SUPPORTING INFORMATION

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1 SUPPORTING INFORMATION Molecular clips with extended aromatic sidewalls as receptors for electron acceptor molecules. Synthesis, NMR, photophysical, and electrochemical investigation Barbara Branchi, Vincenzo Balzani, Paola Ceroni,* Mireia Campañá Kuchenbrandt, Frank-Gerrit Klärner,* Dieter Bläser, Roland Boese Table of contents General Experimental Details 1 Determination of K a by solid-liquid extraction experiments 2 1 H NMR spectra of the new compounds 1 H-NMR spectra of 1a at two different concentrations 10 1 H-NMR spectra of 1c at two different concentrations 11 1 H-NMR spectra of 2a at two different concentrations 11 K a and max by solid-liquid extraction and subsequent 1 H NMR analysis 12 max, K a,g for the formation of host-guest complexes 14 1 H NMR titrations 15 General Experimental Details 1 H NMR, 1 C NMR, DEPT H, H-COSY, C, H-COSY, NOESY, HMQC, HMBC and 1 H NMR titration experiments: the undeuterated portion of the solvent was used as an internal reference. Position of the protons of the methylene bridges in the clip molecules are indicated by the letters i (innen, towards the centre of the molecule) and a (aussen, away from the centre of the molecule). All melting points are uncorrected. Column chromatography: silica gel mm. All solvents were distilled prior to use. 1

2 The electrostatic potential surfaces (EPS) shown in Figure 2 were calculated by the use of computer program SPARTAN 04 Version (Wavefunction Inc.) and the pdb files containing the atomic coordinates for the calculated structures are included. Fluorescence spectra were performed on air-equilibrated solutions. Determination of K a by solid-liquid extraction experiments K a [RS] = [R] [S] [S] sat = [S] (1) K a = ([R] 0 ([S] 0 [S] 0 [S] sat + [S] sat ) )[S] sat [R] 0 = [R] + [RS] (2) [S] 0 = [S] + [RS] [S] sat [R] 0 [S] 0 = Saturation concentration of the guest molecule in pure solvent = Total concentration of the host molecule = Total concentration of the guest molecule The saturation concentration [NDCA] sat in chloroform was determined by the use of UV/Vis spectroscopy. The molar extinction coefficient of NCDA at the wavelength = 64 nm was determined in acetonitrile in which NDCA is soluble. Then the solvent was distilled off in vacuo from a saturated solution of NDCA in ml of chloroform and the solid residue was dissolved in 10 ml of acetonitrile and the saturation concentration [NDCA] sat was determined from the extinction E measured in the UV/Vis spectrum of this solution and the known extinction coefficient by the use of the Lambert-Beer law. The saturation concentrations [1,8-DNAQ] sat and [1,5-DNAQ] sat by means of cyclohexene as internal standard in the 1 H NMR spectra of a saturated solution of these two compounds in CDCl. 2

3 1 H NMR spectra of the new compounds OAc O CH O a b 7 a b 19 a b 14 b 1 18 a a 15 a a 5 4 1a Figure S1. 1 H NMR spectrum (top), HMQC (bottom left) and HMBC (bottom right) of 1a.

4 OH HO a a a a 4 1b Figure S2. 1 H NMR spectrum (top), HMQC (bottom left) and HMBC (bottom right) of 1b. 4

5 OMe O CH b 26 7 b b a 6 a a 5 4 1c Figure S. 1 H NMR spectrum (top), HMQC (bottom left) and HMBC (bottom right) of 1c. 5

6 OAc 9 18 O O CH a a Figure S4. 1 H NMR spectrum (top), HMQC (bottom left) and HMBC (bottom right) of 2a. 6

7 OAc O 15 CH O a Figure S5. 1 H NMR spectrum (top), HMQC (bottom left) and HMBC (bottom right) of a. 7

8 a 10b a a b 6a 6 5 8,9-dimethylfluoranthene Figure S6. 1 H NMR spectrum of 8,9-dimethylfluoranthene. Br Br Br a 10b 11 a 12 8 a 1 4 6b 7 6a Br Figure S7. 1 H NMR spectrum of 6. 8

