Supporting Information. Impact of Molecular Flexibility on Binding Strength and Self-Sorting of Chiral -Surfaces

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1 Supporting Information Impact of Molecular Flexibility on Binding Strength and Self-Sorting of Chiral -Surfaces Marina M. Safont-Sempere, a Peter Osswald, a Matthias Stolte, a Matthias Grüne, a Manuel Renz, b Martin Kaupp, b Krzysztof Radacki, c Holger Braunschweig, c and Frank Würthner *a a Universität Würzburg, Institut für Organische Chemie and Röntgen Research Center for Complex Material Systems, Am Hubland, 9774 Würzburg, Germany. wuerthner@chemie.uni-wuerzburg.de b Technische Universität Berlin, Institut für Chemie, Theoretische Chemie, Sekr. C 7, Straße des 17. Juni 135, 1623 Berlin, Germany c Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, 9774 Würzburg, Germany Table of Contents: 1. 1 H NMR Spectra of 3b,c and 4b,c S2 2. Optical properties of the monomers S4 3. X-ray diffraction analysis of 3a S5 4. Vapor pressure osmometry S6 5. Optical properties of the dimers S9 6. Quantification of chiral self-sorting and effect of temperature S1 7. Theoretical studies S28 S1

2 1. 1 H NMR Spectra of 3b,c and 4b,c 1 H NMR spectrum of 3b 1 H NMR spectrum of 3c S2

3 1 H NMR spectrum of 4b 1 H NMR spectrum of 4c S3

4 2. Optical properties of the monomers 1 1 P-enantiomer / M 1 cm a 3b 3c M-enantiomer / 1 3 M 1 cm / nm Figure S1. Bottom panel: UV/Vis absorption spectra of racemic solution in CM at M. Top panel: C spectra of P enantiomer (solid lines) and M enantiomers (dashed lines) in CM at M. Figure corresponds to macrocycles 3a c. / 1 3 l mol 1 cm a 3b 3c I fl / a.u Figure S2. UV/Vis absorption (5 1 6 M, solid lines) and normalized emission fluorescence spectra (~1 7 M, dashed lines) in CM of 3a c: 3a (black line), 3b (red line) and 3c (blue line). S4

5 3. X-Ray diffraction analysis of (P)-3a The crystal data of (P)-3a were collected on a Bruker X8APEX diffractometer with a CC area detector and multi-layer mirror monochromated Mo Kα radiation. The structure was solved using direct methods, refined with the Shelx software package (Sheldrick, G., Acta Cryst. 28, A64, ) and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in structure factors calculations. All hydrogen atoms were assigned to idealized geometric positions. Crystal data for (P)-3a: C 52 H 44 N 2 O 9, M r = 84.89, red square, mm 3, monoclinic space group C2, a = (8) Å, b = (7) Å, c = (8) Å, β = (2), V = (5) Å 3, Z = 8, ρ calcd = g cm 3, µ =.88 mm 1, F() = 3536, T = 1(2) K, R 1 =.911, wr 2 =.2431, 8996 independent reflections [2θ 52.5 ] and 1127 parameters. Crystallographic data have been deposited with the Cambridge Crystallographic ata Center as supplementary publication no. CCC These data can be obtained free of charge from the Cambridge Crystallographic ata Centre via The crystals were grown from dichloromethane/ethanol mixture and includ solvent molecules. As the geometry of both used solvents is similar, it was not possible to precisely localize them in four accessible voids. The Platon squeeze function was used to remove contribution of the solvent to the structure factors (Sluis, P. v. d.; A. L. Spek, A. L. Acta Cryst. 199, A46, ). The both perylene bisimide molecules found in asymmetrical unit show librational movements. The rigid-body analysis (Schomaker, V.; Trueblood, K. N. Acta Cryst. 1968, B24, 63 76) reveals that a center which gives symmetric rotation tensor is placed unsymmetrical above perylene bisimide system (see Figure S3. The calculation with disordered model of rigid molecules with additional isotropic restrains gives quite reasonable R 1 index of around 1%, i.e. 2% worse than from anisotropic refinement (see Figure S3. S5

6 Figure S3. The view depicting the librational movement of one of (P)-3aa molecules found in asymmetric unit. The blue cross marks center of rotation foundd with Schomaker and Trueblood method. Model obtained by rigid-body refinement of two disordered molecules. Figure S4. Closest distances in i dimer A (left) and dimer B (right) observedd in the solid state structure of (P)-3a. S6

7 4. Vapor pressure osmometry Signal c -1 / kg mol -1 Benzil 79 K cal = c / mol kg -1 Signal c -1 / kg mol -1 4b K mean = c / mol kg -1 Signal c -1 / kg mol c K mean = c / mol kg -1 Figure S5. VPO measurements of benzil (calibration curve), 4b and 4c in n-hexane at 45 C. The obtained signal divided into the measured concentration against the concentration in mol kg 1 is represented. The shown K values are in each case the extrapolated value of the y axis when x =. S7

