 11 14 13 10 10 12

308 28 27 26 23 27 28 29

309 23 26 25 26 26 34 28

310 15 14 16 16 16 19 17

311 4 3 4 3 3 6 3

312 2 1 4 1 2 2 3

313 0 2 1 3 2 1 1

314 0 3 2 0 0 3 1

315 2 1 0 2 1 1 1

316 1 2 1 0 1 1 3

317 1 2 1 3 1 1 0

318 2 1 2 2 2 2 5

319 1 1 1 3 2 1 2

320 2 3 2 3 3 3 2

321 2 2 1 1 1 1 1

322 1 1 2 2 1 4 2

323 3 2 2 2 1 2 1

0

100

200

300

400

500

600

300 350 400 450 500

wavelength (nm)

compound 2

0.2 equiv. TBAI

0.4 equiv. TBAI

0.6 equiv. TBAI

0.8 equiv. TBAI

1.0 equiv. TBAI

1.2 equiv. TBAI

1.4 equiv. TBAI

1.6 equiv. TBAI

1.8 equiv. TBAI

2.0 equiv. TBAI

2.5 equiv. TBAI

3.0 equiv. TBAI

4.0 equiv. TBAI

5.0 equiv. TBAI


S26

324 3 1 1 1 1 0 2

325 3 2 1 2 2 1 1

326 2 1 1 2 2 2 1

327 2 2 2 2 2 1 2

328 1 2 2 2 1 2 1

329 3 1 1 2 1 3 0

330 1 3 3 2 1 1 2

331 2 2 2 2 1 3 1

332 3 3 2 2 2 2 2

333 1 2 2 2 2 1 2

334 2 1 1 3 1 1 0

335 1 3 1 3 0 2 2

336 1 3 1 2 2 1 1

337 1 2 2 1 1 3 3

338 3 2 1 2 4 3 2

339 1 3 1 1 4 1 1

340 3 3 1 3 2 2 2

341 2 5 2 3 2 3 2

342 1 3 3 3 2 5 3

343 4 2 2 2 2 2 1

344 4 1 3 3 2 2 2

345 2 3 3 2 2 2 2

346 5 4 4 4 2 2 4

347 3 4 3 3 4 2 1

348 6 4 3 3 4 3 3

349 4 3 4 4 3 3 3

350 6 7 5 4 4 3 3

351 7 6 7 3 4 4 4

352 10 6 6 5 5 5 5

353 9 8 8 8 8 8 6

354 16 13 10 10 11 11 9

355 21 18 16 16 14 13 10

356 30 24 24 21 19 17 16

357 39 34 32 29 25 22 21

358 59 50 43 39 36 29 30

359 75 72 60 54 47 42 36

360 105 95 82 74 65 59 60

361 141 123 102 100 87 73 70

362 179 160 143 124 106 98 95

363 215 191 169 150 135 124 115

364 257 239 195 185 157 154 135

365 309 281 238 223 199 185 170

366 358 325 291 260 232 209 201

367 407 374 326 304 271 247 241

368 453 417 367 344 305 282 274

369 498 449 404 370 331 309 292

370 507 492 441 396 365 339 326


S27

371 557 504 462 427 377 358 348

372 583 533 477 447 409 386 370

373 583 540 493 467 427 400 392

374 592 549 498 465 430 408 386

375 593 536 503 465 436 412 387

376 573 549 488 467 426 405 393

377 579 538 493 457 420 405 394

378 554 521 473 449 413 392 379

379 541 511 469 448 403 384 365

380 537 507 464 441 390 372 359

381 526 476 452 418 393 361 355

382 524 485 443 413 383 360 338

383 511 465 435 401 375 341 331

384 489 458 421 395 358 348 326

385 472 451 410 385 346 341 323

386 476 456 406 386 358 342 322

387 468 435 399 379 341 321 320

388 451 424 389 369 332 325 309

389 435 423 375 356 326 314 299

390 434 393 359 341 309 309 296

391 420 393 359 335 310 298 286

392 396 382 341 330 304 285 281

393 381 355 327 310 283 268 261

394 364 334 316 290 278 260 247

395 347 314 298 288 256 249 236

396 317 305 282 273 251 235 228

397 313 293 261 258 236 224 217

398 285 278 249 238 218 213 204

399 277 250 243 220 211 203 189

400 252 238 223 211 192 188 185

401 234 227 205 195 179 173 167

402 224 214 192 183 171 168 158

403 205 199 183 175 165 151 150

404 198 194 167 165 158 143 143

405 175 169 165 152 138 140 140

406 167 162 152 141 135 134 125

407 155 151 145 135 126 119 118

408 150 149 130 135 116 114 111

409 145 138 119 123 114 108 102

410 135 129 116 115 106 99 99

411 127 121 114 109 103 94 92

412 126 120 105 102 97 90 86

413 121 115 101 96 86 85 84

414 110 99 92 95 86 81 82

415 96 98 94 91 77 81 73

416 102 89 86 86 74 77 74

417 92 90 80 77 75 69 66


S28

418 92 84 76 73 71 65 66

419 81 80 71 69 64 66 60

420 82 78 67 70 61 63 56

421 78 73 67 67 56 57 55

422 73 70 65 61 59 56 49

423 64 66 59 65 52 51 46

424 65 61 60 55 53 49 46

425 59 58 52 53 46 48 46

426 61 52 47 49 47 43 42

427 56 50 44 45 43 41 40

428 50 51 48 41 40 36 38

429 49 44 45 41 38 38 37

430 46 45 41 40 37 36 31

431 45 40 42 35 35 29 29

432 39 37 39 35 31 29 32

433 38 38 33 32 28 30 29

434 35 32 33 31 28 28 26

435 31 33 30 31 26 24 25

436 33 30 30 29 25 23 23

437 30 27 28 26 23 23 24

438 28 30 26 27 24 25 24

439 30 24 24 28 22 21 20

440 26 23 25 25 23 21 18

441 27 24 22 21 20 20 18

442 21 24 21 20 19 19 17

443 22 23 22 19 17 17 17

444 21 17 16 17 15 17 14

445 19 20 17 17 15 17 16

446 19 18 17 15 13 14 12

447 18 17 17 14 15 13 12

448 15 16 13 14 14 13 14

449 16 14 15 14 12 13 12

450 13 14 13 14 10 12 12

451 12 12 13 13 10 11 10

452 13 13 11 12 12 9 10

453 13 13 12 11 10 10 9

454 11 11 13 11 9 9 8

455 11 10 12 10 9 9 9

456 10 12 9 9 7 8 8

457 10 10 8 10 8 7 8

458 8 7 9 9 8 7 7

459 8 6 9 9 7 7 8

460 8 8 8 7 7 9 9

461 7 8 9 9 9 6 5

462 7 8 8 7 7 6 5

463 7 7 5 6 7 7 5

464 9 9 7 6 6 5 5


S29

465 6 6 7 7 5 5 6

466 6 7 7 5 5 5 4

467 8 7 5 5 4 5 4

468 6 4 6 6 5 4 4

469 5 5 5 4 5 3 5

470 5 4 5 5 4 4 5

471 6 5 4 3 4 4 4

472 4 3 4 4 3 2 4

473 5 4 3 4 5 5 3

474 5 4 4 4 4 3 3

475 5 4 3 4 3 4 4

476 5 4 3 3 3 4 3

477 4 4 5 3 4 4 2

478 5 3 4 4 3 3 4

479 5 4 3 3 3 3 5

480 5 3 5 5 5 3 3

481 3 3 4 3 3 2 2

482 3 4 3 4 4 2 3

483 6 5 2 3 3 3 2

484 3 2 2 4 2 2 3

485 4 3 1 2 2 2 3

486 4 3 1 3 3 2 2

487 3 4 2 1 2 2 2

488 3 3 2 3 3 2 2

489 3 4 3 4 1 2 3

490 3 4 3 2 2 4 2

491 3 2 3 3 1 2 3

492 2 3 3 3 2 2 3

493 1 3 2 3 2 2 2

494 2 1 5 1 1 2 1

495 3 3 1 1 3 2 3

496 2 1 2 3 1 1 2

497 2 2 2 3 1 1 1

498 3 2 1 2 2 2 2

499 2 4 2 2 4 1 1

500 3 3 4 2 2 2 3


S30

1.4 equiv. TBAI

1.6 equiv. TBAI

1.8 equiv. TBAI

2.0 equiv. TBAI

2.5 equiv. TBAI

3.0 equiv. TBAI

4.0 equiv. TBAI

5.0 equiv. TBAI

3 1 1 1 2 1 3 1

2 1 1 2 1 1 2 3

1 1 3 2 2 2 1 2

1 0 0 1 1 0 1 2

1 0 3 1 2 2 0 2

2 1 1 2 2 2 3 1

3 3 5 3 4 3 6 5

15 13 14 14 14 15 20 21

29 28 29 30 34 38 48 45

35 32 36 31 40 40 46 52

18 18 19 15 25 20 26 27

4 5 3 4 5 6 7 8

1 2 1 1 1 2 1 3

1 1 2 1 2 3 2 0

2 2 2 1 1 2 2 1

1 1 1 2 1 1 1 1

