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SUPPORTING INFORMATION

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1H NMR stack plot of a CDCl3–DMSO (10:1, v/v) solution of 4e. (4.0 × 10-3 M) upon addition of KSO3CF3 (Fig. S32). S21~S22 – Changes in chemical shifts of ...

Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2015

SUPPORTING INFORMATION Manuscript title: Positive and negative allosteric effects of thiacalix[4]arene-based receptors having urea and crown–ether moieties Author(s): Hirotsugu Tomiyasu,a Zhao Jiang-Lin,a Xin–Long Ni,b Xi Zeng,b Mark R. J. Elsegood,c Beth Jones,c Carl Redshaw,d Simon J. Teat,e and Takehiko Yamato a* a

Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo–machi 1, Saga 840–8502 Japan, E–mail: [email protected]–u.ac.jp b Department Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang, Guizhou, 550025, China. c Chemistry Department, Loughborough University, Loughborough LE11 3TU, UK. d Department of Chemistry, The University of Hull, Cottingham Road, Hull, Yorkshire, HU6 7RX, UK e ALS, Berkeley Lab, 1 Cyclotron Road, Bereleley, CA 94720, USA.

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Contents (S1 to S22 are the page numbers) S1~S2 – Title, authors and description of supporting information content S3~S9 – 1H NMR and 13C NMR spectra of all compounds 2, 3, 4a~e (Fig. S1~S14) S10~S11 – X–ray crystal structures of receptor 4b and 4e S12 – Experimental Section of 1H NMR and UV-vis titration experiments S13~S15 – 1H NMR stack plots of solutions of 4a~e upon addition of Bu4NCl (Fig. S17~S21) 1

Benesi-Hildebrand plot of 4e for various concentrations of Cl– ion at 298K by the H NMR

titration method (Fig. S22) S16 – Concentration-dependent 1H NMR spectra of 4e (Fig. S23)

Benesi-Hildebrand plot of 4e for various concentrations of Cl- ion at 298K by the UV-vis titration method (Fig. S24) S17– Job's plot showing the 1:1 binding of 4e to Cl– ion from the fluorescence method (Fig. S25) The solution color of reseptor 4e (2.5µM) (Fig. S26) S18~S20 – UV–vis absorption spectra of 4e (2.5µM) upon the addition of increasing concentrations of various anions (Fig. S27~31) 1

H NMR stack plot of a CDCl3–DMSO (10:1, v/v) solution of 4e -3

(4.0 × 10 M) upon addition of KSO3CF3 (Fig. S32) S21~S22 – Changes in chemical shifts of protons and the selective absorption behaviour of receptor 4e towards K+ ion by 1H NMR and UV–vis titration experiments (Fig. S33~S36)

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Figure S1. 1H–NMR spectra of 2 (300 MHz, CDCl3, 293 K).

Figure S2. 13C–NMR spectra of 2 (75 MHz, CDCl3, 293 K).

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Figure S3. 1H–NMR spectra of 3 (300 MHz, CDCl3, 293 K).

Figure S4. 13C–NMR spectra of 3 (75 MHz, CDCl3, 293 K).

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Figure S5. 1H–NMR spectra of 4a (300 MHz, CDCl3–DMSO, 293 K).

Figure S6. 13C–NMR spectra of 4a (75 MHz, CDCl3–DMSO, 293 K).

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Figure S7. 1H–NMR spectra of 4b (300 MHz, CDCl3–DMSO, 293 K).

Figure S8. 13C–NMR spectra of 4b (75 MHz, CDCl3–DMSO, 293 K).

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Figure S9. 1H–NMR spectra of 4c (300 MHz, CDCl3–DMSO, 293 K).

Figure S10. 13C–NMR spectra of 4c (100 MHz, CDCl3–DMSO, 293 K).

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Figure S11. 1H–NMR spectra of 4d (300 MHz, CDCl3–DMSO, 293 K).

Figure S12. 13C–NMR spectra of 4d (100 MHz, CDCl3–DMSO, 293 K).

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Figure S13. 1H–NMR spectra of 4e (300 MHz, CDCl3–DMSO, 293 K).

Figure S14. 13C–NMR spectra of 4e (100 MHz, CDCl3–DMSO, 293 K).

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X–ray crystal structure of receptor 4b

a)

c)

b)

Figure S15. a) X–ray crystal structure of the asymmetric unit of receptor 4b. H–bonds shown as dashed lines. b) & c) One of two similar molecules in the asymmetric unit is shown in two orientations rotated by approx. 90°. H atoms not involved in H-bonding, minor disorder components, and solvent of crystallization are omitted for clarity.

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X–ray crystal structure of receptor 4e

Figure S16. X–ray crystal structure of the asymmetric unit of receptor 4e. H–bonds shown as dashed lines. H atoms not involved in H-bonding, minor disorder components, and solvent of crystallization are omitted for clarity.

