Supporting Information

Transcription

1 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 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_ _sm_miscellaneous_information.pdf

2 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, , China, buwf@lzu.edu.cn Yun Zhang and Xin Chen National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai, , 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 C). 1 H NMR (400 MHz, CDCl 3, Me 4 Si) δ 7.41 (d, J(H,H) = 8.4 Hz, 4H), (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), (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, ESI-MS calcd for [C 33 H 20 I 2 O+H] , found : 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

3 yellow solid (143 mg, 45% yield, m.p C). 1 H NMR (400MHz, CDCl 3, Me 4 Si) δ= (m, 7H), (m, 5H), (m, 12H), 7.78 (s, 3H), 7.87 (d, J(H,H) = 8.0 Hz, 4H), (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, ESI-MS calcd for [C 49 H 30 O+H] , found 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 C). 1 H NMR (400MHz, CDCl 3, Me 4 Si) δ= 3.81 (s, 4H), 2

4 (m, 10H), (m, 8H), (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, ESI-MS calcd for [C 56 H 39 N+H] , found : 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 C). 1 H NMR (400 MHz, CDCl 3, Me 4 Si) δ= 3.84 (s, 8H), (m, 8H), (m, 8H), 6.82 (d, J(H,H) = 8.4 Hz, 2H), (m, 4H), 7.04 (s, 1H), 7.12 (d, J(H,H) = 8.4 Hz, 2H), (m, 2H), 7.53 (d, J(H,H) = 8.4 Hz, 4H), 7.60 (d, J(H,H) = 8.4 Hz, 4H), (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, ESI-MS calcd for [C 50 H 46 Br 2 O 8 +H] , found : 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 C). 1 H NMR (400MHz, CDCl 3, Me 4 Si) δ 3.84 (s, 8H), (m, 8H), (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), (m, 6H), (m, 1H), (m, 4H), (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, ESI-MS calcd for [C 66 H 56 O 8 +H] , found

5 Scheme S2 Synthetic routes of the control compound 3 4

6 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 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

7 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 ( 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

8 and eq of TFA 1.5 eq of P 1 -t-bu I / a. u / nm Figure S5. Fluorescence spectra of 2 and 3 ( and moll -1, the total concentration is 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, 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

9 Figure S7. Fluorescence decay profiles at 480 nm excited at 315 at room temperature: 1 (orange dots, 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, 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

10 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] ± ± ± ± 0.57 TFA-1[c] 1.31 ± ± ± ± [d] 1.01 ± ± ± ± [e] 0.98 ± ± ± ± 0.40 TFA-1[f] 1.24 ± ± ± ± [g] 0.98 ± ± ± ± 0.40 [a] 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] 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

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

12 Figure S C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 1 (δ ppm). Figure S13. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of 2. 11

13 Figure S C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 2. Figure S C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 2 (δ ppm). 12

14 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 S C NMR spectrum (100 MHz, in CDCl 3, 25 o C) of 3. 13

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

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

17 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

18 Figure S C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 9. Figure S C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 9 (δ ppm). 17

19 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 S C NMR spectrum (100 MHz, in CDCl 3, 25 o C) of

20 Figure S C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 10 (δ ppm). Figure S29. 1 H NMR spectrum (400 MHz, in CDCl 3, 25 o C) of

21 Figure S C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 11. Figure S C NMR spectrum (150 MHz, in CDCl 3, 25 o C) of 11 (δ ppm). 20

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

23 References: [1] Kotha, S.; Kashinath, D.; Lahiri, K.; Sunoj, R. B. Eur. J. Org. Chem. 2004, 19, [2] Wang, X.; Ervithayasuporn, V.; Zhang, Y.; Kawakami, Y. Chem. Commun. 2011, 47, [3] Lee, Y.-G.; Koyama, Y.; Yonekawa, M.; Takata, T. Macromolecules 2010, 43,