2 2 2 2 0 1 2 3

1 2 2 1 1 2 3 2

3 3 3 1 2 0 3 1

1 2 3 1 2 0 2 2

1 2 1 3 2 2 1 2

1 1 2 1 3 1 1 2

1 0 1 2 1 2 1 2

2 1 2 3 0 2 1 1

1 2 1 3 0 1 4 2

2 2 3 1 3 1 1 1

2 1 1 3 1 2 1 2

0 1 2 2 1 1 1 2

2 2 2 1 1 1 1 1

1 4 1 2 2 2 1 1

1 1 0 1 2 1 2 2

1 3 2 1 2 1 1 1

2 2 3 2 2 3 3 2

1 1 1 1 1 2 3 2

2 2 1 0 1 3 0 2

1 2 1 4 1 1 3 2

2 1 2 2 2 2 1 1

1 1 1 2 1 1 1 3

1 2 2 2 2 1 1 2

2 1 3 3 3 2 1 2

1 2 3 2 1 2 1 2

2 2 3 3 3 2 2 2

3 3 3 1 2 2 2 2

1 2 2 5 2 2 3 2

1 2 4 2 1 2 3 2


S31

2 4 3 2 3 2 2 2

2 3 3 3 2 2 1 3

4 3 3 4 2 3 3 3

3 3 3 2 3 2 2 2

2 2 4 2 4 3 2 3

3 4 3 3 4 2 8 2

5 5 5 3 4 4 4 2

5 5 3 4 5 5 3 4

6 7 6 5 5 5 4 5

8 8 9 9 6 8 7 7

11 10 10 10 8 8 9 11

15 14 14 12 12 12 9 9

22 19 18 19 16 16 15 14

28 27 28 22 22 21 18 21

36 37 34 36 30 28 26 30

51 50 48 41 43 39 37 37

63 63 59 58 53 51 46 46

81 84 75 79 71 63 64 61

105 104 98 95 86 87 81 74

131 125 124 117 108 103 99 91

161 150 151 144 133 126 125 122

183 178 176 170 161 151 145 135

218 209 203 198 190 172 169 167

246 241 238 225 219 205 203 199

283 269 265 253 238 232 222 222

311 291 295 279 266 254 250 247

325 325 311 307 288 276 271 273

353 336 330 326 315 304 307 298

364 353 354 343 323 313 318 305

373 360 352 345 335 326 326 310

374 367 364 351 338 322 328 329

365 359 353 348 340 321 333 319

359 354 357 349 333 326 333 319

352 358 346 335 332 318 320 316

343 336 343 329 318 311 307 310

343 323 330 326 315 313 314 299

327 327 329 319 302 297 304 300

313 318 314 312 296 291 303 290

314 318 314 308 299 283 292 279

318 311 312 303 293 279 288 280

302 296 303 300 280 274 283 275

299 295 290 297 276 268 274 281

295 290 294 291 277 272 269 265

298 280 290 277 271 270 261 265

288 277 284 274 265 255 256 259

274 269 264 266 256 250 254 251

261 254 258 256 252 242 252 256


S32

261 253 249 244 242 230 243 241

247 241 244 241 232 225 235 228

231 236 241 230 223 221 219 215

224 223 225 216 210 209 221 211

221 216 209 207 196 197 203 203

202 200 200 194 191 197 200 192

195 192 186 184 183 178 189 177

180 183 183 177 166 162 173 173

173 168 165 165 159 157 161 164

164 155 157 155 152 146 156 156

151 145 147 141 141 141 147 143

141 140 140 137 134 132 136 136

136 131 128 128 124 122 133 127

121 125 125 121 116 118 121 123

117 112 115 112 112 105 108 114

102 106 110 103 103 102 104 104

104 102 102 106 100 96 96 105

98 96 96 94 92 91 93 94

92 92 91 90 93 88 95 93

89 90 84 85 86 85 85 85

84 81 83 78 83 77 77 84

82 80 77 80 72 72 77 76

76 72 73 70 72 71 73 71

71 70 73 69 67 70 71 69

71 67 69 65 68 62 70 66

67 62 68 64 63 61 64 61

62 61 63 62 63 57 62 59

61 57 61 59 56 60 57 60

56 56 52 52 51 52 54 53

54 52 55 56 54 47 52 53

48 49 53 47 49 46 50 48

44 49 50 44 48 46 44 51

42 44 44 45 40 41 39 45

42 43 44 40 42 37 41 42

42 43 38 40 36 38 39 40

38 36 39 36 37 40 39 36

34 36 33 34 34 33 34 33

39 34 35 32 35 32 32 31

31 31 34 31 30 30 31 30

31 32 27 29 29 29 31 29

27 28 28 29 25 27 28 27

30 28 30 30 26 24 24 25

25 25 27 25 24 23 26 26

25 25 24 24 24 23 24 24

24 22 24 23 20 21 21 24

23 21 22 23 23 20 22 20

20 23 21 22 21 19 22 19


S33

21 21 20 18 19 19 20 20

19 20 17 19 17 18 20 19

21 16 19 16 16 17 18 17

18 17 17 16 16 19 17 18

18 15 15 15 15 17 15 15

16 14 14 14 13 15 15 14

15 14 14 14 15 13 14 15

14 14 15 12 12 13 13 14

13 11 13 12 12 11 14 13

12 11 11 11 9 10 13 13

10 11 10 12 11 9 12 12

12 11 12 12 9 10 12 9

12 9 10 11 9 11 10 9

10 10 10 10 11 8 10 10

10 9 7 10 9 11 10 10

7 8 8 8 7 9 8 8

8 8 9 8 7 9 8 8

7 8 7 8 8 8 5 8

9 9 8 7 8 9 6 7

7 8 7 7 7 7 6 7

6 8 6 6 6 6 7 6

7 6 6 6 8 6 6 5

7 6 6 8 6 7 7 7

5 5 6 8 6 5 4 6

6 5 6 5 6 5 8 6

5 5 6 6 4 5 5 6

5 5 5 5 4 5 5 5

5 6 5 4 5 4 7 7

4 5 4 4 5 5 7 6

4 7 4 5 5 5 4 5

4 5 4 4 3 3 4 4

4 5 4 3 3 5 5 4

4 3 4 3 5 3 3 4

4 4 4 5 3 5 5 3

4 5 4 5 3 2 4 6

4 4 4 4 3 2 4 6

2 4 3 3 4 3 3 3

3 5 4 4 3 3 2 2

4 4 4 4 4 2 4 2

3 4 3 3 2 4 4 2

3 3 3 4 5 1 4 4

3 2 3 2 3 3 2 5

5 3 3 2 3 5 3 2

2 4 3 2 3 2 4 3

2 2 2 1 2 3 3 4

2 3 2 3 2 1 2 2

2 3 2 2 3 4 2 3


S34

1 3 3 3 2 2 3 4

2 2 2 3 2 1 3 4

4 3 2 3 3 2 2 3

3 2 3 3 1 2 2 2

3 2 3 1 1 3 3 3

2 1 2 2 1 3 4 1

3 1 3 3 3 2 4 2

1 1 2 3 4 1 2 3

3 1 2 2 2 2 2 1

2 2 1 2 3 1 2 3

3 2 2 2 2 2 3 3

1 2 2 2 1 1 1 2

2 2 1 3 2 3 2 2

2 2 2 3 3 2 1 2

3 1 1 2 2 3 1 1


S35

Figure S17. Fluorescence binding isotherms of receptor 2 (c = 10-5 M) with tetraethylammonium

chloride and bromide in CHCl3 (ex = 304 nm; em = 377 nm; slit width = 5nm). The association

constants could not be accurately determined at this host concentration.

Titration with tetraethylammonium chloride.

TEA chloride

[H] = 10-5 M

Ka = 2×108 M-1



S36

Titration with tetraethylammonium bromide.

TEA bromide

[H] = 10-5 M

Ka = 2.7×108 M-1



S37

Figure S18. Fluorescence titration of receptor 2 (c = 10-5 M) with tetraethylammonium chloride in

CHCl3 (ex = 304 nm; em = 377 nm; slit width = 5nm).

wavelength compound 2 0.2 equiv. TEACl

0.4 equiv. TEACl

0.6 equiv. TEACl

0.8 equiv. TEACl

1.0 equiv. TEACl 1.2 equiv. TEACl

300 2 2 2 1 1 1 0

301 1 1 3 2 1 1 1

302 1 2 1 3 2 2 1

303 1 0 2 1 1 1 2

304 0 1 1 1 1 1 1

305 1 1 1 1 1 2 1

306 4 6 4 3 3 4 2

307 14 16 17 16 19 16 17

308 31 34 29 37 39 38 38

309 32 39 35 40 39 39 42

310 18 19 18 19 24 19 20

311 3 5 3 5 5 5 6

312 1 2 2 3 1 2 1

313 0 3 2 1 2 1 3

314 2 2 0 1 2 2 2

315 2 1 2 1 0 1 2

316 2 1 1 1 1 2 1

317 3 2 1 3 1 2 2

318 2 1 1 2 2 2 1

319 1 1 2 1 2 1 0

320 2 2 1 2 2 4 1

321 1 2 0 1 1 2 2

0

100

200

300

400

500

600

300 350 400 450 500

wavelength (nm)

