SUPPLEMENTARY INFORMATION

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1 In the format provided by the authors and unedited. SUPPLEETARY IFRATI DI: 1.138/CE.2812 Thermally bisignate supramolecular polymerization K. Venkata Rao, Daigo iyajima*, Atsuko ihonyanagi and Takuzo Aida* * To whom correspondence should be addressed. daigo.miyajima@riken.jp (D..); aida@macro.t.u-tokyo.ac.jp (T.A.) Table of Contents 1. General... S2 2. Synthesis and Characterization 2.1. Synthesis of (S) PR 2... S Synthesis of (S) PR Cu... S Synthesis of (R) PR Cu... S Synthesis of (S) PR Zn... S6 3. Analytical Data and 13 C R Spectroscopy... S ALDI-TF ass Spectrometry... S12 4. Supplementary Figures (Figs )... S14 5. Supplementary References... S33 ATURE CEISTRY acmillan Publishers Limited, part of Springer ature. All rights reserved.

2 1. General Unless otherwise noted, all commercial reagents were used as received. 1 (25 or 4 or 55 C) and 13 C (45 C) R spectra were recorded using a JEL model J- ECA5 spectrometer, operating at 5 and 125 z, respectively, where chemical shifts (δ in ppm) were determined using tetramethylsilane as an internal reference. atrix-assisted laser desorption ionization time-of-flight (ALDI-TF) mass spectrometry was performed in the reflector mode using a Brucker model autoflex T speed spectrometer. Electronic absorption spectra were recorded using a JASC model V-76 UV/VIS spectrophotometer with a screw capped quartz cell of 1 mm optical path length. Circular dichroism (CD) spectra were recorded using a JASC model J-15 CD spectrophotometer with a screw capped quartz cell of 1 mm optical path length. Dynamic light scattering (DLS) measurements were performed using alvern type Zetasizer ano ZSP and Beckman Coulter type Delsaax-pro. Infrared spectra were recorded using a JASC model FT/IR-61Plus Fourier Transform Infrared spectrometer. Tapping-mode atomic force microscopy (AF) images were recorded using an Asylum Research type CypherS AF microscope, where all samples were deposited on a silicon wafer by dip coating at designated temperatures and dried under air before the measurement. Diameter of PR Cu was estimated using the Avagadro 1.2. molecular editor and visualization tool. Temperature-dependent viscosity profiles were obtained by an Anton Paar CR 31 rehometer. 2

3 2. Synthesis and Characterization 5, 1, 15, 2-Tetrakis(4 -carboxyphenyl)porphine and 1-hexanol were purchased from Aldrich and Tokyo Chemical Industry (TCI), respectively. Compounds 1 55, 2, 3 56 and (S) PR 57 Cu were synthesized according to the literature methods Synthesis of (S) PR 2 R R R R R Cl Cl R + 2 R R R ipr2et C2Cl2 Cl 1 Cl 2 R R R R = (S) PR2 R R R To a C 2 Cl 2 (1 ml) solution of 1 (85 mg,.98 mmol) were successively added amide amine 2 (37 mg,.59 mmol) and,-diisopropylethylamine (ipr 2 Et, 5 µl, 2.86 mmol) upon stirring at C. The mixture was allowed to warm slowly to 25 C and stirred in the dark for 44 h in an Ar atmosphere. The reaction mixture was diluted with C 2 Cl 2 (1 ml) and then washed successively with sat. 4 Cl aq (2 ml), 1 a aq (2 ml) and brine (2 ml). The organic phase separated was evaporated to dryness under reduced pressure after being dried over anhydrous a 2 S 4. The residue was subjected to column chromatography (Si 2, C 2 Cl 2 /e 3/1 v/v) to allow isolation of (S) PR 2 as violet solid (127 mg,.39 mmol) in 4% yield. 1 R (5 z, CDCl 3, 4 C) δ (ppm) 8.72 (br, 8), 8.12 (br, 16), 7.54 (br, 4), 7.33 (br, 4), 7.15 (s, 8), (m, 24 ), 3.9 (br, 8), 3.84 (br, 8), (m, 12),.9.88 (dd, J = 2.3 and 6.6 z, 36),.83 (d, J = 6.3, 24),.76 (d, J = 6.3, 48), 2.98 (s, 2); 13 C R (125 z, CDCl 3, 45 C) δ (ppm) 168.7, 168.6, 153.3, 145., 141.5, 134.3, 133.3, 128.8, 125.5, 119.1, 15.9, 71.8, 67.7, 41.6, 41.1, 39.3, 39.2, 37.5, 37.4, 37.4, 37.4, 36.5, 29.9, 29.7, 28., 28., 27.9, 24.7, 24.6, 22.7, 22.6, 22.6, 22.5, 19.6, ALDI-TF mass: m/z calculated, for compound (S) PR 2 [ + ] +, ; Found: [ + ] +,