9 OAc O CH 12 1 O 18 7 a b b a 1 6 a a 4 9a Figure S8. 1 H NMR spectrum of 9a. 9

10 OAc OAc 1a Figure S9. 1 H-NMR spectra of 1a at two different concentrations (2 mm and 6 mm). The concentration dependence observed for the signals of the protons attached to the benzo[k]- fluoranthene side walls indicate a weak self-association 10

11 OMe OMe 1c Figure S10. 1 H-NMR spectra of 1c at two different concentrations (2 mm and 6 mm). There is no concentration dependence observed. OAc OAc 2a Figure S11. 1 H-NMR-Spectra of 2a at two different concentrations (2 mm and 4 mm). There is no concentration dependence observed. 11

12 Determination of K a and max by solid-liquid extraction and subsequent 1 H NMR analysis a) b) 12

13 c) Figure S12. 1 H NMR spectra of the saturated solution of the pure guest molecule, mixture of guest molecule and 1a as host molecule, and pure 1a in CDCl. Saturation concentration of the guest molecule: a) [NDCA] sat = M, b) [1,8-DNAQ] sat = M, and c) [1,5-DNAQ] sat = M. 1

14 Table S1. The maximum complexation-induced 1 H NMR shifts of the guest protons ( max = 0 - complex ), association constants (K a [M -1 ]), and Gibbs enthalpies (G [kcal/mol]) determined for the formation of host-guest complexes by 1 H NMR titration experiments in CDCl at 298 K. Guest Host 1a (R = OAC) Host 1c (R = OMe) K a G max K a G max TCNB [(1c) 2 G] [(1c)G].0.5 TCNQ [(1c) 2 G] [(1c)G] KS NDCA TNF (a) (b) (b) (c) (H a ), 2.1 (H b ) 2.0 (H c ), 1.7 (H d ) 0.9 (H e ) (H a ),.4 (H b ) 1.6 (H c ), 1.4 (H d ) 0.8 (H e ) (a) (H a ) 2.1 (H c ) 1.9 (H e ) AQ (H a ), 0.5 (H b ) 1,8-DNAQ (a) (H a ), 2.5 (H b ) 1.5 (H c ) 1,5-DNAQ (a) (H a ), 2.7 (H b ) 1. (H c ) (H a ) 2.1 (H c ) 1.9 (H d ) (a) (H a ), 1.5 (H b ) 0.9 (H c ) (a) (H a ), 1.7 (H b ) 0.9 (H c ) determined by (a) solid-liquid extraction, (b) spectrofluorimetric titration, (c) spectrophotometric titration 14

15 Table S2. Total host concentration [R] 0, total guest concentration [S] 0, and association constants K a determined from the solid-liquid extraction experiments. [R] 0 [mol/l] 1a a) [S] 0 [mol/l] K a b) [M -1 ] [R] 0 [mol/l] 1c a) [S] 0 [mol/l] K a b) [M -1 ] NCDA ,8-DNAQ ,5-DNAQ a) Determined by integration of the up-field shifted guest signals in the 1 H-NMR spectra of the host-guest mixtures shown in Figure S. b) Calculated from the concentrations [R] 0, [S] 0, and [S] sat by the use of equation (2), experimental section. 1 H NMR titrations Receptor: Solvent: T [ C]: Substrate: 1a CDCl TCNB M R [g/mol]: Ms [g/mol]: m R [mg]: NC NC CN CN 0 [ppm] = 8.2 m S [mg]: V 0 [ml]: [S] 0 [mm] : V [ml] [R] 0 [M] obs (H) [ppm] obs (H) [ppm] calc (H) [ppm]