8 Table S1. Comparison of the experimental ee values with those calculated from integral ratios of signal pairs of H a,h a, H b,h b and H c,h c for 4b ( and 4c (. % ee experimental % ee calculated H a,h a H b,h b H c,h c [a] [a] [a] [a] [a] [a] [a] 8 [a] [a] [a] [a] As the signals are superimposed, no accurate calculation of the % ee is possible. [a] % ee experimental % ee calculated H a,h a H b,h b H c,h c 7 7 [a] [a] [a] 3 [a] [a] [a] [a] As the signals are superimposed, no accurate calculation of the % ee is possible. [a] [a] S8

9 5. Optical properties of the dimers 1,2 4b (n=2) 1,,8 1,2 4c (n=3) 1,,8 I Fl / u.a.,6,4 I Fl / u.a.,6,4,2,2, / nm, Figure S6. Normalized concentration-dependent fluorescence spectra of 4b ( and 4c ( in n- hexane at M (dashed line) to M (solid line) at RT measured in a front face set up. / nm Table S2. Fluorescence lifetimes of 4a c measured at 61 and 535 nm (excitation wavelength 525 nm) at a concentration of M in n-hexane at RT using front face set up. f / ns (ra (M) (P) 4a 4b 4c 61 nm ± ± ± nm 3.9 ± ±.4 3. ±. 61 nm ± ± ± nm 4.2 ± ± ± nm ± ± ± nm 3.57 ± ± ±.1 S9

10 6. Quantification of chiral self-sorting and effect of temperature Table S3. imerization constants of racemate and pure enantiomers of PBI 4b obtained from two independent studies by nonlinear regression analysis at selected wavelengths and multilinear fit of the data at 331K, respectively. Sample / M 1 (ra-4b (M)-4b (P)-4b 6 nm 51 nm 514 nm 518 nm 522 nm 539 nm 33 ± 3 33 ± 51 ± 6 48 ± 46 ± 3 54 ± 6 34 ± 3 33 ± 4 52 ± 51 ± 4 47 ± 3 52 ± 4 36 ± 3 31 ± 4 57 ± 6 52 ± 4 47 ± 6 53 ± 36 ± 4 33 ± 67 ± 1 6 ± 7 49 ± 59 ± 8 39 ± 8 32 ± 9 8 ± 28 8 ± 2 ± 82 ± ± 7 29 ± 6 4 ± 6 66 ± 9 ± ± Multilinear fit (error ± 15 %) Table S4. imerization constants of racemate and pure enantiomers of PBI 4c obtained from two independent studies by nonlinear regression analysis at selected wavelengths and multilinear fit of the data at 331 and 298 K, respectively. Sample / M 1 (ra-4c (M)-4c (P)-4c 8 nm 512 nm 516 nm 52 nm 524 nm 54 nm 61 ± 7 73 ± 6 99 ± ± 9 99 ± 13 7 ± 7 6 ± 74 ± 4 12 ± 1 94 ± 6 14 ± 9 8 ± 6 6 ± 71 ± 4 98 ± 8 94 ± 7 16 ± 9 88 ± 6 63 ± 6 71 ± 1 ± 9 93 ± 8 99 ± 9 8 ± 6 64 ± 7 7 ± 6 96 ± ± ± ± 7 91 ± ± ± ± 4 9 ± 2 19 ± 18 Multilinear fit (error ± 15 %) S1

11 / 1 3 M -1 cm / 1 3 M -1 cm = 323 M -1 6 nm; = 33 ± 3 51 nm; = 34 ± nm; = 36 ± nm; = 36 ± nm; = 39 ± nm; = 38 ± nm; = 33 ± 51 nm; = 33 ± nm; = 31 ± nm; = 33 ± 522 nm; = 32 ± nm; = 29 ± = 32 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S7. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (ra-4b in n-heptane at 331 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S11

12 / 1 3 M -1 cm / 1 3 M -1 cm nm; K.9 = 46 ± 3 51 nm; K.8 = 47 ± nm; = 47 ± nm; = 49 ± nm; = ± nm; K.5 = 67 ± nm; = 54 ± 6 51 nm; = 52 ± nm; = 53 ± 518 nm; = 59 ± nm; = 82 ± nm; = 36 ± = 7 M = 54 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S8. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (P)-4b in n-heptane at 331 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S12

