Supporting Information

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1 Supporting Information Photo-controlled reversible guest uptake, storage and release by azobenzene-modified microporous multi-layer films of pillar[5]arenes Tomoki Ogoshi,,,,* Shu Takashima and Tada-aki Yamagishi Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, , Japan JST, PRESTO, Honcho, Kawaguchi, Saitama, , Japan WPI Nano Life Science Institute, Kanazawa University, Kakuma-machi, Kanazawa, , Japan Table of Contents General Methods Compounds Synthesis NMR and MS Spectra Photoisomerization Uptake of p-dmb by trans-azo-nl Films Fluorescence Change by Complexation between 1L Film and NaOS Fluorescence Change by Photo-isomerization of azo-1l Film References S2-S3 S4 S5-S6 S7-S14 S15 S16 S17 S18 S19 S1

2 S1. General Methods Materials. All solvents and reagents were used as supplied. Pillar[5]arenes with 10 cationic (P+), anionic (P-), and bromide moieties (1) were synthesized according to the previous papers. S1-S3 Measurements. The 1 H NMR spectra were recorded at 500 MHz and 13 C NMR spectra were recorded at 125 MHz with a JEOL-ECA500 spectrometer. UV-vis absorption spectra were recorded with a JASCO V-670. LbL Film Assembly. Quartz substrates were sonicated in concentrated nitric acid for 30 min and finally washed with methanol for three times, and dried for 12 h at 100 o C to generate anionic silanol moieties on the surface. First, the substrate was immersed in P+ in aqueous solution for 2 h to introduce P+ molecules onto the anionic substrate surface. The immersing time (2 h) was enough to reach equilibrium state. The sample was washed with a large amount of water to remove excessive un-modified P+ molecules and dried for 2 h at 25 o C under reduced pressure to obtain the cationic monolayer (1L). Then, 1L was immersed into P- in aqueous solution for 2 h to introduce P- molecules onto 1L of P- molecules, and washed with a large amount of water and dried in a vacuum for 2 h at 25 o C to give the bilayer with anionic surface (2L). Multi-layer films (nl, n is numbers of deposited times) were obtained by repeating the alternating immersion steps in P+ and P- solutions. To attach azobenzene valves onto the micropore outlets, we used an aqueous solution of cationic pillar[5]arene with one azobenzene moiety (Figure 1a, azo-p+) instead of P+. Host-guest Complexation. For the complexation, the multi-layered films were immersed in p-dnb (40 mm) in chloroform, and then washed with a large amount of chloroform to remove the p-dnb on the surface of the film. The film was dried in a vacuum before UV vis measurement. To induce the release of the p-dnb in the channels, the multi-layered films were immersed in a chloroform solution containing excess competitive guest 1,4-dicyanobutane (4.48 M), and then washed with a large amount of chloroform to remove 1,4-dicyanobutane on the surface of the film. The film was dried in a vacuum before UV vis measurement. Isomerization Conversions between Trans and Cis Forms in azo-1l Film. The isomerization conversions were calculated from the absorbance at λ max for the π-π* S2

3 absorption of the trans isomer at time according to the equation: [cis] / [trans] = (1 A/A 0 ) / (1 - cis / trans ) The cis / trans value in the present study was determined from the absorption spectra and 1 H NMR spectra of trans-p+ in DMSO-d 6 solution in the initial state and in the photo-stationary state. S3

4 S2. Compounds trans-azo-p+-model P+ P- N O 2Br - O N trans-azo-p+ P+-model p-dnb 1,4-Dicyanobutane Sodium 1-octanesulfonate (NaOS) S4

5 S3. Synthesis trans-azo-p+. To a solution of pillar[5]arene with 10 bromide groups S3 (1, 467 mg, mmol) in acetonitrile (10 ml), anhydrous potassium carbonate (152 mg, 1.10 mmol) and 4-(2-Phenyldiazenyl)phenol (54.5 mg, mol) was heated at 80 o C for 24 h, then cool to room temperature, the product was collected by vacuum filtration. Column chromatography (silica gel; dichloromethane : hexane = 1 : 1) afforded a white solid (2, 187 mg, mmol, Yield: 38%). 2 (180 mg, mmol) and trimethylamine (25% in ethanol, 2 ml, 3.00 mmol) were added to ethanol (5 ml). The solution was refluxed for 24 h. Then, the solvent was removed by evaporation. To the residue, deionized water (20 ml) was added, thoroughly washed with chloroform. After removing the organic layer, the water was removed by evaporation to obtain azo-p+ as a solid (213 mg, mmol, Yield 91%). The 1 H NMR spectrum of azo-p+ is shown in Figure S1. 1 H NMR (500 MHz, DMSO-d 6, 25 o C) δ (ppm): 7.97 (d, 2H), 7.85 (d, 2H), (m, 3H), 7.30 (d, 2H), (m 10H), (br, 50H), (br, 81H). The 13 C NMR spectrum of azo-p+ is shown in Figure S2. 13 C NMR (125 MHz, DMSO-d 6, 25 o C) δ (ppm): 161.2, 151.9, 149.8, 148.9, 148.8, 148.7, 148.6, 148.5, 146.3, 131.0, 129.4, 128.4, 128.2, 128.0, 127.9, 124.8, 122.2, 115.6, 115.4, 68.2, 67.6, 64.6, S5