16 ,5,0 2,5 obs [ppm] 2,0 1,5 K a = (9.2 ± 0.4) 10 2 M -1 max (H) =.84 ppm 1,0 0,5 0,0 0,000 0,001 0,002 0,00 0,004 0,005 [R] 0 [M] TCNB@1a: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 2.55 (d, 2H,H-27i, H-28i), 2.56 (s, 6H, -CH ), 2.76 (d, 2H, H-27a, H-28a), 4.40 (s, 4H, H-9, H-11, H-22, H-24), 4.41 (s, 2H, TCNB), 7.55 (s, 4H, H-8, H-12, H-21, H-), 7.59 (dd, 4H, H-2, H-5, H-15, H-18), 7.7 (d, 4H, H-, H-4, H-16, H-17), 7.94 (d, 4H, H-1, H-6, H-14, H-19), 7.96 (s, 4H, H-7, H-1, H-20, H-26). Receptor: Solvent: T [ C]: Substrate: 1a CDCl TCNQ M R [g/mol]: Ms [g/mol]: m R [mg]: NC NC CN CN 0 [ppm] = m S [mg]: V 0 [ml]: [S] 0 [mm] : V [ml] [R] 0 [M] obs (H) [ppm] obs (H) [ppm] calc (H) [ppm]

17 2,0 1,8 1,6 1,4 obs [ppm] 1,2 1,0 0,8 0,6 K a = (5.8 ± 0.2) 10 2 M -1 max (H) = 2.67 ppm 0,4 0,2 0,0 0,000 0,001 0,002 0,00 0,004 0,005 [R] 0 [M] TCNQ@1a: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 2.47 (s, 6H, -CH ), 2.56 (d, 2H,H-27i, H-28i), 2.77 (d, 2H, H-27a, H-28a), 4.1 (s, 4H, H-9, H-11, H-22, H-24), 4.89 (s, 4H, TCNQ), 7.46 (dd, 4H, H-2, H-5, H-15, H-18), 7.59 (s, 4H, H-8, H-12, H-21, H-), 7.64 (d, 4H, H-, H-4, H-16, H-17), 7.64 (d, 4H, H-1, H-6, H-14, H- 19), 7.9 (s, 4H, H-7, H-1, H-20, H-26). Receptor: Solvent: T [ C]: Substrate: 1a CDCl Kosower salt d b a O 0 (H a ) [ppm] = c N 0 (H b ) [ppm] = (H c ) [ppm] = I O e 0 (H d ) [ppm] = (H e ) [ppm] = M R [g/mol]: Ms [g/mol]: m R [mg]: m S [mg]: V 0 [ml]: [S] 0 [mm] : V [ml] [R] 0 [M] obs (H b ) [ppm] obs (H b ) [ppm] calc (H b ) [ppm]

18 1,6 obs [ppm] 1,4 1,2 1,0 0,8 0,6 0,4 0,2 K a = (4.8 ± 0.1) 10 2 M -1 max (H a ) = 1.85 ppm max (H b ) = 2.1 ppm max (H c ) = 2.04 ppm max (H d ) = 1.71 ppm max (H e ) = 0.89 ppm 0,0 0,000 0,001 0,002 0,00 0,004 0,005 [R] 0 [M] KS@1a: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 0.10 (H, KS, H d ), 2.51 (d, 2H,H-27i, H-28i), 2.56 (s, 6H, -CH ), 2.67 (d, 2H, H-27a, H-28a),.09 (2H, KS, H c ),.20 (H, KS, H e ), 4.6 (s, 4H, H-9, H-11, H-22, H- 24), 4.89 (s, 4H, KS), 6.71 (2H, KS, H a ), 7.8 (2H, KS, H b ), 7.61 (dd, 4H, H-2, H-5, H-15, H-18), 7.74 (s, 4H, H-8, H-12, H-21, H-), 7.74 (d, 4H, H-, H-4, H-16, H-17), 8.08 (d, 4H, H-1, H-6, H-14, H-19), 8. (s, 4H, H- 7, H-1, H-20, H-26). Receptor: Solvent: T [ C]: Substrate: NC CN a e O 2 N b c d NO 2 NO 2 1a CDCl TNF 0 (H a ) [ppm] = (H b ) [ppm] = (H c ) [ppm] = (H d ) [ppm] = (H e ) [ppm] = M R [g/mol]: Ms [g/mol]: m R [mg]: m S [mg]: V 0 [ml]: [S] 0 [mm] : V [ml] [R] 0 [M] obs (H c ) [ppm] obs (H c ) [ppm] calc (H c ) [ppm]