4 2.2. Synthesis of (S) PR Cu R R R R R R R R R R R R CuCl2 C2Cl2/ e (5:1) Cu R R R (S) PR2 R R R R R R (S) PRCu R R R To a C 2 Cl 2 (5 ml) solution of (S) PR 2 (24 mg,.75 mmol) was added a e (1 ml) solution of CuCl 2 (1.1 mg,.75 mmol), and the mixture was stirred in the dark for 4 h at 5 C in an Ar atmosphere. After being allowed to cool to room temperature, the reaction mixture was diluted with C 2 Cl 2 (1 ml) and then washed with water (2 ml). The organic phase separated was isolated and then evaporated to dryness under reduced pressure after being dried over anhydrous a 2 S 4. The residue was subjected to column chromatography (Si 2, C 2 Cl 2 /e 15/1 v/v), followed by re-precipitation with C 2 Cl 2 /e (1/1 v/v), to allow isolation of (S) PR Cu as violet solid (16 mg,.48 mmol) in 64% yield. 1 R (5 z, pyridine-d 6, 25 C) δ (ppm) 9.76 (br), 7.96 (br), 4.23 (m), 4.1 (br), 2.6 (m), 1.91 (br), 1.73 (br) (m), 1.6 (d, J = 6.3 z, 36), (m); 13 C R (125 z, CDCl 3, 45 C) δ (ppm), 168.6, 153.2, 141.4, 128.7, 4.2, 38.9, 38.2, 3.9, 29.8, 23.2, 22.5, 2.3. ALDI-TF mass: m/z calculated, for compound (S) PR Cu [ + ] +, ; Found: [ + ] +, R = 4

5 2.3. Synthesis of (R) PR Cu R R R R R Cl Cl R + 2 R R R ipr2et C2Cl2 Cl 1 Cl 3 R R R R = (R) PR2 R R R R R R R R R CuCl2 C2Cl2/e (5:1) Cu R R R R = (R) PRCu R R R (R) PR Cu was synthesized using amide amine 3, according to the same procedure as that used for (S) PR Cu. 1 R (5 z, pyridine-d 6, 25 C) δ (ppm) 9.76 (br), 7.95 (br), 4.23 (m), 4.11 (br), 2.6 (m), 1.91 (br), 1.73 (br) (m), 1.6 (d, J = 6.3 z, 36), (m); 13 C R (125 z, CDCl 3, 45 C) δ (ppm), 153.2, 115.1, 1.5, 4.1, 39.3, 38.2, 29.7, 27.9, 27.8, 22.5, 2.3. ALDI-TF mass: m/z calculated, for compound (R) PR Cu [ + ] +, ; Found: [ + ] +,

6 2.4. Synthesis of (S) PR Zn R R R R R R R R R R R R Zn(Ac)2 C2Cl2/e (5:1) Zn R R R (S) PR2 R R R R R = (S) PRZn R R R R R To a C 2 Cl 2 (1 ml) solution of (S) PR 2 (127 mg,.39 mmol), Zn(Ac) 2 (42.8 mg,.195 mmol) in e (2 ml) was added, and the mixture was stirred in the dark for 24 h at 9 C in an Ar atmosphere. After cooling to room temperature, the reaction mixture was diluted with C 2 Cl 2 (3 ml) and washed with water (4 ml), then dried over anhydrous a 2 S 4 and evaporated to dryness under reduced pressure. The residue was subjected to column chromatography (Si 2, C 2 Cl 2 /e 25/1 v/v), followed by re-precipitation with C 2 Cl 2 /e (8/1 v/v), to allow isolation of (S) PR Zn as violet solid (15 mg,.32 mmol) in 81% yield. 1 R (5 z, CDCl 3, 55 C) δ (ppm) 8.81 (s, 8), 8.17 (br, 8), 8.6 (br, 8), 7.33 (br, 4), 7.13 (br, 4), 7.6 (s, 8), (m, 24), 3.76 (br, 8), 3.71 (br, 8), (m, 12),.89 (d, J = 6.3 z, 36),.83 (d, J = 6.8, 24),.76 (d, J = 6.9, 48); 13 C R (125 z, CDCl 3, 45 C) δ (ppm) 168.6, 153.2, 153.1, 149.7, 146.3, 141.5, 134.5, 131.8, 128.6, 125.2, 119.9, 15.8, 71.8, 67.7, 39.4, 39.3, 39.2, 37.6, 37.5, 37.4, 36.5, 29.9, 29.7, 28., 27.9, 24.7, 22.7, 22.6, 22.5, 19.6, ALDI-TF mass: m/z calculated, for compound (S) PR Zn [] +, ; Found: [] +,