6 64.4, 62.9, 62.5, 62.0, 53.1, 52.9, 29.2, , HRESIMS spectra of azo-p+ is shown in Figure S3: m/z of C 94 H 150 Br 9 N 11 O [M 2Br] 2+, [M 3Br] 3+, [M 4Br] 4+, [M 5Br] 5+. trans-azo-p+-model. To a solution of 1,4-bis(2-bromoethoxy)benzene S4 (972 mg, 3.00 mmol) in acetone (10 ml), anhydrous potassium carbonate (622 mg, 4.50 mmol) and 4-(2-Phenyldiazenyl)phenol (595 mg, 3.00 mol) was heated at 70 o C for 12 h, then cool to room temperature, the product was collected by vacuum filtration. Column chromatography (silica gel; dichloromethane : hexane = 1 : 4) afforded a solid (573 mg, 1.30 mmol, Yield: 43%). The obtained product (500 mg, 1.13 mmol) and trimethylamine (25% in ethanol, 7.5 ml, 11.3 mmol) were added to ethanol (7.5 ml). The solution was refluxed for 24 h. Then, the solvent was removed by evaporation. To the residue, deionized water (20 ml) was added, thoroughly washed with chloroform. After removing the organic layer, the water was removed by evaporation to obtain trans-azo-p+-model as a solid (539 mg, 1.08 mmol, 95%). The 1 H NMR spectrum of trans-azo-p+-model is shown in Figure S4. 1 H NMR (500 MHz, CD 3 OD, 25 o C) δ (ppm): (m, 4H), 7.50 (t, 2H), 7.44 (t, 1H), (m, 6H), (m, 8H), (m, 9H). The 13 C NMR spectrum of trans-azo-p+-model is shown in Figure S5. 13 C NMR (125 MHz, CD 3 OD, 25 o C) δ (ppm): 130.4, 126.2, 123.6, 116.9, HRESIMS: m/z Calcd for C 25 H 30 N 3 O 3 [M-Br] + : found N N Br N N O O OH N O O K 2 CO 3 O Br Br - N S6

7 S4. NMR and MS Spectra Figure S1 1 H NMR spectrum of trans-azo-p+ in DMSO-d 6 at 25 o C. S7

8 Figure S2 13 C NMR spectrum of trans-azo-p+ in DMSO-d 6 at 25 o C. S8

9 S9

10 S10

11 S11

12 Figure S3 HRESIMS spectra of trans-azo-p+. S12

13 Figure S4 1 H NMR spectrum of trans-azo-p+-model in CD 3 OD at 25 o C. S13

14 Figure S5 13 C NMR spectrum of trans-azo-p+-model in CD 3 OD at 25 o C. S14

15 S5. Photoisomerization Figure S6 Absorbance changes of the UV spectra of trans-azo-5l at 354 nm as a function of cycles upon alternating UV light irradiation for 5 minutes and heating at 80 o C for 1 h. S15

16 Figure S7 Isomerization of azobenzene moieties in azo-1l film by UV light irradiation for 5 minutes and heating at 80 o C for 1 h. S16

17 S6. Uptake of p-dmb by trans-azo-nl films Figure S8 Absorbance at 293 nm versus immersion time for the trans-azo-nl films. S17

18 S7. Fluorescence Change by Complexation between P+-1L Film and NaOS Figure S9 Monitoring complexation between 1L film and sodium 1-octanesulfonate (NaOS) by fluorescence change (excited at 293 nm) from the 1,4-dialkocybenzene units of P+ in (a) 1L and (b) P+-model-1L films. The complexation lowered the mobility of the units, which led to increasing fluorescence intensity (Figure S9a), while the fluorescence in the unit model did not change even after complexation with NaOS (Figure S9b). S18

19 S8. Fluorescence Change by Photoisomerization of azo-1l Film Figure S10 Fluorescence changes (excited at 293 nm) of (a) azo-1l and (b) azo-p+-model films by photo-isomerization from trans to cis form. The fluorescence from the 1,4-dialkoxybenzene in trans state was larger than 1.3 times larger than that in cis state (Figure S10a). The change did not found in a film prepared form the unit model of azo-p+ (Figure S10b). These results suggest inclusion of the cis from azobenzene moiety into the pillar[5]arene cavity to inhibit the complexation with p-dnb. S19

20 References S1) Ogoshi, T.; Hashizume, M.; Yamagishi, T.; Nakamoto, Y. Chem. Commun. 2010, 46, S2) Ma, Y.; Ji, X.; Xiang, F.; Chi, X.; Han, C.; He, J.; Abliz, Z.; Chen, W.; Huang, F. Chem. Commun. 2011, 47, S3) Nierengarten, I.; Guerra, S.; Holler, M.; Karmazin-Brelot, L.; Barbera, J.; Deschenaux, R.; Nierengarten, J. F. Eur. J. Org. Chem. 2013, S4) Pinto, M. R.; Kristal, B. M.; Schanze, K. S. Langmuir 2003, 19, S20