compound 2

0.2 equiv. TEACl

0.4 equiv. TEACl

0.6 equiv. TEACl

0.8 equiv. TEACl

1.0 equiv. TEACl

1.2 equiv. TEACl

1.4 equiv. TEACl

1.6 equiv. TEACl

1.8 equiv. TEACl

2.0 equiv. TEACl

2.5 equiv. TEACl

3.0 equiv. TEACl

4.0 equiv. TEACl

5.0 equiv. TEACl


S38

322 1 1 1 3 2 2 1

323 0 0 0 1 1 1 2

324 1 0 1 2 4 1 1

325 1 1 1 0 2 1 2

326 0 2 1 2 0 1 0

327 1 1 0 4 0 1 2

328 0 2 2 2 1 3 2

329 1 1 2 1 1 1 0

330 1 1 0 3 1 2 1

331 2 2 1 1 2 1 1

332 2 2 1 1 1 2 0

333 1 1 3 2 1 0 1

334 1 1 1 2 1 1 0

335 1 2 1 2 0 1 1

336 1 1 2 1 1 1 1

337 2 1 1 1 0 3 1

338 2 3 1 1 1 2 3

339 2 1 2 1 1 2 1

340 3 1 1 1 1 1 3

341 1 1 3 1 1 3 1

342 0 2 2 4 1 2 2

343 2 2 1 2 1 2 1

344 2 4 2 1 1 1 3

345 2 2 2 1 1 1 2

346 2 0 2 2 2 3 1

347 3 3 2 2 4 1 1

348 5 3 3 2 1 3 3

349 5 3 2 3 3 3 2

350 2 4 2 3 2 4 3

351 5 6 3 4 5 3 4

352 7 5 6 4 4 6 2

353 9 9 8 8 5 5 8

354 13 13 9 9 8 9 7

355 19 16 14 17 14 13 10

356 25 25 20 19 18 17 15

357 41 32 29 27 24 20 21

358 54 46 38 38 34 27 26

359 73 68 60 49 43 42 39

360 104 89 82 72 59 54 53

361 137 116 100 89 85 66 67

362 180 150 131 115 100 92 83

363 212 189 163 143 128 112 115

364 254 216 202 173 157 145 141

365 297 266 221 210 192 168 167

366 339 298 280 249 225 206 195

367 377 337 322 290 264 241 225

368 411 377 347 322 293 279 265


S39

369 445 413 389 356 331 315 300

370 462 445 410 391 363 346 338

371 487 458 437 426 397 373 375

372 498 489 456 450 422 405 413

373 505 509 481 458 450 418 419

374 525 509 492 476 458 441 439

375 514 502 486 477 460 437 453

376 506 509 502 477 469 448 455

377 498 497 493 483 451 454 462

378 492 484 476 469 464 436 454

379 485 481 475 453 455 435 439

380 476 466 461 449 442 431 436

381 465 458 449 440 437 418 420

382 458 443 433 439 427 401 416

383 450 435 429 429 414 400 428

384 446 437 434 418 403 393 402

385 432 418 413 415 394 380 390

386 406 411 407 403 389 379 388

387 411 401 396 402 378 373 386

388 401 399 387 392 368 353 371

389 388 389 375 378 367 353 366

390 370 366 362 371 349 344 352

391 357 364 359 360 340 325 345

392 338 338 340 341 339 318 329

393 323 333 339 330 326 311 319

394 310 310 305 305 314 296 298

395 295 301 300 300 286 279 305

396 278 286 286 280 279 272 281

397 258 267 279 263 268 260 272

398 245 250 256 266 245 246 249

399 235 233 244 247 228 231 240

400 217 216 224 227 216 211 221

401 205 201 213 218 210 205 217

402 196 199 204 204 196 190 199

403 176 183 184 192 182 178 185

404 167 174 177 179 175 166 177

405 161 156 160 166 162 161 166

406 146 145 152 150 148 149 158

407 143 142 145 145 149 141 142

408 127 133 138 137 133 136 133

409 125 125 133 127 127 123 130

410 116 117 116 120 122 117 126

411 105 107 114 114 108 111 115

412 99 104 109 108 109 107 105

413 99 95 100 106 109 103 106

414 96 93 93 99 101 96 102

415 90 87 95 94 88 90 90


S40

416 85 82 88 83 90 84 90

417 83 85 85 84 82 81 87

418 75 79 76 76 76 77 85

419 76 76 79 75 73 72 80

420 67 71 73 68 69 72 73

421 66 65 64 67 66 72 67

422 62 60 64 63 66 67 62

423 58 60 59 62 60 61 64

424 53 56 60 58 56 58 58

425 53 55 50 54 53 53 57

426 47 48 50 53 50 49 53

427 47 45 49 47 51 48 49

428 44 45 45 45 45 43 43

429 40 43 45 41 43 42 42

430 38 38 38 45 39 43 43

431 38 35 38 38 37 39 38

432 32 34 33 35 34 36 38

433 31 32 37 35 36 32 36

434 30 30 32 33 33 33 34

435 32 32 31 28 32 32 30

436 28 29 28 28 32 27 30

437 24 26 27 27 27 26 30

438 23 24 25 27 25 24 28

439 21 26 27 22 24 26 27

440 21 23 24 21 24 22 23

441 21 22 23 22 21 21 25

442 18 21 20 18 21 21 23

443 18 17 19 21 20 21 22

444 16 18 17 16 17 17 22

445 17 17 14 20 17 18 18

446 16 14 17 16 18 18 14

447 13 16 14 14 16 15 16

448 12 13 15 16 16 15 14

449 13 11 14 13 15 12 16

450 11 15 14 11 11 12 16

451 10 13 10 15 13 12 14

452 10 11 10 12 13 12 11

453 10 11 12 11 10 11 10

454 10 9 10 10 11 9 10

455 11 9 9 10 9 9 10

456 7 10 10 9 9 7 10

457 10 7 9 9 7 10 11

458 8 7 11 8 7 7 10

459 7 7 6 8 8 9 7

460 8 8 6 8 8 7 7

461 5 6 7 7 6 6 8

462 6 8 6 7 7 6 9


S41

463 5 5 7 5 5 8 6

464 5 5 8 5 7 7 7

465 4 6 5 5 6 8 5

466 5 6 5 5 5 5 8

467 5 5 4 6 3 5 5

468 4 6 6 4 6 6 4