19 2,5 obs [ppm] 2,0 1,5 1,0 0,5 0,0 0,000 0,001 0,002 0,00 0,004 0,005 [R] 0 [M] K a = (2.2 ± 0.6) 10 M -1 max (H a ) = 1.61 ppm max (H b ) = n.d. max (H c ) = 2.07 ppm max (H d ) = n.d. max (H e ) = 1.9 ppm TNF@1a: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 2.57 (d, 2H,H-27i, H-28i), 2.67 (s, 6H, -CH ), 2.78 (d, 2H, H-27a, H-28a), 4.8 (s, 4H, H-9, H-11, H-22, H-24), 6.16 (d, 1H, TNF, H c ), 7.0 (dd, 4H, H-2, H-5, H- 15, H-18), 7.1 (s, 4H, H-7, H-1, H-20, H-26), 7.16 (s, 4H, H-8, H-12, H-21, H-), 7. (d, 4H, H-1, H-6, H- 14, H-19), 7.2 (d, 4H, H-, H-4, H-16, H-17), 7.60 (d, 1H, TNF, H e ), 8.08 (d, 1H, TNF, H a ). Receptor: Solvent: T [ C]: Substrate: 1a CDCl AQ M R [g/mol]: Ms [g/mol]: m R [mg]: b a O 0 (H a ) [ppm] = m S [mg]: V 0 [ml]: O 0 (H b ) [ppm] = [S] 0 [mm] : 1.7 V [ml] [R] 0 [M] obs (H a ) [ppm] obs (H a ) [ppm] calc (H a ) [ppm]

20 0,5 0,4 obs [ppm] 0, 0,2 K a = (4.4 ± 0.1) 10 M -1 max (H a ) = 0.2 ppm max (H b ) = 0.19 ppm 0,1 0,0 0,000 0,001 0,002 0,00 0,004 0,005 [R] 0 [M] AQ@1a: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 2.17 (s, 6H, -CH ), 2.19 (d, 2H,H-27i, H-28i), 2.8 (d, 2H, H-27a, H-28a), 4.15 (s, 4H, H-9, H-11, H-22, H-24), 7.58 (m, 4H, AQ, H a ), 7.90 (dd, 4H, H-2, H-5, H-15, H-18), 7.9 (d, 4H, H-, H-4, H-16, H-17), 8.14 (m, 4H, AQ, H b ), 8.21 (s, 4H, H-8, H-12, H-21, H-), 9.15 (d, 4H, H-1, H-6, H-14, H-19), (s, 4H, H-7, H-1, H-20, H-26). Receptor: Solvent: T [ C]: Substrate: 1c CDCl TCNB M R [g/mol]: Ms [g/mol]: m R [mg]: NC NC CN CN 0 [ppm] = 8.0 m S [mg]: V 0 [ml]: [S] 0 [mm] : V [ml] [R] 0 [M] obs (H) [ppm] obs (H) [ppm]

21 K a = (1.6 ± 0.2) 10 2 M -1 max (H) =.49 ppm K a (2:1)= 46 ± 44 M -1 max (H) = 2.8 ppm The evaluation was performed using the HOSTEST program. Receptor: Solvent: T [ C]: Substrate: 1c CDCl TCNQ M R [g/mol]: Ms [g/mol]: m R [mg]: NC NC CN CN 0 [ppm] = m S [mg]: V 0 [ml]: [S] 0 [mm] : V [ml] [R] 0 [M] obs (H) [ppm] obs (H) [ppm]