7 3. Analytical Data and 13 C R Spectroscopy ppm Supplementary Figure 1. 1 R spectrum of (S) PR 2 in CDCl 3 at 4 C ppm Supplementary Figure 2. 1 R spectrum of (S) PR Cu in pyridine-d 6 at 25 C. 7

8 ppm4 2 Supplementary Figure 3. 1 R spectrum of (R) PR Cu in pyridine-d 6 at 25 C. 8

9 ppm Supplementary Figure 4. 1 R spectrum of (S) PR Zn in CDCl 3 at 55 C ppm Supplementary Figure C R spectrum of (S) PR 2 in CDCl 3 at 45 C. 9

10 ppm Supplementary Figure C R spectrum of (S) PR Cu in CDCl 3 at 45 C ppm Supplementary Figure C R spectrum of (R) PR Cu in CDCl 3 at 45 C. 1

11 ppm Supplementary Figure C R spectrum of (S) PR Zn in CDCl 3 at 45 C. 11

12 3.2. ALDI-TF ass Data [ + ] m/z Supplementary Figure 9. ALDI-TF mass spectrum of (S) PR 2 using dithranol (DT) as a matrix [ + ] m/z Supplementary Figure 1. ALDI-TF mass spectrum of (S) PR Cu using DT as a matrix. 12

13 3314. [ + 2] [ + a] m/z Supplementary Figure 11. ALDI-TF mass spectrum of (R) PR Cu using DT as a matrix [] [ + a] m/z Supplementary Figure 12. ALDI-TF mass spectrum of (S) PR Zn using DT as a matrix. 13

14 4. Supplementary Figures 4.1. Self-assembling behaviors of 2 C (S)PRCu at.6 Absorbance b 2 C P dodecane* P.2 3 (S)PRCu at 2 C 6 CCl3.4 PRCu (1 µ) in CCl3 and dodecane* at CD (mdeg) a (S) CCl3 dodecane* c 8 nm 25 nm Supplementary Figure 13. (a) Electronic absorption and (b) CD spectra of (S)PRCu (1 µ) in CCl3 (red) and dodecane* (blue). (c) Tapping-mode AF image of (S) PRCu (1 µ) in dodecane contacting 3% CCl3 (v/v) dip-coated onto a silicon wafer at 25 C. The height profile (bottom) was obtained along the white line in c. nly bundled supramolecular polymers of (S)PRCu were observed without CCl3. 14

15 4.2. Supramolecular polymerization of (S) PR Cu (1 µ) in dodecane* at 2 and 11 C a Absorbance (S) PRCu in dodecane* 2 C 11 C P b CD (mdeg) (S) PRCu in dodecane* 2 C 11 C P Supplementary Figure 14. (a) Electronic absorption and (b) CD spectra of (S) PR Cu (1 µ) in dodecane* at 2 C (blue) and 11 C (red). 15

16 4.3. Supramolecular polymerization of (S) PR Cu and (R) PR Cu (1 µ) at 2 C a CD (mdeg) (R) PRCu at 2 C P CCl3 dodecane* b CD (mdeg) in dodecane* at 2 C (S) PRCu (R) PRCu Supplementary Figure 15. (a) CD spectra of (R) PR Cu (1 µ) in CCl 3 (red) and dodecane* (green) at 2 C. (b) CD spectra of polymeric (S) PR Cu (blue) and (R) PR Cu (green) (1 µ) in dodecane* at 2 C. 16

17 4.4. Depolymerization of polymeric (S) PR Cu (1 µ) in dodecane* with 1 vol% C 6 13 at 2 C a Absorbance (S) PRCu in dodecane* (1 vol% C613) at 2 C b CD (mdeg) (S) PRCu in dodecane* (1 vol% C613) at 2 C Supplementary Figure 16. (a) Electronic absorption and (b) CD spectra of (S) PR Cu in dodecane* (1 vol% C 6 13 ) at 2 C. 17