469 4 5 5 6 5 6 6

470 4 4 4 6 5 5 7

471 4 3 4 4 3 6 5

472 3 4 4 4 4 4 4

473 5 4 5 6 3 4 4

474 2 6 7 3 4 3 3

475 5 3 3 2 2 3 3

476 3 4 4 3 3 4 3

477 3 3 6 4 3 3 5

478 4 4 4 3 3 3 4

479 3 3 4 5 2 2 4

480 4 3 2 4 4 2 3

481 2 2 4 3 4 3 2

482 4 2 2 3 3 2 2

483 3 3 3 3 3 2 7

484 2 2 1 2 3 2 3

485 2 1 2 3 2 3 2

486 2 3 3 3 2 3 2

487 2 1 3 3 2 4 2

488 1 3 2 2 2 3 2

489 1 2 3 2 2 3 1

490 1 3 2 2 2 2 4

491 0 2 2 2 2 3 2

492 3 1 3 3 3 3 0

493 2 2 2 3 3 3 2

494 2 1 1 5 2 2 1

495 2 3 2 2 1 1 2

496 1 1 2 3 2 2 2

497 3 2 3 3 1 1 2

498 1 2 2 2 3 3 0

499 1 4 2 2 2 2 1

500 1 1 2 2 1 3 4


S42

1.4 equiv. TEACl

1.6 equiv. TEACl

1.8 equiv. TEACl

2.0 equiv. TEACl

2.5 equiv. TEACl

3.0 equiv. TEACl

4.0 equiv. TEACl

5.0 equiv. TEACl

0 1 1 2 4 1 0 3

2 1 2 1 3 3 2 0

0 2 1 0 2 2 3 2

2 2 0 2 1 1 1 1

2 2 1 2 1 2 1 3

1 2 2 3 2 1 2 1

3 6 4 4 7 5 6 7

17 17 21 18 22 23 24 28

36 40 46 51 54 50 59 72

40 42 51 55 50 61 65 67

20 22 28 30 29 36 35 38

4 6 6 7 6 7 8 9

2 2 2 2 3 2 1 4

0 2 2 1 2 2 1 3

2 2 1 4 1 1 3 1

2 1 2 2 0 2 1 3

2 2 1 1 2 4 0 1

1 3 2 1 2 1 1 0

1 1 4 2 2 2 2 3

1 1 1 2 3 3 2 3

0 2 1 1 4 3 2 1

1 3 2 3 1 2 0 2

1 2 1 2 3 2 2 0

1 1 2 1 2 2 0 2

2 1 3 1 2 3 3 0

2 1 2 1 0 1 1 1

1 2 3 2 1 2 1 1

0 1 1 2 1 5 3 2

2 4 1 3 3 2 2 2

0 0 0 1 0 2 2 1

3 2 1 4 1 3 1 2

2 1 2 3 2 2 2 2

3 2 2 6 1 1 1 1

1 2 2 2 1 1 2 2

1 1 1 2 1 2 3 1

0 1 2 3 1 3 2 1

2 1 1 2 2 3 2 1

0 2 2 2 1 0 4 3

1 2 1 3 2 3 4 3

0 3 2 1 3 2 1 2

3 1 1 4 3 2 2 1

2 3 3 2 3 2 3 2

1 1 2 3 3 2 1 3

2 2 0 3 3 2 3 2

1 2 4 2 1 3 3 3


S43

1 1 2 2 2 3 2 3

2 2 3 2 3 1 2 3

2 3 2 2 2 3 2 3

1 5 4 2 2 4 1 3

2 2 3 1 3 4 2 5

3 5 2 3 4 3 2 4

5 5 3 3 3 3 4 5

5 4 3 9 5 5 5 5

7 4 8 6 5 9 6 6

8 5 9 6 8 9 9 9

13 10 13 11 11 10 13 11

17 15 12 16 13 19 15 14

19 22 18 20 20 19 21 19

28 29 25 28 24 28 27 31

39 35 35 37 37 37 34 38

50 50 50 48 49 53 47 49

72 63 68 62 65 64 68 67

92 84 87 83 76 81 87 85

108 101 102 97 99 99 99 106

135 127 128 126 120 118 121 132

165 159 151 160 153 153 147 162

198 196 181 176 187 179 189 193

220 227 216 220 223 223 214 218

270 258 258 256 249 255 254 266

300 294 290 296 276 282 289 299

338 331 340 329 319 337 326 321

374 373 366 362 352 346 354 356

402 409 397 397 393 388 386 390

440 434 417 431 399 414 419 425

439 439 439 439 439 439 439 439

470 456 460 457 447 442 451 461

467 471 456 459 441 446 452 462

464 469 449 464 448 463 451 473

461 455 463 461 446 458 456 457

470 452 446 447 439 436 450 459

444 440 452 445 426 452 439 450

429 438 444 435 431 425 428 440

437 435 437 426 422 416 429 434

418 411 414 419 405 407 408 405

404 419 410 409 397 403 402 412

398 406 388 404 382 389 377 397

398 392 386 377 379 393 399 385

390 383 380 389 370 382 386 385

378 371 367 384 378 374 372 375

361 364 355 374 354 360 360 370

364 361 352 356 355 346 360 349

351 344 347 349 332 356 352 355


S44

336 345 347 341 327 331 334 337

328 330 319 334 322 329 318 321

324 319 325 316 310 309 306 322

302 308 303 300 295 295 298 303

287 292 281 281 280 291 292 293

279 276 279 282 273 271 273 284

258 264 256 261 255 259 258 273

251 250 246 253 242 247 246 243

240 226 230 230 226 232 229 242

217 224 221 224 217 215 217 227

204 203 213 204 204 214 209 216

189 199 195 191 192 193 192 196

187 183 185 188 176 180 173 188

175 176 174 176 166 173 181 172

162 157 158 162 156 161 159 167

151 147 148 156 144 153 151 159

145 143 139 146 139 140 140 146

137 137 143 142 134 140 134 139

125 128 129 130 127 130 129 123

123 123 125 124 122 119 119 127

117 114 112 116 118 112 112 117

116 112 109 112 106 104 103 112

103 103 103 104 103 103 96 106

93 100 97 103 98 95 95 98

91 90 90 93 99 93 92 91

87 85 88 90 87 84 89 86

79 92 85 87 81 86 85 88

82 83 81 79 78 82 79 84

73 76 75 75 75 76 78 79

72 69 70 73 72 72 66 69

72 66 67 73 66 70 69 71

63 66 64 64 64 64 61 63

61 65 59 56 56 53 60 61

58 59 59 57 57 58 57 58

54 52 58 57 53 54 55 56

56 49 51 51 50 51 50 54

52 51 45 49 49 46 52 53

46 47 44 47 45 44 44 45

44 46 45 41 47 43 43 43

42 40 41 44 40 44 40 42

39 37 41 41 39 39 37 38

40 35 38 34 36 34 40 37

30 36 36 34 35 37 36 34