13 / 1 3 M -1 cm / 1 3 M -1 cm nm; K.9 = 51 ± 6 6 nm; K.9 = 48 ± 51 nm; K.8 = 52 ± 51 nm; = 51 ± nm; = 57 ± nm; = 52 ± nm; = 67 ± nm; = 6 ± nm; = 8 ± nm; K.6 = 8 ± nm; K.5 = 4 ± nm; = 66 ± = 2 M = 499 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S9. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (M)-4b in n-heptane at 331 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S13

14 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 994 ± nm; = 89 ± 9 M nm; = 12 ± nm; K = 94 ± 6 M nm; = 983 ± nm; K 52 nm; K.7 = 1 ± 9 = 94 ± 7 M nm; K 524 nm; K.6 = 961 ± 13 = 93 ± 8 M nm; = 142 ± nm; = 93 ± 11 M nm; = 142 ± 26 M = 9 M = 9 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S1. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (M)-4c in n-heptane at 331 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S14

15 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 99 ± 13 M nm; = 14 ± 9 M nm; = 16 ± 9 M nm; = 99 ± 9 M nm; = 99 ± 13 M nm; = 9 ± 2 M nm; = 7 ± 7 M nm; = 8 ± 6 M nm; = 88 ± 6 M nm; = 8 ± 6 M nm; = 711 ± 7 M nm; = 19 ± 18 M = 9 M = 91 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S11. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (P)-4c in n-heptane at 331 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S15

16 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 61 ± 7 M nm; = 6 ± M nm; = 6 ± M nm; = 63 ± 6 M nm; = 64 ± 7 M nm; = 91 ± 13 M nm; = 73 ± 6 M nm; = 74 ± 4 M nm; = 71 ± 4 M nm; = 71 ± M nm; = 7 ± 6 M nm; = 77 ± 8 M = 72 M = 71 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S12. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (ra-4c in n-heptane at 331 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S16

17 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 78 ± 9 M nm; =249 ± 48 M nm; = 13 ± 1 M nm; = 13 ± 1 M nm; = 14 ± 12 M nm; = 78 ± 9 M nm; = 178 ± 22 M nm; = 22 ± 24 M nm; = 17 ± 27 M nm; = 67 ± 7 M mon / 1 3 M -1 cm = 121 M -1 / 1 3 M -1 cm = 119 M Figure S13. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (P)-4a in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S17

18 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 136 ± 2 M nm; = 28 ± 3 M nm; = 116 ± 12 M nm; = 11 ± 1 M nm; = 97 ± 1 M nm; = 77 ± 1 M nm; = 152 ± 9 M nm; = 141 ± 8 M nm; = 136 ± 12 M nm; = 72 ± 9 M mon / 1 3 M -1 cm = 121 M -1 / 1 3 M -1 cm = 1211 M Figure S14. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (M)-4a in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S18

19 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 88 ± 9 M nm; = 64 ± M nm; = 5 ± 4 M nm; = 52 ± 4 M nm; = 42 ± 6 M nm; = 5 ± 8 M nm; = 53 ± 4 M nm; = 51 ± 4 M nm; = 4 ± M nm; = 51 ± 8 M / 1 3 M -1 cm = 6 M -1 / 1 3 M -1 cm = Figure S15. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (ra-4a in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S19

20 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 181 ± 16 M nm; = 181 ± 12 M nm; = 182 ± 12 M nm; = 171 ± 16 M nm; = 137 ± 3 M nm; = 214 ± M nm; = 163 ± 16 M nm; = 17 ± 1 M nm; = 174 ± 9 M nm; = 169 ± 14 M nm; = 18 ± 19 M nm; = 353 ± 84 M = 181 M = 18 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S16. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (P)-4b in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S2

21 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 24 ± 13 M nm; K.8 = 21 ± 9 M nm; K.7 = 197 ± 9 M nm; = 196 ± 14 M nm; = 182 ± 3 M nm; = 189 ± 28 M nm; = 254 ± 26 M nm; = 24 ± 19 M nm; = 232 ± 18 M nm; = 251 ± 3 M nm; = 198 ± 56 M nm; = 136 ± 1 M = 19 M = 199 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S17. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (M)-4b in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S21

22 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 121 ± 9 M nm; = 123 ± 7 M nm; = 119 ± 7 M nm; = 14 ± 11 M nm; K.6 = 91 ± 18 M nm; K.5 = 133 ± 19 M nm; = 12 ± 1 M nm; = 19 ± 9 M nm; = 13 ± 8 M nm; = 92 ± 9 M nm; = 76 ± 14 M nm; = 1 ± 16 M = 119 M = 127 M -1 / 1 3 M -1 cm / 1 3 M -1 cm Figure S18. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (ra-4b in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S22