22 K a = (1.2 ± 0.1) 10 2 M -1 max (H) = 2.88 ppm K a (2:1)= 229 ± 2 M -1 max (H) = 2.76 ppm The evaluation was performed using the HOSTEST program. Receptor: Solvent: T [ C]: Substrate: 1c CDCl TNF M R [g/mol]: Ms [g/mol]: m R [mg]: O 2 N b a NC NO 2 CN c e d NO 2 0 (H a ) [ppm] = (H b ) [ppm] = (H c ) [ppm] = (H d ) [ppm] = (H e ) [ppm] = m S [mg]: V 0 [ml]: [S] 0 [mm]: V [ml] [R] 0 [M] obs (H c ) [ppm] obs (H c ) [ppm] calc (H c ) [ppm]

23 2,5 obs [ppm] 2,0 1,5 1,0 0,5 K a = (6.9 ± 0.8) 10 M -1 max (H a ) = 1.50 ppm max (H b ) = n. d. ppm max (H c ) = 2.14 ppm max (H d ) = 1.86 ppm max (H e ) = n. d. ppm 0,0 0,000 0,002 0,004 0,006 0,008 [R] 0 [M] TNF@1c: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 2.67 (d, 2H,H-27i, H-28i), 2.78 (d, 2H, H-27a, H- 28a), 4.44 (s, 6H, -CH ), 4.75 (s, 4H, H-9, H-11, H-22, H-24), 6.09 (d, 1H, TNF, H c ), 6.49 (s, 4H, H-8, H-12, H- 21, H-), 6.72 (d, 1H, TNF, H d ), 6.78 (dd, 4H, H-2, H-5, H-15, H-18), 7.00 (s, 4H, H-7, H-1, H-20, H-26), 6.88 (d, 4H, H-1, H-6, H-14, H-19), 6.85 (d, 4H, H-, H-4, H-16, H-17), 8.18 (d, 1H, TNF, H a ). Rezeptor: Lösungsmittel: T [ C]: Substrat: d c I N b a e O O 1c CDCl Kosower Salt 0 (H a ) [ppm] = (H b ) [ppm] = (H c ) [ppm] = (H d ) [ppm] = M R [g/mol]: Ms [g/mol]: m R [mg]: m S [mg]: V 0 [ml]: [S] 0 [mm] : (H e ) [ppm] = V [ml] [R] 0 [M] obs (H a ) [ppm] obs (H a ) [ppm] calc (H a ) [ppm]

24 0,7 0,6 0,5 K a = (5.0 ± 0.4) 10 M -1 max (H a ) =.75 ppm obs [ppm] 0,4 0, max (H b ) =.4 ppm max (H c ) = 1.65 ppm 0,2 0,1 0,0 0,000 0,001 0,002 0,00 0,004 0,005 [R] 0 [M] max (H d ) = 1.6 ppm max (H e ) = 0.80 ppm KS@1c: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 0.47 (t, H, KS, H d ), 2.72 (d, 2H, H-27a, H-28a), 2.60 (d, 2H, H-27i, H-28i),.0 (s, H, KS, H e ),.51 (q, 2H, KS, H c ), 4.00 (s, 6H, -CH ), 4.57 (s, 4H, H-9, H-11, H- 22, H-24), 4.8 (d, 2H, KS, H a ), 6.12 (d, 2H, KS, H b ), 7.60 (dd, 4H, H-2, H-5, H-15, H-18), 7.62 (s, 4H, H-8, H- 12, H-21, H-), 7.59 (d, 4H, H-, H-4, H-16, H-17), 7.97QR(d, 4H, H-1, H-6, H-14, H-19), 8.11QR(s, 4H, H-7, H- 1, H-20, H-26). Receptor: Solvent: T [ C]: Substrate: 2a CDCl TNF M R [g/mol]: Ms [g/mol]: m R [mg]: O 2 N NC CN a e b c d NO 2 NO 2 0 (H a ) [ppm] = (H b ) [ppm] = (H c ) [ppm] = (H d ) [ppm] = (H e ) [ppm] = m S [mg]: V 0 [ml]: [S] 0 [mm] : V [ml] [R] 0 [M] obs (H d ) [ppm] obs (H d ) [ppm] calc (H d ) [ppm]