33 34 32 37 31 30 32 34

33 30 31 32 33 32 31 29

30 28 28 28 26 30 31 33

31 27 26 29 28 26 26 28


S45

28 27 29 27 27 24 25 27

24 26 22 25 25 24 23 25

24 23 22 24 25 22 24 24

22 20 25 20 21 21 23 23

20 21 23 24 20 21 21 24

20 19 21 21 23 21 21 21

17 17 20 19 18 19 16 21

18 17 18 19 20 18 17 16

16 18 18 17 17 19 18 18

14 16 16 15 15 16 15 15

14 15 15 14 14 15 14 14

13 15 17 11 14 16 14 15

13 12 15 14 14 14 13 15

11 13 13 12 12 13 11 14

12 12 11 14 11 13 11 11

12 11 12 9 13 10 12 12

9 9 10 8 12 10 11 9

10 9 12 11 13 10 10 10

11 9 9 8 9 12 7 10

9 12 7 9 9 9 9 12

8 6 8 9 9 10 9 9

9 8 6 8 9 7 11 8

10 8 9 10 8 8 8 7

7 9 8 8 7 6 5 6

6 8 12 8 8 9 7 6

8 9 6 7 6 7 8 7

7 6 6 6 6 7 6 6

6 5 7 7 9 5 5 7

5 8 5 5 6 7 7 4

7 6 6 7 8 5 5 6

5 6 5 7 6 8 5 5

3 6 5 5 5 5 5 7

4 4 5 5 6 4 4 3

4 4 5 4 6 6 4 5

5 5 5 5 6 5 6 5

5 4 4 4 4 5 4 4

3 3 5 4 4 3 3 4

4 4 6 7 4 5 4 4

2 4 3 3 1 4 4 3

4 4 3 5 5 4 3 4

4 4 3 5 5 5 3 4

3 4 2 4 3 2 4 3

3 3 4 4 3 5 5 6

3 3 4 3 2 3 1 3

2 3 2 4 2 2 2 3

5 3 3 1 2 5 3 4

4 3 2 3 3 2 3 2


S46

3 4 4 2 2 4 5 4

3 3 2 3 1 2 1 3

2 3 2 2 3 6 2 3

2 3 2 3 2 2 3 3

3 3 2 2 2 3 5 3

2 2 2 3 3 2 3 4

2 2 1 2 3 2 3 1

3 2 2 3 4 1 3 3

1 2 3 2 3 1 4 4

2 3 1 1 3 2 3 2

1 2 3 1 2 4 4 2

2 2 2 2 2 2 2 4

2 4 2 2 1 4 2 1

2 2 3 2 2 1 2 2

3 2 1 3 3 1 0 1


S47

Figure S19. Fluorescence titration of receptor 2 (c = 5×10-6 M) with tetraethylammonium bromide in

CHCl3 (ex = 304 nm; em = 377 nm; slit width = 5nm).

TEA bromide

[H] = 5×10-6 M

Ka = 1.1×106 M-1



S48

4. Competitive titration (Fig. S20).

Measurement of binding constants by competitive fluorescence titrations. A competitive

fluorescence titration was carried out to evaluate the association constant for the binding of

tetraethylammonium chloride to receptor 2. The determination of the relative binding constant was

carried out following the protocol described by Davis1 for NMR competitive titrations.

∙∙

∙

∙

∙ ∙∙ ∙

On addition of tetraethylammonium chloride to a preformed complex of receptor 2 with bromide,

fluorescence intensity (F) was partially restored from an initial value of 152 ( ∙ ) to 226 a.u. ( ∙ ),

and the proportion of 2 existing as ∙ can be obtained from:

∙ ∙

∙ ∙

Kexch can then be estimated from each point of the titration and averaged.

1 J. P. Clare, A. J. Ayling, J. -B. Joos, A. L. Sisson, G. Magro, M. N. Pérez-Payán, T. N. Lambert, R. Shukla, B. D. Smith and A. P. Davis, J. Am. Chem.

Soc., 2005, 127, 10739.


S49

Figure S20. Fluorescence competitive titration of the preformed complex between receptor 2 (c =

5×10-6 M) and TEABr (c = 2×10-5 M) (2·TEABr) with tetraethylammonium chloride in CHCl3 (ex =

304 nm; em = 377 nm; slit width = 5nm).


∙5 102 10

∙ 152

∙ 230


S50

Fobserved (a. u.)

[G]/[H] [2·Cl] Kexch

185 0.776 2.115×10‐6 7.108

191 0.953 2.5×10‐6 7.726

195 1.123 2.756×10‐6 7.627

200 1.446 3.076×10‐6 6.956

202 1.599 3.205×10‐6 6.786

204 1.746 3.333×10‐6 6.791

208 2.096 3.589×10‐6 6.861

211 2.418 3.782×10‐6 7.019

226 10.48 4.743×10‐6 7.645

7.17

∙∙

∙

∙⟹ ∙ ∙ 7.17 1.1 10 .


S51

6. 1H NMR titrations with halides in DMSO-d6 (Fig. S21-S24).

Figure S21. Plots of the 1H NMR spectra (5-18 ppm) corresponding to the titration of receptor 2 with

TBAF in DMSO-d6.

NH sulfonamide

receptor 2 in DMSO-d6

NH carbazole


S52

receptor 2 + 3.25 equiv. TBAF

NH carbazole

NH sulfonamide

receptor 2 + 10 equiv. TBAF

HF2-

NH carbazole


S53

Figure S22. NMR titration curve for the binding of receptor 2 with TEACl in DMSO-d6.

TEA chloride


[H] = 3.62 ×10-3 M

Ka = 2.1×102 M-1

Chemical shifts (ppm) added volume (mL)


S54

Figure S23. NMR titration curve for the binding of receptor 2 with TEABr in DMSO-d6.

TEA bromide


[H] = 5.81 ×10-3 M

Ka = 25 M-1

Chemical shifts (ppm) added volume (mL)


S55

Figure S24. NMR titration curve for the binding of receptor 2 with DMSO in CDCl3.

TEA bromide


[H] = 9.29×10-3 M

Ka = 7.1 × 102 M-1

added volume (mL) Chemical shifts (ppm)


S56

7. Selected binding curves with oxoanions (Fig. S25-S26).

Figure S25. NMR titration curves for the binding of receptor 2 with oxoanions (as their TBA salts).

