Supporting Information

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1 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2011 Molecular Implementation of Sequential and Reversible Logic Through Photochromic Energy Transfer Switching Patricia Remón, [a] Martin Hammarson, [b] Shiming Li, [b] Axel Kahnt, [b] Uwe Pischel,* [a] and Joakim AndrØasson* [b] chem_ _sm_miscellaneous_information.pdf

2 Supporting Information Contents: 1) Synthesis General Methods and Materials 2) Synthesis Procedures 3) Comparison of Absorption and Fluorescence Spectra of the Dyads (3-SP, 4-SP) and the Model Compounds (1-SP, 3-M, 4-M) 4) Sequential Logic with 3-MEH + and 4-MEH + 5) Cycling of the Dyads 3-SP and 4-SP 6) Cycling of 5 7) MR spectra 1

3 1) Synthesis General Methods and Materials 1 H MR (400 MHz) and 13 C MR (100.6 MHz) spectra were recorded on standard spectrometers. In the 1 H MR spectra the chemical shifts are referenced to TMS as internal reference or the residual solvent peak. In the 13 C MR spectra the chemical shifts are referenced to the carbon signal of CDCl 3 (77.2 ppm). High resolution mass spectrometry (HRMS) was performed on a Micromass GCT Mass Spectrometer at the Chemistry Centre of Lund University, Sweden. The masses are reported as the average of three runs. All reactants and reagents used in the synthesis were purchased from Aldrich or Fluka, except methyl 4-bromobutyrate, which was from TCI. All chemicals were used as received without further purification. Tetrahydrofuran (THF) was distilled over a and benzophenone. Ethanol (EtH) was distilled over Mg/I 2. Acetonitrile (MeC) was distilled over CaH 2. All other solvents [methanol (MeH),,-dimethylformamide (DMF), diethylether (Et 2 ), chloroform (CHCl 3 ), dichloromethane (DCM), and ethylacetate (EtAc)] were used as received unless stated otherwise. 2) Synthesis Procedures (except for 2-SP, which is described in the Experimental Section of the manuscript) -(2-Aminoethyl)-4-amino-1,8-naphthalimide H 2 Scheme 1 + H 2 H 2 EtH reflux H 2 H 2 A solution of 4-amino-1,8-naphthalic anhydride (250 mg, 1.2 mmol) and ethylenediamine (786 µl, 11.7 mmol) in 10 ml EtH was heated to reflux for 4 h and then stirred for 1.5 h at room temperature. Then the solvent was evaporated under reduced pressure. The resulting residue was treated with little water; the solid was filtered and then washed with copious amounts of water and some diethylether. 154 mg (50% yield) of the product were obtained as solid, which was used in the synthesis of 2- SP and 2-M without further purification. 1 H MR (400 MHz, [D 6 ]DMS, 25ºC) δ = 8.60 (d, J = 8.3 Hz, 1H; Ar-H), 8.42 (d, J = 7.2 Hz, 1H; Ar-H), 8.18 (d, J = 8.3 Hz, 1H; Ar-H), 7.65 (t, J = 7.8 Hz, 1H; Ar-H), 7.44 (br. s, 2H; Ar-H 2 ), 6.83 (d, J = 8.3 Hz, 1H; Ar-H), 4.01 (t, J = 7.0 Hz, 2H; CH 2 ), 2.74 (t, J = 7.0 Hz, 2H; CH 2 ), 1.52 ppm (br. s, 2H; H 2 ). -(2-Aminoethyl)dansylamide S 2 Cl Scheme 2 + H 2 H 2 CHCl 3 reflux S H H 2 A solution ethylenediamine (745 µl, 11.1 mmol) in 12 ml dry CHCl 3 was heated to reflux under nitrogen atmosphere. To this solution dansylchloride (200 mg, 0.74 mmol) 2