18 4.5. Supramolecular polymerization of (S) PR Cu (1 µ) in dodecane* with 5.5 vol% of C 6 13 at 11, 5 and 2 C (S) PRCu in dodecane* (5.5 vol% C613) DLS Counts 11 C 5 C 2 C 2 C (CCl3) ydrodynamic Diameter (nm) 1 4 Supplementary Figure 17. DLS size distribution profiles of (S) PR Cu (1 µ) in dodecane* with 5.5 vol% C 6 13 at 2 C (blue), 5 C (green) and 11 C (red). As a reference for the hydrodynamic diameter of monomeric (S) PR Cu, DLS profile of (S) PR Cu (1 µ) in CCl 3 at 2 C (black) is also shown. 18

19 4.6. Supramolecular polymerization of (S) PR Cu (1 µ) in C* with 3 vol% of C 6 13 at 1, 15 and 8 C a Absorbance c (ε εmono)/(εpoly εmono) (S) PRCu in C* (3 vol% C613) 8 C 15 C 1 C P (S) PRCu in C* (3 vol% C613) P Temperature ( C) P 9 b CD (mdeg) d DLS Counts.1 (S) PR Cu in C* (3 vol% C613) 8 C 15 C 1 C P (S) PRCu in C* (3 vol% C613) 8 C 15 C 1 C 2 C (CCl3) ydrodynamic Diameter (nm) Supplementary Figure 18. (a) Electronic absorption spectra and (b) circular dichroism (CD) spectra of (S) PR Cu (1 µ) in C* with 3 vol% C 6 13 at 1 C (blue), 15 C (green) and 8 C (red). (c) Temperature-dependent changes ( 1 C to 9 C) in the electronic molar absorptivity of (S) PR Cu (1 µ) at 388 nm in C* with 3 vol% C 6 13 upon cooling at a rate of 1 C/min. ere, ε mono and ε poly are molar absorptivities of monomer and supramolecular polymer of (S) PR Cu at 388 nm, respectively. (d) DLS size distribution profiles of (S) PR Cu (1 µ) in C* with 3 vol% C 6 13 at 1 C (blue), 15 C (green) and 8 C (red). As a reference for the hydrodynamic diameter of monomeric (S) PR Cu, DLS profile of (S) PR Cu in CCl 3 at 2 C (black) is also shown. 19

20 4.7. Temperature-dependent electronic molar absorptivity profiles of (S) PR Cu (1., 8., 6. and 2.5 µ) in dodecane* (5.5 vol% C 6 13 ) (ε εmono)/(εpoly εmono) (S) PRCu (5.5 vol% C613) in dodecane* 1.2 P 1. µ P.9 8. µ 6. µ µ Temperature ( C) 1 Supplementary Figure 19. Temperature-dependent electronic molar absorptivity profiles of (S) PR Cu in dodecane* (5.5 vol% C 6 13 ) at 1. µ (blue), 8. µ (green), 6. µ (black) and 2.5 µ (red) monitored at 393 nm upon cooling at a rate of 1 C/min. ε mono and ε poly are molar absorptivities of (S) PR Cu monomer and its supramolecular polymer at 393 nm, respectively. 2

21 4.8. Temperature-dependent electronic molar absorptivity profiles of (S) PR Cu (1, 2 and 3 µ) in dodecane* (5.5, 6. and 6.5 vol% C 6 13 ) (ε εmono)/(εpoly εmono) (S) PRCu in dodecane*(x vol% C613) 1.2 P 1 µ (X = 5.5) 2 µ (X = 6.) P.9 3 µ (X = 6.5) Temperature ( C) Supplementary Figure 2. Temperature-dependent (1 C 2 C) electronic molar absorptivity profiles of (S) PR Cu in dodecane* at 1 µ (blue, 5.5 vol% C 6 13 ), 2 µ (green, 6. vol% C 6 13 ) and 3 µ (red, 6.5 vol% C 6 13 ) monitored at 393 nm upon cooling at a rate of 1 C/min. ε mono and ε poly are molar absorptivities of (S) PR Cu monomer and its supramolecular polymer at 393 nm, respectively. 21

22 4.9. Supramolecular polymerization of (S) PR 2 (1 µ) in dodecane* with 5.5 vol% C 6 13 at, 4 and 11 C Absorbance (S) PR2 in dodecane* (5.5 vol% C613) 11 C 4 C C P Supplementary Figure 21. Electronic absorption spectra of (S) PR 2 (1 µ) in dodecane* with 5.5 vol% C 6 13 at (blue), 4 (green) and 11 C (red). 22