Titration with tetrabutylammonium m-nitrobenzoate.

TBA m-nitrobenzoate

[H] = 2.14×10-3 M

Ka = 2.9×104 M-1



S57


TBA hydrogen sulfate

[H] = 2.46×10-3 M

Ka = 8.8×104 M-1



S58


TBA ClO4

[H] = 2.45×10-3 M

Ka = 2.4×103 M-1



S59

Figure S26. NMR titration curves for the binding of Schreiner thiourea with anions at 298K in CDCl3.

Titration with tetrabutylammonium m-nitrobenzoate.

TBA m-nitrobenzoate

[H] = 2.63×10-3 M

Ka = 1.4×104 M-1



S60

Titration with tetraethylammonium chloride.

TEA chloride

[H] = 2.60×10-3 M

Ka = 8.9×103 M-1



S61

8. ORTEP diagrams and X-ray crystal structure data (Figures S27-S32).

Figure S27. ORTEP diagram and X-ray crystal structure data for the receptor 1. The solvent molecule

(C6H12) has been omitted for clarity (CCDC 83281, corresponds to Figure 1 in the manuscript).

Crystal data: 2(C28H43N3O4S2), C6H12, M = 1183.74, monoclinic, space group P21/n (nº 14), a =

17.7484(4) Å, b = 15.5301(4) Å, c = 26.3541(7) Å, ==90°, =, V = 6962.7(3) Å3, Z

= 4, Dc = 1.129 Mg/m3, m = (Cu-K) = 1.665 mm-1, F(000) = 2560. 48691 reflections were collected at

3.85 2 67.12 and merged to give 11833 unique reflections (Rint = 0.0374), of which 9300 with I >

2 were considered to be observed. Final values are R = 0.0741, wR = 0.2275, GOF = 1.029,

max/min residual electron density 0.677 and -0.385 e. Å-3.


S62

Figure S28. ORTEP diagram and X-ray crystal structure data for the receptor 2 (CCDC 83282,

corresponds to Figure 2 in the manuscript).

Crystal data: 2C36H31N3O4F12S2, M = 1723.52, monoclinic, space group C2/c (nº 15), a = 25.4032(11)

Å, b = 25.5614(11) Å, c = 23.8466(8) Å, = = 90°, =V = 15458.8(11) Å3, Z = 8, Dc =

1.481 Mg/m3, m = (Cu-K) = 2.1645 mm-1, F(000) = 7040. 35827 reflections were collected at 2.45

2 67.27 and merged to give 12216 unique reflections (Rint = 0.0533), of which 7925 with I > 2

were considered to be observed. Final values are R = 0.1261, wR = 0.3797, GOF = 1.055, max/min

residual electron density 0.849 and -0.739 e. Å-3.


S63

Figure S29. ORTEP diagram and X-ray crystal structure data for the complex between receptor 2 and

TEACl. The counter ion has been omitted for clarity. (CCDC 83283, corresponds to Figure 3 in the

manuscript).

Crystal data: C36H31N3O4F12S2, C8H20NCl, M = 1027.46, orthorhombic, space group Pna21 (nº 33),

a = 18.6703(5) Å, b = 10.3143(3) Å, c = 25.8835(6) Å, = == 90°, V = 4984.4(2) Å3, Z = 4,

Dc = 1.369 Mg/m3, m = (Cu-K) = 12.251 mm-1, F(000) = 2128. 21673 reflections were collected

at 3.41 2 67.27 and merged to give 7899 unique reflections (Rint = 0.0308), of which 6157 with

I > 2 were considered to be observed. Final values are R = 0.0739, wR = 0.2217, GOF = 1.089,

max/min residual electron density 1.364 and -0.523 e. Å-3.


S64


TEABr. The counter ion has been omitted for clarity. (CCDC 83284, corresponds to Figure 4 in the

manuscript).

Crystal data: C36H31N3O4F12S2, C8H20NBr, M = 1071.92, orthorhombic,space group Pna21 (nº

33), a = 18.7203(5) Å, b = 10.3816(3) Å, c = 25.9329(6), = == 90°, V = 5040.0(2) Å3, Z =

4, Dc = 1.413 Mg/m3, m = (Cu-K) = 12.668 mm-1, F(000) = 2200. 24282 reflections were

collected at 3.41 2 67.19 and merged to give 6893 unique reflections (Rint = 0.0301), of which

5926 with I > 2 were considered to be observed. Final values are R = 0.0527, wR = 0.1505,

GOF = 1.048 max/min residual electron density 1.093 and -0.839 e. Å-3.


S65


TBAI. The counter ion has been omitted for clarity. (CCDC 83285, corresponds to Figure 5 in the

manuscript).

Crystal data: C36H31N3O4F12S2, C8H20NI, M = 1118.91, orthorhombic, space group Pna21 (nº 33), a =

18.8303(5) Å, b = 10.4962(3) Å, c = 26.0580(7) Å, = == 90°, V = 5150.3(2) Å3, Z = 4, Dc =

1.443 Mg/m3, m = (Cu-K) = 16.408 mm-1, F(000) = 2272. 24273 reflections were collected at 3.39

2 67.27 and merged to give 7779 unique reflections (Rint = 0.0401), of which 6379 with I > 2

were considered to be observed. Final values are R = 0.0440, wR = 0.1169, GOF = 1.021, max/min

residual electron density 1.029 and -0.996 e. Å-3.


S66

Figure S32. Two views of the crystalline packing 2·TEACl.


S67

9. Modellization studies (Figures S33-S35).

Figures and cartesian coordinates of optimized structures of the complexes of receptor 2 with anions.

Complex with TEACl.

Figure S33. Optimized structure of the complex between receptor 2 and TEACl (B3LYP/6-31G** level

of theory).

Cartesian coordinates

C -1.14482 -0.21099 -2.10257 C -3.46252 -0.81982 -2.40373 C -0.76906 -1.45374 -2.68093 N -0.01063 0.49798 -1.77628 C -3.11093 -2.05532 -2.97499 H -4.50169 -0.53930 -2.30076 C 0.68132 -1.47612 -2.68499 C -1.74660 -2.35492 -3.10246 C 1.09781 -0.24787 -2.11247 H 0.00517 1.42007 -1.35972 C 1.62648 -2.41360 -3.11360


S68

H -1.43833 -3.30139 -3.53657 C 2.46912 0.02136 -1.98786 C 2.99619 -2.15815 -2.99367 H 1.27917 -3.34644 -3.54216 C 3.39090 -0.92825 -2.42635 S 3.05365 1.51751 -1.21419 H 4.44244 -0.68573 -2.33038 O 4.45868 1.70153 -1.58151 O 2.06519 2.57628 -1.48781 C -4.17054 -3.06979 -3.44849 C -3.99761 -4.39337 -2.66645 H -4.13216 -4.23357 -1.59211 H -4.73973 -5.12893 -2.99577 H -3.00659 -4.83220 -2.81780 C -5.60769 -2.56319 -3.22136 H -6.31941 -3.31303 -3.58086 H -5.82348 -2.39084 -2.16265 H -5.80510 -1.63630 -3.77009 C -3.98519 -3.33753 -4.96066 H -4.11437 -2.41760 -5.54011 H -2.99192 -3.73749 -5.18661 H -4.72386 -4.06660 -5.31141 C 4.07820 -3.16006 -3.44101 C 4.92422 -3.58433 -2.21660 H 5.69330 -4.30370 -2.51938 H 5.43249 -2.73759 -1.74765 H 4.29693 -4.06030 -1.45584 C 3.46767 -4.42861 -4.06553 H 2.83566 -4.97089 -3.35452 H 2.86952 -4.19996 -4.95403 H 4.26899 -5.10712 -4.37400 C 4.99532 -2.49787 -4.49603 H 4.42376 -2.19691 -5.38019 H 5.49601 -1.60854 -4.10297 H 5.77300 -3.19987 -4.81634 C -2.50368 0.09888 -1.96607 S -3.03798 1.59739 -1.16460 N -2.93856 1.35363 0.49644 O -2.02076 2.63271 -1.42587 O -4.43909 1.83021 -1.51971 H 1.99243 1.47262 0.79285 N 2.95941 1.30204 0.45278 C 3.65515 0.27560 1.13798 C 4.98264 -0.05130 0.83938 C 2.99198 -0.39744 2.17713 C 5.61892 -1.07060 1.55052 H 5.50888 0.48368 0.05915 C 3.65843 -1.38690 2.89473 H 1.96672 -0.13246 2.41669 C 4.97283 -1.74293 2.58364 H 5.47930 -2.52190 3.13863