23 6 6 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 569 ± 94 M nm; K.8 = 466 ± 36 M nm; K.7 = 411 ± 2 M nm; = 38 ± 3 M nm; = 358 ± 3 M nm; = 26 ± 49 M nm; = 516 ± 68 M nm; = 438 ± 22 M nm; = 414 ± 21 M nm; = 378 ± 28 M nm; = 354 ± 3 M nm; = 197 ± 36 M / 1 3 M -1 cm = 374 M -1 / 1 3 M -1 cm = 394 M Figure S19. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (P)-4c in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S23

24 6 6 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 547 ± 8 M nm; K.8 = 486 ± 4 M nm; K.7 = 46 ± 31 M nm; = 451 ± 31 M nm; = 444 ± 3 M nm; = 359 ± 72 M nm; = 697 ± 158 M nm; = 522 ± 61 M nm; = 476 ± 4 M nm; = 45 ± M nm; = 532 ± 89 M nm; = 19 ± 39 M / 1 3 M -1 cm = 389 M -1 / 1 3 M -1 cm = 39 M Figure S2. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (M)-4c in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S24

25 / 1 3 M -1 cm / 1 3 M -1 cm nm; = 448 ± 69 M nm; K.8 = 356 ± 2 M nm; K.7 = 313 ± 18 M nm; = 283 ± 2 M nm; = 258 ± 26 M nm; = 133 ± 28 M nm; = 421 ± 66 M nm; = 344 ± 23 M nm; = 39 ± 17 M nm; = 294 ± 2 M nm; = 266 ± 26 M nm; = 173 ± 37 M / 1 3 M -1 cm = 2997 M -1 / 1 3 M -1 cm = 297 M Figure S21. Illustration of the applied data acquisition and evaluation procedure based on two independent experiments (left and right). Concentration-dependent UV/Vis absorption spectra of (ra-4c in n-heptane at 298 K ([M] = M to M), molar fraction of monomer wavelengths indicated in the inset, and results from the multilinear fit routine showing the S25

26 Table S5. imerization binding constants of racemate and pure enantiomers of PBI 4a as obtained from two independent studies by nonlinear regression analysis at selected wavelengths and multilinear fit of the data at 298K, respectively. Sample [M 1 ] (ra-4a (M)-4a (P)-4a 6 nm 512 nm 516 nm 521 nm 541 nm 88 ± 9 5 ± ± 2 28 ± 3 78 ± ± ± 53 ± ± ± 9 13 ± ± 22 5 ± 4 51 ± 4 97 ± ± 8 13 ± 9 22 ± ± 4 4 ± 97 ± ± ± ± ± 6 51 ± 8 77 ± 1 72 ± 9 78 ± 9 67 ± 7 Multilinear fit (error ± 15 %) Table S6. imerization binding constants of racemate and pure enantiomers of PBI 4b as obtained from two independent studies by nonlinear regression analysis at selected wavelengths and multilinear fit of the data at 298K, respectively. Sample [M 1 ] (ra-4b (M)-4b (P)-4b 6 nm 51 nm 514 nm 518 nm 522 nm 121 ± 9 12 ± 1 24 ± ± ± ± ± 7 19 ± 9 21 ± 9 24 ± ± ± ± 7 13 ± ± ± ± ± 9 14 ± ± ± ± ± ± ± ± ± ± ± 3 18 ± nm 133 ± 19 1 ± ± ± ± 353 ± 84 Multilinear fit (error ± 15 %) S26

27 Table S7. imerization binding constants of racemate and pure enantiomers of PBI 4c as obtained from two independent studies by nonlinear regression analysis at selected wavelengths and multilinear fit of the data, respectively, at 298 K. Sample [M 1 ] 8 nm 512 nm 516 nm 52 nm 524 nm 54 nm Multilinear fit (error ± 15 %) (ra-4c 448 ± 356 ± 313 ± 283 ± 258 ± 133 ± ± 344 ± 39 ± 294 ± 266 ± 173 ± (M)-4c 547 ± 486 ± 46 ± 451 ± 444 ± 359 ± ± 522± 476 ± 45 ± 532 ± 19 ± (P)-4c 569 ± 466 ± 411 ± 38 ± 358 ± 26 ± ± ± ± ± ± ± , / 1 3 M 1 cm ,8,6,4,2 564 nm; K = 458 ± 84 M nm; K = 581 ± 3 M nm; K = 588 ± 3 M nm; K = 57 ± 61 M / nm, Figure S22. Concentration-dependent UV/Vis absorption spectra of 2 in n-heptane at 331 K ([M] = M to M) and molar fraction of monomer species and dimerization constants obtained from nonlinear regression analysis at selected wavelengths indicated in the inset applying the equal K model. Arrows indicate changes upon increasing concentration. S27

28 7. Theoretical studies Figure S23. Two different structures found after energy minimization of the homodimer. Structure showing ecliptic orderr with slight rotational displacements andd structure with a rotational displacemen nt of about 3. S28