Internal Probing of the Supramolecular Organization of Pyrene-Based Organogelators

Figure A: ¹H-NMR ([D1]-Chloroform) spectrum of compound 3.

Figure B: ¹H-NMR ([D6]-DMSO) spectrum of compound 1.

Compound 1 Compound 3

Figure C: ¹H-NMR ([D6]-DMSO) spectrum of intermediate 4.

Figure D: ¹H-NMR ([D6]-DMSO) spectrum of compound 2.

Compound 4

Compound 2

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.2 0.8

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Hydrogen bonding (f)^h

Po lar (f_p

)

Dispersion (f_d) CH₃CN

C₁₆H₃₄

CCl₄ DMF

DMSO

AcOEt tBuOH

OctOH

1,4-Dioxane CHCl₃

oDCBTCB

CB Tetralin

Toluene p-xylene CHCl₂-CHCl₂

Figure S1. Teas diagram showing the positions of the tested solvents (solvents in which the gels formed are marked in red).

Figure S2. ¹H-NMR spectra at variable temperature (VT) of compound 1 in DMSO-D6 (left) and in C2D2Cl4 (right) [1] = 2 mg/mL.

T (K)

280 300 320 340 360 380 400

(ppm)

-0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2

T (K)

280 300 320 340 360 380 400

(ppm)

-0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2

Figure S3. Variations of the chemical shifts of compound 1 according to the temperature in DMSO-D6 (left) and C2D2Cl4 (right).

Figure S4. DSC thermogram of organogels obtained from compound 1 in oDCB ([1] = 10 mg/mL).

Figure S6. Evolution of the emission spectra of 1 (C = 10^-4 mol.L^-1) upon lowering temperature in DMSO.

Figure S7. Evolution of the emission spectra of 1 (C = 10^-5 mol.L^-1) upon lowering temperature in DMSO.

Figure S8. Evolution of the UV-vis absorption spectrum of compound 2 in DMSO upon decreasing the temperature;

top left: C = 10^-5 mol.L^-1 (l = 10 mm); top right: C = 10^-4 mol.L^-1 (l = 10 mm); bottom: C = 10^-3 mol.L^-1 (l = 1 mm).

Figure S9. Evolution of the emission spectrum of compound 2 in DMSO upon decreasing the temperature;

top left: C = 10^-5 mol.L^-1; top right: C = 10^-4 mol.L^-1; bottom: C = 10^-3 mol.L^-1; exc = 344 nm).

Figure S11. Evolution of the emission spectrum of 2 in oDCB (C = 10^-4 mol.L^-1) upon decreasing the temperature;

exc = 344 nm.

Figure S12. Emission spectra of compound 1 in oDCB ([1] = 10^-5 M) in the absence (red) and in the presence (blue) of tetrabutylammonium acetate ([TBAAc] = 2.5 x 10^-2 M) – exc = 344 nm