S69

C 7.04371 -1.39845 1.19270 C 2.92489 -2.14550 3.97151 F 7.88920 -0.39991 1.53308 F 7.48167 -2.52015 1.79999 F 7.18592 -1.58146 -0.14496 F 3.76619 -2.56071 4.94664 F 1.96463 -1.39913 4.55091 F 2.32590 -3.25250 3.47472 C -3.64275 0.33121 1.17577 C -2.99051 -0.33676 2.22396 C -4.97021 0.00632 0.86769 C -3.66627 -1.31893 2.94430 H -1.96713 -0.07183 2.47136 C -5.61498 -1.00422 1.58161 H -5.49469 0.54614 0.09018 C -4.97822 -1.67209 2.62538 H -5.49574 -2.43757 3.18946 C -2.94480 -2.06570 4.03754 C -7.00594 -1.40853 1.17285 F -2.00199 -1.30718 4.63019 F -3.79881 -2.48441 4.99992 F -2.32615 -3.16860 3.55652 F -7.72398 -0.36401 0.70881 F -6.97700 -2.33429 0.17786 F -7.69679 -1.95907 2.19333 H -1.96908 1.51407 0.83370 Cl 0.02267 1.74684 1.63824 C 0.99558 4.89411 0.42864 H 0.41761 3.97091 0.48721 H 1.73736 4.76347 -0.35725 C -1.06319 6.25166 0.95916 H -1.71530 7.00288 0.51011 H -0.56780 6.71095 1.81693 C -0.61437 5.50850 -1.36886 H -1.39197 6.24087 -1.59677 H -1.09975 4.56158 -1.13812 C 0.83056 7.26849 -0.28622 H 1.21324 7.55668 0.69350 H 1.68659 6.99178 -0.90376 N 0.03881 5.98726 -0.06759 C 0.07515 8.43389 -0.91646 H 0.77678 9.26809 -1.00967 H -0.29502 8.20714 -1.91846 H -0.75926 8.78286 -0.30396 C 0.31992 5.32049 -2.55797 H 1.07053 4.54680 -2.38668 H -0.30286 4.97816 -3.38979 H 0.81122 6.24348 -2.87867 C 1.67048 5.15444 1.76734 H 2.27420 4.26791 1.97755 H 2.34092 6.01841 1.76486


S70

H 0.96115 5.24848 2.59271 C -1.87496 5.03669 1.39217 H -2.60610 5.38546 2.12826 H -2.42847 4.58224 0.56906 H -1.26953 4.25672 1.86005

Complex with TEAClO4 .

Figure S34. Optimized structure of the complex between receptor 2 and TEAClO4 (B3LYP/6-31G**

level of theory).

Cartesian coordinates

C 1.37599 0.18387 2.03737 C 3.72090 -0.30197 2.33264 C 1.06393 -0.88365 2.91932 N 0.20781 0.77436 1.60247 C 3.43525 -1.36293 3.21051 H 4.74366 -0.04664 2.09204 C -0.38411 -0.92097 3.01289


S71

C 2.08858 -1.64422 3.48454 C -0.86126 0.12456 2.18513 H 0.14586 1.62854 1.06279 C -1.28439 -1.73216 3.71189 H 1.83124 -2.46688 4.14464 C -2.24117 0.34327 2.07521 C -2.66410 -1.52462 3.61298 H -0.89481 -2.52742 4.33654 C -3.11757 -0.47687 2.78348 S -2.87643 1.60820 0.99245 H -4.17791 -0.27730 2.68761 O -4.27485 1.84965 1.34630 O -1.90114 2.71638 0.99165 C 4.54886 -2.22886 3.83208 C 4.44699 -3.66455 3.26291 H 4.60294 -3.66434 2.17999 H 5.21083 -4.30730 3.71457 H 3.46989 -4.11414 3.46567 C 5.95572 -1.68649 3.51312 H 6.70676 -2.30959 4.00864 H 6.17075 -1.71297 2.44102 H 6.08990 -0.66049 3.87210 C 4.38499 -2.26780 5.36921 H 4.44886 -1.26227 5.79775 H 3.42688 -2.70079 5.67207 H 5.17637 -2.87834 5.81705 C -3.69665 -2.39844 4.35089 C -4.55675 -3.15938 3.31369 H -5.29640 -3.78688 3.82335 H -5.10005 -2.48335 2.64845 H -3.93263 -3.80952 2.69189 C -3.02361 -3.43350 5.27195 H -2.39935 -4.13699 4.71142 H -2.40303 -2.95572 6.03766 H -3.79119 -4.01881 5.78755 C -4.61139 -1.50530 5.22202 H -4.02998 -0.95782 5.97115 H -5.16244 -0.77323 4.62479 H -5.34865 -2.12143 5.74780 C 2.71371 0.46523 1.74175 S 3.13413 1.69194 0.52265 N 2.76830 1.02586 -0.97725 O 2.17598 2.80801 0.65015 O 4.57375 1.93810 0.60051 H -1.88779 1.21134 -1.00459 N -2.80386 1.01717 -0.57769 C -3.44524 -0.17588 -0.99148 C -4.72148 -0.52662 -0.53499 C -2.78540 -1.00898 -1.90561 C -5.30055 -1.72263 -0.95960 H -5.25461 0.12798 0.14230


S72

C -3.39326 -2.18604 -2.33631 H -1.81690 -0.72196 -2.29667 C -4.64920 -2.56286 -1.86016 H -5.10870 -3.48628 -2.18727 C -6.68021 -2.06466 -0.46350 C -2.63411 -3.09386 -3.27258 F -7.63806 -1.37107 -1.11724 F -6.96462 -3.37515 -0.61084 F -6.82060 -1.76571 0.85389 F -3.45413 -3.97003 -3.89510 F -1.98176 -2.39696 -4.22203 F -1.70865 -3.82163 -2.60534 C 3.22839 -0.25272 -1.37232 C 2.34133 -1.10044 -2.05086 C 4.53613 -0.67920 -1.11731 C 2.76042 -2.36431 -2.45443 H 1.33950 -0.75711 -2.27592 C 4.92663 -1.96280 -1.50320 H 5.24146 -0.01369 -0.63607 C 4.05208 -2.81424 -2.17463 H 4.37232 -3.79975 -2.48830 C 1.77890 -3.29310 -3.12548 C 6.30106 -2.44468 -1.12586 F 1.16792 -4.09292 -2.22003 F 0.81387 -2.62053 -3.77984 F 2.39362 -4.10567 -4.01385 F 7.21322 -1.45091 -1.15043 F 6.31401 -2.94966 0.13979 F 6.74043 -3.42702 -1.93795 H 1.80458 1.25368 -1.25496 C -0.90670 5.25918 -0.64175 H -0.30107 4.40240 -0.93217 H -1.55635 4.93925 0.17061 C 1.08944 6.75173 -1.06665 H 1.73200 7.46101 -0.54284 H 0.52879 7.30420 -1.82291 C 0.80060 5.63780 1.13589 H 1.59180 6.33744 1.41447 H 1.27131 4.74123 0.73737 C -0.74702 7.49753 0.43135 H -1.19172 7.92803 -0.46614 H -1.55887 7.09874 1.04172 N 0.05793 6.29152 -0.03407 C 0.01988 8.57091 1.19712 H -0.69410 9.35552 1.46430 H 0.45836 8.20013 2.12576 H 0.80488 9.04076 0.60069 C -0.04820 5.27039 2.34745 H -0.81315 4.52600 2.11881 H 0.63013 4.81559 3.07551 H -0.51344 6.13313 2.83204