4 in 10 ml dry CHCl 3 was added slowly during a period 2 h. The mixture was kept at reflux for 4 h. After cooling to room temperature the reaction mixture was washed with 2 15 ml water. After drying the organic phase with a 2 S 4 the solvent was removed under reduced pressure. The crude product was further purified by flash chromatography (Si 2 ) using DCM/MeH (95/5) as eluent. 65 mg (30% yield) of a solid product were obtained. 1 H MR (400 MHz, [D 6 ]DMS, 25 ºC) δ = 8.45 (d, J = 8.5 Hz, 1H; Ar-H), 8.29 (d, J = 8.7 Hz, 1H; Ar-H), 8.10 (dd, J = 7.3, 1.2 Hz, 1H; Ar-H), (m, 2H; Ar-H), 7.25 (d, J = 7.5 Hz, 1H; Ar-H), 2.82 (s, 6H; (CH 3 ) 2 ), 2.74 (t, J = 6.6 Hz, 2H; CH 2 ), 2.44 ppm (t, J = 6.6 Hz, 2H; CH 2 ). 3-(Aminomethyl)perylene This product was synthesized in a multistep procedure shown in Scheme 3. The first four intermediate products were synthesized according to published methods: 3- formylperylene, [1] 3-(hydroxymethyl)perylene, [2] 3-(bromomethyl)perylene, [3] 3- (azidomethyl)perylene. [4] The final step was accomplished by using a modified procedure (described below). H H Br 3 H 2 a b c d e Scheme 3. Reagents and conditions: (a) SnCl 4 /ClCH 2 CH 2 Cl/Cl 2 CHCH 3 /H 2 ; (b) abh 4, THF/EtH, rt, 30 min; (c) CBr 4, PPh 3, DMF, 0 ºC, 10 min; (d) a 3, DCM, rt, 15 h; (e) H 2, 10% Pd/C, MeH, rt, 16h. Methanol (120 ml) was purged with argon for 5 min and added to a flask containing 3- (azidomethyl)perylene (200 mg, 0.65 mmol) and 10% Pd/C (120 mg) under argon atmosphere. The grey-yellow mixture was stirred under a hydrogen atmosphere for 16 h. The Pd/C catalyst was filtered through a short silica pad and washed with hot methanol. The filtrate and washing were combined and methanol was removed under reduced pressure to afford 3-(aminomethyl)perylene in quantitative yield. 1 H MR (400 MHz, CDCl 3, 25 ºC) δ = (m, 4H; Ar-H), 7.92 (d, J = 8.4 Hz, 1H; Ar-H), (m, 2H; Ar-H), (m, 4H; CH 2 ), 4.30 ppm (s, 2H; CH 2 ). Compound 1-SP 1'-(3-Carboxypropyl)-3',3'-dimethyl-6-nitrospiro[2H-1]benzopyran-2,2'-indoline (1-SP) was prepared according to published or modified procedures (Scheme 4): 1-(3- carbomethoxypropyl)-3,3-dimethyl-2-methyleneindoline, [5] 1'-(3-carbomethoxypropyl)- 3',3'-dimethyl-6-nitrospiro[2H-1]benzopyran-2,2'-indoline (see below), 1'-(3- carboxypropyl)-3',3'-dimethyl-6-nitrospiro[2h-1]benzopyran-2,2'-indoline. [6] 3

