Supporting Information

Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013 ph-controlled Reversible Formation of a Supramolecular Hyperbranched Polymer Showing Fluorescence Switching Bingran Yu, [a] Baoyan Wang, [a] Shuwen Guo, [a] Qian Zhang, [a] Xiaorui Zheng, [a] Haitao Lei, [a] Weisheng Liu, [a] Weifeng Bu,* [a] Yun Zhang, [b] and Xin Chen [b] chem_201204315_sm_miscellaneous_information.pdf

Supporting Information Reversible Formation of a Supramolecular Hyperbranched Polymer Accompanies a Fluorescence Switch Controlled by Acid-Base Reaction Bingran Yu, Shuwen Guo, Baoyan Wang, Qian Zhang, Xiaorui Zheng, Haitao Lei, Weisheng Liu, and Weifeng Bu* Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, State Key Laboratory of Applied Organic Chemistry, and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu, 730000, China, E-mail: buwf@lzu.edu.cn Yun Zhang and Xin Chen National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai, 200083, China 10: 1,3,5-tris(p-iodophenyl)benzene [1] 4 (0.68 g, 1.0 mmol), 4-formylphenylacetylene [2] (0.13 g, 1.0 mmol), Pd(PPh 3 ) 4 (0.58g, 0.05mmol), CuI (19.0mg, 0.10mmol), ipr 2 NH (0.20g, 2.0mmol), and THF (20 ml) were added to a Schlenk tube under an argon atmosphere and the resulting mixture was stirred for 48 h at 50 C. The crude product was obtained by removing the solvent under a reduced pressure, which was further purified by column chromatography on silica gel (CH 2 Cl 2 /petroleum ether = 1/1). 10 was isolated as a yellow solid (130 mg, 19% yield, m.p. 108 109 C). 1 H NMR (400 MHz, CDCl 3, Me 4 Si) δ 7.41 (d, J(H,H) = 8.4 Hz, 4H), 7.65-7.91 (m, 9H), 7.71 (s, 2H), 7.81 (d, J(H,H) = 8.4 Hz, 2H), 7.88 (d, J(H,H) = 8.4 Hz, 2H), 10.03 (s, 1H); 13 C NMR (150 MHz, CDCl 3, Me 4 Si) δ 89.7, 93.3, 93.8, 122.1, 125.1, 125.2, 127.5, 129.3, 129.8, 132.3, 132.5, 135.6, 138.2, 140.4, 141.3, 141.8, 141.9, 191.6 ESI-MS calcd for [C 33 H 20 I 2 O+H] + 686.9682, found 686.9679. 11: 10 (0.34g, 0.5mmol), ethynylbenzene (0.20 g, 2.0 mmol), Pd(PPh 3 ) 4 (0.58g, 0.05mmol), CuI (19.0 mg, 0.10 mmol), Et 3 N (0.20 g, 2.0 mmol), and toluene (20 ml) were added to a Schlenk tube under an argon atmosphere and the resulting mixture was stirred for 48 h at 110 C. The crude product was obtained by removing the solvent under a reduced pressure, which was further purified by column chromatography on silica gel (CH 2 Cl 2 /petroleum ether = 1/1). 11 was isolated as a 1

yellow solid (143 mg, 45% yield, m.p. 65 68 C). 1 H NMR (400MHz, CDCl 3, Me 4 Si) δ= 7.33-7.37 (m, 7H), 7.56-7.58 (m, 5H), 7.66-7.73 (m, 12H), 7.78 (s, 3H), 7.87 (d, J(H,H) = 8.0 Hz, 4H), 10.02 (s, 1H), 13 C NMR (150 MHz, CDCl 3, Me 4 Si) δ= 89.3, 89.6, 90.6, 93.4, 122.0, 122.9, 123.3, 125.3, 125.5, 127.4, 127.5, 128.5, 129.7, 129.7, 131.8, 132.3, 132.3, 132.5, 132.6, 135.6, 140.6, 141.5, 141.7, 142.0, 191.6. ESI-MS calcd for [C 49 H 30 O+H] + 635.2375, found 635.2345. Scheme S1 Synthetic routes of the control compound 2 2: 11 (0.13g, 0.2 mmol), benzylamine (32 mg, 0.3 mmol), and toluene (10 ml) were added to a Schlenk tube under an argon atmosphere and the mixture was stirred for 24 h at 110 C. The solvent was removed under a reduced pressure, which produce a yellow solid. NaBH 4 (0.19 g, 0.5 mmol) was added in a THF solution (15 ml) of the yellow solid. The resulting mixture was stirred at 50 C for overnight. The mixture was filtered to remove the insoluble impurities. The solvent was evaporated under a reduced pressure to generate a crude product. And then 2 was isolated as a yellow solid by recrystallizing the crude product from dichloromethane and methanol (126 mg, 87% yield, m.p. 97 99 C). 1 H NMR (400MHz, CDCl 3, Me 4 Si) δ= 3.81 (s, 4H), 2