S73

C -1.72989 5.74139 -1.82747 H -2.29671 4.87728 -2.18056 H -2.44433 6.52709 -1.56811 H -1.11807 6.06644 -2.67157 C 1.92676 5.65540 -1.71415 H 2.63779 6.15173 -2.38209 H 2.50602 5.07843 -0.99056 H 1.33411 4.96402 -2.31575 O -0.07939 1.48747 -1.66454 Cl -0.16956 1.94897 -3.13762 O -0.17537 3.44433 -3.15835 O -1.43904 1.42036 -3.69139 O 1.02012 1.41948 -3.84328 Complex with TEABz .

Figure S35. Optimized structure of the complex between receptor 2 and TEABz (B3LYP/6-31G** level

of theory).

Cartesian coordinates C -1.50090 0.10744 -2.26229 C -3.87035 -0.31257 -2.39079 C -1.26511 -0.99992 -3.11852 N -0.30090 0.67597 -1.90238


S74

C -3.66642 -1.40819 -3.25040 H -4.86791 -0.02521 -2.08715 C 0.17817 -1.09039 -3.26849 C -2.34712 -1.74280 -3.59526 C 0.71899 -0.03221 -2.49843 H -0.18627 1.53980 -1.38649 C 1.03575 -1.95745 -3.95617 H -2.15823 -2.59759 -4.23769 C 2.10519 0.14759 -2.42900 C 2.42424 -1.79238 -3.89596 H 0.60745 -2.76515 -4.53816 C 2.93660 -0.72802 -3.12146 S 2.77387 1.43627 -1.39357 H 4.00556 -0.56334 -3.05718 O 4.18240 1.62208 -1.74582 O 1.83543 2.57191 -1.45953 C -4.84005 -2.25984 -3.77433 C -4.73736 -3.68436 -3.17796 H -4.82213 -3.65488 -2.08732 H -5.54543 -4.31639 -3.56294 H -3.78756 -4.16510 -3.43228 C -6.20897 -1.67479 -3.37590 H -7.00648 -2.29195 -3.80143 H -6.34975 -1.66722 -2.29108 H -6.34400 -0.65562 -3.75334 C -4.78027 -2.33801 -5.31755 H -4.85249 -1.34120 -5.76481 H -3.85240 -2.79706 -5.67165 H -5.61130 -2.94158 -5.69829 C 3.41038 -2.73341 -4.61508 C 4.26375 -3.48001 -3.56135 H 4.97863 -4.14646 -4.05680 H 4.83392 -2.79610 -2.92684 H 3.62996 -4.08876 -2.90820 C 2.68428 -3.78178 -5.47865 H 2.04658 -4.43828 -4.87760 H 2.06606 -3.31424 -6.25252 H 3.42044 -4.41566 -5.98250 C 4.33842 -1.91157 -5.54046 H 3.76138 -1.37595 -6.30145 H 4.92640 -1.17467 -4.98583 H 5.04343 -2.57514 -6.05272 C -2.80595 0.44155 -1.89373 S -3.07103 1.69397 -0.65712 N -2.54896 1.01609 0.79059 O -2.11629 2.79075 -0.90423 O -4.50640 1.96691 -0.57656 H 1.72142 1.09874 0.61465 N 2.65544 0.90246 0.18778 C 3.34242 -0.22936 0.68437 C 4.60686 -0.61228 0.22173


S75

C 2.73065 -0.97165 1.70917 C 5.22413 -1.74613 0.75414 H 5.10668 -0.03127 -0.54165 C 3.37902 -2.07888 2.24622 H 1.75985 -0.65971 2.07576 C 4.62782 -2.48662 1.76873 H 5.12211 -3.35649 2.18228 C 6.58594 -2.11982 0.23286 C 2.71508 -2.90724 3.31646 F 7.54515 -1.28155 0.68511 F 6.94627 -3.37022 0.58954 F 6.63102 -2.05747 -1.12300 F 3.59950 -3.27144 4.27420 F 1.70685 -2.25016 3.92478 F 2.20283 -4.05122 2.80843 C -3.02596 -0.24130 1.22909 C -2.10479 -1.14396 1.77310 C -4.37807 -0.60062 1.14647 C -2.53547 -2.38347 2.24187 H -1.06118 -0.85425 1.82433 C -4.77934 -1.86518 1.57636 H -5.10345 0.10011 0.75325 C -3.87196 -2.76471 2.13710 H -4.19827 -3.73639 2.48388 C -1.51532 -3.29842 2.86810 C -6.20897 -2.28170 1.36102 F -0.43115 -3.44156 2.07446 F -1.07344 -2.80657 4.05035 F -2.01052 -4.53044 3.10813 F -7.06586 -1.24803 1.49121 F -6.39048 -2.78004 0.10609 F -6.59626 -3.24729 2.21952 H -1.53822 1.18322 0.96852 C 1.16502 5.30625 -0.05863 H 0.62589 4.42805 0.29971 H 1.78358 5.00155 -0.90081 C -0.81989 6.78615 0.45797 H -1.51230 7.46705 -0.04047 H -0.20222 7.37709 1.13680 C -0.69709 5.55419 -1.69314 H -1.51114 6.23268 -1.95783 H -1.12965 4.68736 -1.19738 C 0.86252 7.47814 -1.22999 H 1.36803 7.96733 -0.39644 H 1.63348 7.06209 -1.88059 N 0.12814 6.28603 -0.63350 C 0.01221 8.49017 -1.99182 H 0.68285 9.27147 -2.36168 H -0.49041 8.05562 -2.85848 H -0.73434 8.97894 -1.36209 C 0.05755 5.10175 -2.93788


S76

H 0.83101 4.36513 -2.71383 H -0.67472 4.60796 -3.58368 H 0.49127 5.92614 -3.51091 C 2.02773 5.84308 1.07367 H 2.64851 5.00435 1.39690 H 2.69213 6.66108 0.78007 H 1.44417 6.13956 1.94752 C -1.58705 5.71378 1.22233 H -2.18587 6.23216 1.97843 H -2.27613 5.15565 0.58593 H -0.93498 4.99937 1.73144 C 0.30267 2.16259 2.43499 O 0.21029 1.16872 1.61078 O 0.46626 3.35212 2.09558 C 0.21246 1.85594 3.91767 C 0.04065 0.55237 4.39771 C 0.31315 2.90683 4.84049 C -0.03184 0.30126 5.76783 H -0.03472 -0.27010 3.70017 C 0.24078 2.66039 6.20945 H 0.45304 3.91129 4.45681 C 0.06716 1.35484 6.67740 H -0.16352 -0.71818 6.11830 H 0.32113 3.48377 6.91421 H 0.01176 1.16104 7.74513


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