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Experimental Section Selective absorption behaviours of receptors 4a~e to various anions. The UV–vis titration experiments of 4a~e were investigated by addition of anions (100 µL) (7.5 mM in CH3CN solution) to 3 mL of 4a~e solution (2.5 µM in CDCl3–DMSO, 10:1, v/v), respectively. The excitation wavelength was 343 nm. K+ titration of receptor 4e solution determined by absorption. The UV-vis titration experiment of 4e was investigated by adding increasing concentrations of KSO3CF3 (50 µL) (3.8 mM in CH3CN solution) to 3 mL of 4e solution (2.5 µM in CDCl3–DMSO, 10:1, v/v) in a cuvette. The spectra were recorded immediately after mixing. The excitation wavelength was 343 nm. Selective absorption behaviours of receptor 4e •K+ to various anions. The fluorescent response of L•K+ to different anions was investigated by addition of KSO3CF3 (50 µL) (4.5 mM in CH3CN) to 3 mL of 4e solution (2.5 µM in CDCl3–DMSO, 10:1, v/v) in a cuvette. The experiment was then further carried out by addition of anion (100 µL) (7.5 mM in CH3CN solution) to the 4e •K+ solution. The UV–vis spectra were recorded immediately after mixing. The excitation wavelength was 343 nm. 1

H NMR titration experiments of 4e, 4e •K+, 4e •K+ with Cl- and 4e •K+ with Br-. The 1H NMR titration experiment was investigated by addition 10 µL of KSO3CF3 (2.2 ×10‒1 M) to the solution of 4e (CDCl3–DMSO, 10:1, v/v) (4 × 10-3M) in NMR tube (560 µL). Then further experiment was carried out by addition of increasing concentrations of Bu4NCl or Bu4NBr in CH3CN solution (2.2 × 10‒1 M). The spectra were recorded after mixing and the temperature of the NMR probe was kept constant at 298K.

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Figure S17. 1H NMR stack plot of a CDCl3–DMSO (10:1, v/v) solution of 4 a -1

(4.0 × 10-3 M) upon addition of Bu4NCl in CD3CN. Ka = 6816 (±545) M .

Figure S18. 1H NMR stack plot of a CDCl3–DMSO (10:1, v/v) solution of 4 b -1

(4.0 × 10-3 M) upon addition of Bu4NCl in CD3CN. Ka = 6945 (±625) M .

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Figure S19. 1H NMR stack plot of a CDCl3–DMSO (10:1, v/v) solution of 4 c -1

(4.0 × 10-3 M) upon addition of Bu4NCl in CD3CN. Ka = 3021 (±242) M .

Figure S20. 1H NMR stack plot of a CDCl3–DMSO (10:1, v/v) solution of 4 d -1

(4.0 × 10-3 M) upon addition of Bu4NCl in CD3CN. Ka = 34411 (±2400) M .

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Figure S21. 1H NMR stack plot of a CDCl3–DMSO (10:1, v/v) solution of 4 e -1

(4.0 × 10-3 M) upon addition of Bu4NCl in CD3CN. Ka = 34411 (±2400) M .

Figure S22. Benesi-Hildebrand plot of 4e for various concentrations of Cl– ion at 298K by the 1H NMR titration method. The associate constant (Ka) was calculated to be 34411 (±2753) M-1.

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Figure S23. Concentration-dependent 1H NMR spectra of 4e in CDCl3–DMSO (10:1, v/v). (a = 4.0 × 10-2 M, b = 4.0 × 10-3 M, c = 8.0 × 10-4 M, d = 4.0 × 10-4). *Denotes the solvent peak.

Figure S24. Benesi-Hildebrand plot of 4e for various concentrations of Clat 298K by the UV-vis titration method. The associate constant (Ka) was calculated to be 34152 (±2732) M-1.

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Figure S25. Job's plot showing the 1:1 binding of 4e to Cl– ion from the UV-vis titration method at 390 nm in CH2Cl2–DMSO (10:1, v/v).

Figure S26. The solution color of reseptor 4e (2.5µM) in the absence and presence of 5 equivalents of various anions.

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Figure S27. UV–vis absorption spectra of 4e (2.5µM) upon the addition of increasing concentrations of Br– ion in CH2Cl2–DMSO (10:1, v/v).

Figure S28. UV–vis absorption spectra of 4e (2.5µM) upon the addition of increasing concentrations of I– ion in CH2Cl2–DMSO (10:1, v/v).

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Figure S29. UV–vis absorption spectra of 4e (2.5µM) upon the addition of increasing concentrations of AcO– ion in CH2Cl2–DMSO (10:1, v/v).

Figure S30. UV–vis absorption spectra of 4e (2.5µM) upon the addition of increasing concentrations of PhCO2– ion in CH2Cl2–DMSO (10:1, v/v).

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Figure S31. UV–vis absorption spectra of 4e (2.5µM) upon the addition of increasing concentrations of H2PO4– ion in CH2Cl2–DMSO (10:1, v/v).

Figure S32. 1H NMR stack plot of a CDCl3–DMSO (10:1, v/v) solution of 4 e (4.0 × 10-3 M) upon addition of KSO3CF3 in CD3CN. Binding mode of receptor

4e upon complexation with K+ ion.

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Figure S33. UV–vis absorption spectra of receptor 4e (2.5 µM) upon the addition of KSO3CF3 (0-50 µM) in CH2Cl2–DMSO (10:1, v/v).

Figure S34. Benesi-Hildebrand plot of 4 e with varied concentrations K+ ion at 298K. The associate constant (Ka) was calculated to be 28536±1998 M-1 in CH2Cl2–DMSO (10:1:1, v/v).

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Figure S35. Job's plot showing the 1:1 binding of 4e to +

K ion from fluorescence methods at 390 nm in CH2Cl2

–DMSO (10:1, v/v).

Figure S36. Proposed positive allosteric behaviour of receptor 4e with Br– and K+ ions. UV–vis absorption spectra of 4e/guest (H/G = 1:1); free 4e (black full line), 4e⊂KSO3CF3 (red full line), Bu4NBr⊃[4e⊂K+] (green broke line), 4e⊂Bu4NBr (blue full line). Solvent: CH2Cl2–DMSO (10:1, v/v). 300 MHz at 298 K.

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