7.24-7.27 (m, 10H), 7.56-7.57 (m, 8H), 7.66-7.67 (m, 12H), 7.78 (s, 4H), 13 C NMR (100 MHz, CDCl 3, Me 4 Si) δ= 51.9, 89.1, 89.5, 90.4, 121.8, 122.7, 123.2, 125.1, 125.3, 127.2, 127.4, 128.4, 129.5, 129.6, 131.6, 132.1, 132.2, 132.4, 140.5, 141.3, 141.6, 141.8. ESI-MS calcd for [C 56 H 39 N+H] + 726.3161, found 726.3195. 14: 1,3,5-tris(p-bromophenyl)benzene [1] 12 (0.54 g, 1.0 mmol), 13 [3] (0.47 g, 1.0 mmol), Pd(PPh 3 ) 4 (0.58g, 0.05mmol), CuI (19.0 mg, 0.10 mmol), i Pr 2 NH (0.20 g, 2.0 mmol), and THF (20 ml) were added to a Schlenk tube under an argon atmosphere and the mixture was stirred for 3 days at 50 C. The crude product was obtained by removing the solvent under a reduced pressure, which was further purified by column chromatography on silica gel (CHCl 3 /acetone = 3/1). 14 was isolated as a yellow solid (150 mg, 16% yield, m.p. 160 163 C). 1 H NMR (400 MHz, CDCl 3, Me 4 Si) δ= 3.84 (s, 8H), 3.92-3.93 (m, 8H), 4.15-4.16 (m, 8H), 6.82 (d, J(H,H) = 8.4 Hz, 2H), 6.87-6.88 (m, 4H), 7.04 (s, 1H), 7.12 (d, J(H,H) = 8.4 Hz, 2H), 7.44-7.48 (m, 2H), 7.53 (d, J(H,H) = 8.4 Hz, 4H), 7.60 (d, J(H,H) = 8.4 Hz, 4H), 7.61-7.70 (m, 3H), 7.73 (s, 2H); 13 C NMR (100 MHz, CDCl 3, Me 4 Si) δ= 69.3, 69.7,69.9, 71.2, 109.7, 113.2, 113.9, 116.5, 121.3, 122.0, 124.9, 125.3, 127.1, 128.4, 128.5, 128.8, 132.0, 139.6, 141.3, 148.8. ESI-MS calcd for [C 50 H 46 Br 2 O 8 +H] + 933.1638, found 933.1663. 3: 14 (0.47g, 0.5mmol), ethynylbenzene (0.20 g, 2.0 mmol), Pd(PPh 3 ) 4 (0.58g, 0.05mmol), CuI (19.0 mg, 0.10 mmol), Et 3 N (0.20 g, 2.0 mmol), and THF (20 ml) were added to a Schlenk tube under an argon atmosphere and the mixture was stirred for 48 h at 110 C. The crude product was obtained by removing the solvent under a reduced pressure, which was further purified by column chromatography on silica gel (CHCl 3 /acetone = 3/1). 14 was isolated as a yellow solid (254 mg, 52% yield, m.p. 151 153 C). 1 H NMR (400MHz, CDCl 3, Me 4 Si) δ 3.84 (s, 8H), 3.93-3.94 (m, 8H), 4.16-4.17 (m, 8H), 6.83 (d, J(H,H) = 8.4 Hz, 2H), 6.89 (s, 4H), 7.06 (s, 1H), 7.14 (d, J(H,H) = 8.0 Hz, 2H), 7.33-7.36 (m, 6H), 7.46-7.47 (m, 1H), 7.56-7.58 (m, 4H), 7.64-7.71 (m, 12H), 7.81 (s, 2H); 13 C NMR (100 MHz, CDCl 3, Me 4 Si) δ= 69.3, 69.8,69.9, 71.2, 89.2, 90.3, 109.7, 113.3, 114.0, 116.7, 121.4, 122.7, 123.2, 125.1, 125.4, 127.2, 128.3, 128.5, 131.6, 132.0, 132.1, 140.2, 140.5, 141.7, 148.8. ESI-MS calcd for [C 66 H 56 O 8 +H] + 977.4088, found 977.4081. 3

Scheme S2 Synthetic routes of the control compound 3 4

Figure S1. MALDI-TOF mass spectrum of TFA-1 measured in the positive-ion mode using CH 2 Cl 2 as the solvent. c b a PPM Figure S2. 1 H NMR spectra (600 MHz CD 2 Cl 2 ) of the mixture of 2 and 3 with a molar ratio of 1:1 at a total concentration of 1 10-3 moll -1 : (a) The original spectrum, (b) after addition of 1.1 eq of TFA, and (c) after further addition of 1.2 equiv of P 1 -t-bu. 5

a b Figure S3. The experimental (a) and theoretical (b) ESI-MS spectra of [2 3 H] +. Figure S4. Fluorescence spectral changes of TFA-1 (8 10-6 moll -1, dichloromethane) upon titration with TFA (P 1 -t-bu/ TFA-1 = 0, 0.5, 1, 1.5, 2.0, 2.5) at both monomeric and excimeric emission bands. 6