25 2,0 1,8 obs [ppm] 1,6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0 0,000 0,001 0,002 0,00 0,004 0,005 0,006 [R] 0 [M] K a = (6.1 ± 0.5) 10 2 M -1 max (H a ) = 1.58 ppm max (H b ) = 1.01 ppm max (H c ) = 1.90 ppm max (H d ) = 2.7 ppm max (H e ) = 1.55 ppm TNF@2a: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 2.49, 2.58 (2d, 2H, H-2a, H-24a), 2.67 (s, 6H, -CH ), 2.72, 2.75 (m, 2H, H-2i, H-24i), 4.6 (s, 2H, H-11, H-18 oder H-9, H-20), 4.6 (s, 2H, H-11, H-18 oder H-9, H-20), 6.21 (dd, 1H, TNF, H d ), 6.4 (d, 1H, TNF, H c ), 6.57 (m, 2H, H-14, H-15), 6.68 (s, 2H, H-7, H-22), 7.12 (s, 2H,H-12, H-17), 7.12 (s, 2H, H-8, H-21), 7.15 (dd, 2H, H-2, H-5), 7.21 (m, 2H, H-1, H-16), 7.27 (d, 2H, H-1, H6), 7.5 (d, 2H, H-, H-4), 7.94 (d, 1H, TNF, H b ), 7.96 (d, 1H, TNF, H e ), 8.10 (d, 1H, TNF, H a ). Receptor: Solvent: T [ C]: Substrate: a CDCl TNF M R [g/mol]: Ms [g/mol]: m R [mg]: O 2 N NC CN a e b c d NO 2 NO 2 0 (H a ) [ppm] = (H b ) [ppm] = (H c ) [ppm] = (H d ) [ppm] = (H e ) [ppm] = m S [mg]: V 0 [ml]: [S] 0 [mm]: V [ml] [R] 0 [M] obs (H a ) [ppm] obs (H a ) [ppm] calc (H a ) [ppm]

26 0,8 0,6 K a = (1.2 ± 0.0) 10 2 M -1 max (H a ) = 1.96 ppm obs [ppm] 0,4 max (H b ) = 1.20 ppm max (Hc) = 1.5 ppm 0,2 max (H d ) = 1.0 ppm max (H e ) = 1.76 ppm 0,0 0,000 0,001 0,002 0,00 0,004 0,005 0,006 0,007 [R] 0 [M] TNF@a: 1 H-NMR (500 MHz, CDCl, C): c [ppm] = 2.51 (s, 6H, -CH ), 2.76 (d, 1H, H-17a), 2.80(d,1H, H-17i), 4.44 (s, 2H, H-9, H-14), 6.54 (s, 2H, H-7, H-16), 6.81 (d, 2H, H-1, H-6), 6.8 (2H, H-11, H-12), 6.89 (d, 1H, TNF, H c ), 6.94 (s, 2H, H-8, H-15), 7.16 (dd, 2H, H-2, H-5), 7.27 (dd, 1H, TNF, H d ), 7.44 (d, 2H, H-, H-4), 7.7 (d, 1H, TNF, H a ), 7.75 (d, 1H, TNF, H b ), 7.75 (d, 1H, TNF, H e ). 26

SUPPLEMENTARY INFORMATION

SUPPLEMENTARY INFORMATION doi:10.1038/nature14137 1. Supplementary Methods 2. Supplementary Text 2.1 Physico-Chemical Properties and Structural Elucidation of Compound 1. 2.2 Physico-Chemical Properties and Structural Elucidation