23 4.1. Supramolecular polymerization of (S) PR Zn (1 µ) in dodecane* with 3. vol% C 6 13 at, 33 and 11 C (S) PRZn in dodecane* (3. vol% C613).4 Absorbance C 33 C C P Supplementary Figure 22. Electronic absorption spectra of (S) PR Zn (1 µ) in dodecane* with 3. vol% C 6 13 at (blue), 33 (green) and 11 C (red). 23

24 4.11. Supramolecular polymerization of vol% of C1225 at 2, 5 and 11 C (S)PRCu in dodecane* (11 vol% C1225) C 5 C 2 C PRCu (1 µ) in dodecane* with 11 b (S)PRCu P.2 in dodecane* (11 vol% C1225) 6 4 CD (mdeg) Absorbance a (S) 2 11 C P 5 C 2 C (ε εmono)/(εpoly εmono) c d 2 C 5 (S)PRCu in dodecane* (11 vol% C1225) P P e 5 C Temperature ( C) 1 f 11 C 1 μm 1 μm 5 nm 7 nm 2 nm 17 nm 6 3 Supplementary Figure 23. (a) Electronic absorption spectra and (b) circular dichroism (CD) spectra of (S)PRCu (1 µ) in dodecane* with 11 vol% C1225 at 2 C (blue), 5 C (green) and 11 C (red). (c) Temperature-dependent changes (2 1 C) in the electronic molar absorptivity of (S)PRCu (1 µ) at 393 nm in dodecane* with 11 vol% C1225 upon cooling at a rate of 1 C/min. ere, εmono and εpoly are molar absorptivities of monomer and supramolecular polymer of (S)PRCu at 393 nm, respectively. (d) (f) Tapping-mode AF images of (S)PRCu. Samples were prepared by dip-coating of a dodecane* (11 vol% C1225) solution of (S) PRCu (1 µ) at 2 C (d), 5 C (e) and 11 C (f) onto a silicon wafer. The height profiles (lower) were obtained along the white lines in d, e and f. 24

25 4.12. Supramolecular polymerization of (S) PR Cu (1 µ) in dodecane* at 2, 5 and 7 C a Absorbance (S) PR Cu in dodecane* 7 C 5 C 2 C P b CD (mdeg) (S) PR Cu in dodecane* 7 C 5 C 2 C P Supplementary Figure 24. (a) Electronic absorption and (b) CD spectra of (S) PR Cu (1 µ) in dodecane* at 2 C (blue), 5 C (green) and 7 C (red). 25

26 4.13. Depolymerization of polymeric (S) PR Cu (1 µ) in dodecane* with 2 vol% C 6 13 at 2 C a Absorbance (S) PR Cu in dodecane* (2 vol% C613) at 2 C b CD (mdeg) (S) PR Cu in dodecane* (2 vol% C613) at 2 C Supplementary Figure 25. (a) Electronic absorption and (b) CD spectra of (S) PR Cu (1 µ) in dodecane* (2 vol% C 6 13 ) at 2 C. 26

27 4.14. Temperature-dependent infrared spectral profiles (17 15 cm 1 ) of (S) PR Cu (3 µ) in the dodecane* (6.5 vol% C 6 13 ) (S) PRCu in dodecane* (6.5 vol% C613) Absorbance (a.u.) -bonded C= 11 C 9 C 6 C 5 C 3 C 2 C Wavenumber (cm 1 ) Supplementary Figure 26. Infrared spectra (amide C= region) of a dodecane* solution (6.5 vol% C 6 13 ) of (S) PR Cu (3 µ) at 11 C (red), 9 C (cyan) 6 C (green), 5 C (orange), 3 C (pink) and 2 C (blue). 27