4800 3600 2 and 3 1.2 eq of TFA 1.5 eq of P 1 -t-bu I / a. u. 2400 1200 0 350 420 490 / nm Figure S5. Fluorescence spectra of 2 and 3 (4 10-6 and 4 10-6 moll -1, the total concentration is 8 10-6 moll -1 in dichloromethane) upon titration with TFA and P 1 -t-bu. Figure S6. Fluorescence decay profiles at 393 nm excited at 315 at room temperature: 1 (orange dots, 8 10-6 moll -1, dichloromethane), TFA-1 obtained upon addition of 2.2 eq of TFA (green), 1 regenerated after addition of 2.4 eq of P 1 -t-bu (cyan), 1 obtained upon addition of 50 eq of the salt of TFA P 1 -t-bu (magenta), TFA-1 obtained after addition of 2.2 eq of TFA (navy), and 1 regenerated by addition of 2.4 equiv of P 1 -t-bu (wine). The fitted curves are represented as full lines. 7

Figure S7. Fluorescence decay profiles at 480 nm excited at 315 at room temperature: 1 (orange dots, 8 10-6 moll -1, dichloromethane), TFA-1 obtained upon addition of 2.2 eq of TFA (green), 1 regenerated after addition of 2.4 eq of P 1 -t-bu (cyan), 1 obtained upon addition of 50 eq of the salt of TFA P 1 -t-bu (magenta), TFA-1 obtained after addition of 2.2 eq of TFA (navy), and 1 regenerated by addition of 2.4 equiv of P 1 -t-bu (wine). The fitted curves are represented as full lines. Figure S8. 1 H NMR spectra (600 MHz, in CD 2 Cl 2, 5.0 10-4 moll -1 ) of TFA-1 (a), 11H 2 2+ Ac 2- obtained by treating 2.4 eq of TBAAc to TFA-1 (b), and 1 (c). 8

Figure S9. Competitive experiments demonstrated that TFA-1 selectively binds acetate ion (a). Fluorescence intensity changes of TFA-1 at 393 nm in dichloromethane (b). Table S1. Luminescence Lifetimes[a] (τ 1 and τ 2 ) for 1 and TFA-1. Sample τ 1 (ns) RW 1 (%) [b] τ 2 (ns) RW 2 (%) [b] 1 1.01 ± 0.10 88.69 ± 4.43 5.65 ± 0.57 11.31 ± 0.57 TFA-1[c] 1.31 ± 0.13 37.70 ± 1.88 5.87 ± 0.59 62.30 ± 3.11 1[d] 1.01 ± 0.10 91.86 ± 4.59 4.76 ± 0.48 8.14 ± 0.41 1[e] 0.98 ± 0.10 91.90 ± 4.56 5.00 ± 0.50 8.10 ± 0.40 TFA-1[f] 1.24 ± 0.12 53.18 ± 2.66 5.52 ± 0.55 46.82 ± 2.34 1[g] 0.98 ± 0.10 91.96 ± 4.60 4.70 ± 0.47 8.04 ± 0.40 [a] 8 10-6 moll -1 CH 2 Cl 2 solutions monitored at 480 nm after excitation at 315 nm. [b] Relative weighting (RW) of component in double exponential fits. [c] Produced by adding 2.2 eq of TFA into the solution of 1. [d] Obtained by treating 2.4 eq of P 1 -t-bu to TFA-1. [e] 8 10-6 moll -1 CH 2 Cl 2 solution together with 50 eq of TFA P 1 -t-bu. [f] Produced by adding 2.2 eq of TFA into the [e] solution. [g] Obtained by treating 2.4 eq of P 1 -t-bu to the [f] solution. 9

Figure S10. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 1. Figure S11. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 1. 10

Figure S12. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 1 (δ 113-143 ppm). Figure S13. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 2. 11

Figure S14. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 2. Figure S15. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 2 (δ 121-143 ppm). 12

O O O O O O O O 3 Figure S16. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 3. O O O O O O O O 3 Figure S17. 13 C NMR spectrum (100 MHz, in CDCl 3, 25 o C) of 3. 13

Figure S18. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 5. Figure S19. 13 C NMR spectrum (100 MHz, in CDCl 3, 25 o C) of 5. 14

Figure S20. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 6. Figure S21. 13 C NMR spectrum (100 MHz, in CDCl 3, 25 o C) of 6. 15

Figure S22 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 8. Figure S23 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 9 16

Figure S24. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 9. Figure S25. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 9 (δ 113-143 ppm). 17

CHO I 10 I Figure S26. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 10. CHO I 10 I Figure S27. 13 C NMR spectrum (100 MHz, in CDCl 3, 25 o C) of 10. 18

Figure S28. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 10 (δ 120-144 ppm). Figure S29. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 11. 19

Figure S30. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 11. Figure S31. 13 C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 11 (δ 113-143 ppm). 20

Figure S32. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 14. Figure S33. 13 C NMR spectrum (100 MHz, in CDCl 3, 25 o C) of 14. 21

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