28 4.15. Van t off analysis for the cool-induced supramolecular polymerization of (S) PR Cu (1., 8., 6. and 2.5 µ) in dodecane* (5.5 vol% C 6 13 ) based on a nucleation-elongation model (S) PRCu (5.5 vol% C613) in dodecane* 1 ΔCool = 44.7 kj mol 1 ΔSCool =.46 kj mol 11 1 K 1 ln(c) Cool R-E 2 = /Te (K 1 ) Supplementary Figure 27. Van t off plot for the supramolecular polymerization of (S) PR Cu upon heating in dodecane* (5.5 vol% C 6 13 ). ere, elongation temperature (T e ) was obtained from the temperature-dependent electronic molar absorptivity profiles (-5 C) shown in Supplementary Figure 19 and C is the concentration of (S) PR Cu. Standard enthalpy ( Cool ) and entropy ( S Cool ) were calculated as 44.7 kj mol 1 and.46 kj mol 1 K 1, respectively from the following equations I III 53. ln (C) = ( *++, )/RT ( S *++, )/R *++, = slope R S *++, = intercept R (I) (II) (III) ote that the definitions of the above symbols are as follows: Δ Cool = Standard enthalpy for supramolecular polymerization upon cooling ΔS Cool = Standard entropy for supramolecular polymerization upon cooling R = Universal gas constant T = Temeparature in kelvin 28

29 4.16. Van t off analysis for the cool-induced supramolecular polymerization (S) PR Cu (1., 8., 6. and 2.5 µ) in dodecane* (5.5 vol% C 6 13 ) based on an isodesmic model (S) PRCu (5.5 vol% C613) in dodecane* 1 Cool Risodesmic 2 = ln(c) /Tm (K 1 ).38 Supplementary Figure 28. Van t off plot for the supramolecular polymerization of (S) PR Cu upon heating in dodecane* (5.5 vol% C 6 13 ). ere, melting temperature (T m ) was obtained at (ε ε mono )/(ε poly ε mono ) =.5 from the temperature-dependent electronic molar absorptivity profiles (-5 C) shown in Supplementary Figure 19 and C is the concentration of (S) PR Cu. 29

30 4.17. Van t off analysis for the heat-induced supramolecular polymerization of (S) PR Cu (1., 8., 6. and 2.5 µ) in dodecane* (5.5 vol% C 6 13 ) based on a nucleation-elongation model (S) PRCu (5.5 vol% C613) in dodecane* 1 11 eat R-E 2 =.9 ln(c) /Te (K 1 ) Supplementary Figure 29. Van t off plot for the supramolecular polymerization of (S) PR Cu upon heating in dodecane* (5.5 vol% C 6 13 ). ere, elongation temperature (T e ) was obtained from the temperature-dependent electronic molar absorptivity profiles shown in Supplementary Figure 19 and C is the concentration of (S) PR Cu. 3

31 4.18. Van t off analysis for the heat-induced supramolecular polymerization of (S) PR Cu (1., 8., 6. and 2.5 µ) in dodecane* (5.5 vol% C 6 13 ) based on an isodesmic model (S) PRCu (5.5 vol% C613) in dodecane* 1 Δeat = kj mol 1 11 ΔSeat = +.31 kj mol 1 K 1 ln(c) eat Risodesmic 2 = /Tm (K 1 ) Supplementary Figure 3. Van t off plot for the supramolecular polymerization of (S) PR Cu upon heating in dodecane* (5.5 vol% C 6 13 ). ere, melting temperature (T m ) was obtained at (ε ε mono )/(ε poly ε mono ) =.5 from the temperature-dependent electronic molar absorptivity profiles (5-1 C) shown in Supplementary Figure 19 and C is the concentration of (S) PR Cu. Standard enthalpy ( eat ) and entropy ( S eat ) were calculated as kj mol 1 and +.31 kj mol 1 K 1, respectively from the equations IV VI 54. ln (C) = ( =>?@ )/RT ( S =>?@ )/R =>?@ = slope R S =>?@ = intercept R (IV) (V) (VI) ote that the definitions of the above symbols are as follows: Δ eat = Standard enthalpy for supramolecular polymerization upon heating ΔS eat = Standard entropy for supramolecular polymerization upon heating R = Universal gas constant T = Temeparature in kelvin 31

32 4.19. Temperature-dependent viscosity profiles of dodecane* (5.5 vol% C 6 13 ) without and with (S) PR Cu (1 µ) 1.6 in dodecane* (5.5 vol% C613) Viscosity (mpa.s) without (S) PRCu with (S) PRCu Temperature ( C) Supplementary Figure 31. Temperature-dependent (2 1 C) viscosity profiles of dodecane* (5.5 vol% C 6 13 ) without (blue) and with (red) (S) PR Cu (1 µ). 32

33 5. Supplementary References [55] elmich, F. et al. Angew. Chem. Int. Ed. 49, 3939 (21). [56] Ghosh, S. et al. Chem. Eur. J. 14, (28). [57] elmich, F. et al. J. Am. Chem. Soc. 132, (21). 33