5 + Br CH 3 a + Br b CH 3 H CH 2 c 2 2 H Scheme 4. Reagents and conditions: (a) CHCl 3, reflux, 24 h; (b) Et 3, THF/CHCl 3, 80 C, overnight; (c) ah, THF, rt, 48 h, followed by neutralization with citric acid. To a mixture of the quaternary bromide salt (3.74 g, 11.0 mmol) and 5- nitrosalicylaldehyde (1.86 g, 11 mmol) in 170 ml THF/CHCl 3 (10/7) TEA (3.3 ml) was added. After the mixture had been heated (80 C) overnight, the solvents were removed under reduce pressure. THF was added to the greenish residue and the appearing colorless needles (Et 3 HBr) were removed by filtration. The filtrate was evaporated under reduced pressure to give a purple solid, which was purified by flash chromatography (Si 2 ) and recrystallization from EtH (2.70 g, 60% yield). The MR data coincided with the published data. [6] HS ester of compound 1-SP The procedure for synthesis of the succinimidyl ester (HS ester) of 1-SP was adopted from the literature. [7] CH H a 2 H Scheme 5. Reagents and conditions: (a) DCC, MeC, rt, 12 h. A solution of 1-SP (394 mg, 1.0 mmol), DCC (619 mg, 1.0 mmol) and - hydroxysuccinimide (345 mg, 1.0 mmol) in dry MeC (25 ml) was stirred at room temperature for 12 h. The precipitated dicyclohexylurea was filtered off and the solvent was removed under reduced pressure. The crude product was purified by flash chromatography with the eluent DCM/MeH (95/5) and recrystallization from EtH/DCM (0.30 g, 60% yield). 1 H MR (400 MHz, CDCl 3, 25 ºC) δ = (m, 2H; Ar-H), 7.20 (dt, J = 7.6, 1.2 Hz, 1H; Ar-H), 7.11 (dd, J = 6.8, 0.8 Hz, 1H; Ar-H), 6.95 (d, J = 10.4 Hz, 1H; vinyl-h), 6.90 (t, J = 7.6 Hz, 1H; Ar-H), 6.75 (d, J = 8.8 Hz, 1H; Ar-H), 6.62 (d, J = 8.0 Hz, 1H; Ar-H), 5.88 (t, J = 10.4 Hz, 1H; vinyl-h), (m, 2H; CH 2 ), 2.86 (br. s, 4H; CH 2 - CH 2 ), 2.67 (t, J = 7.0 Hz, 2H; CH 2 ), (m, 2H; CH 2 ), 1.29 (s, 3H; CH 3 ),

6 ppm (s, 3H; CH 3 ); 13 C MR (100.6 MHz, CDCl 3, 25 ºC) δ = 169.2, 168.4, 159.5, 146.8, 141.1, 136.1, 128.8, 128.0, 126.0, 122.9, 121.9, 121.4, 120.0, 118.6, 115.6, 107.0, 106.6, 52.6, 42.5, 28.2, 26.1, 25.7, 23.6, 20.0 ppm; HRMS (TF, EI+): m/z: calcd for C 26 H : ; found: Dyad 3-SP S H H 2 A solution of succinimidyl ester of 1-SP (49.1 mg, 0.1 mmol) and -(2- aminoethyl)dansylamide (29.3 mg, 0.1 mmol) in THF/DCM (1/2, 10 ml) was stirred at room temperature for 4 hours. Then the mixture was diluted with EtAc, washed with brine and water, and the organic phase was dried over a 2 S 4. The solvents were removed under reduced pressure and the obtained crude product was purified by flash chromatography (Si 2 ) with EtAc/DCM (1/2) as eluent. 40 mg (57% yield) of pure 3- SP were obtained. 1 H MR (400 MHz, CDCl 3, 25 ºC) δ = 8.54 (d, J = 8.8 Hz, 1H; Ar-H), (m, 2H; Ar-H), (m, 2H; Ar-H), 7.56 (t, J = 8.0 Hz, 1H; Ar-H), 7.51 (dd, J = 8.4, 7.6 Hz, 1H; Ar-H), (m, 2H; Ar-H), 7.08 (d, J = 8.8 Hz, 1H; Ar-H), 6.89 (d, J = 10.4 Hz, 1H; vinyl-h), 6.87 (t, J = 7.2 Hz, 1H; Ar-H), 6.73 (d, J = 8.4 Hz, 1H; Ar-H), 6.62 (d, J = 8.0 Hz, 1H; Ar-H), 5.87 (d, J = 10.4 Hz, 1H; vinyl-h), 5.83 (t, J = 5.6 Hz, 1H; H), 5.22 (t, J = 6.0 Hz, 1H; H), (m, 4H; CH 2 ), (m, 2H; CH 2 ), 2.88 (s, 6H; Me 2 ), (m, 2H; CH 2 ), (m, 2H; CH 2 ), 1.27 (s, 3H; CH 3 ), 1.17 ppm (s, 3H; CH 3 ); 13 C MR (100.6 MHz, CDCl 3, 25 ºC) δ = 173.3, 159.7, 152.3, 147.2, 141.0, 136.0, 134.3, 130.9, 130.1, 129.8, 129.6, 128.7, 128.3, 127.9, 126.0, 123.3, 122.9, 122.1, 121.8, 119.7, (2C), 115.6, 115.4, 107.0, 106.9, 52.8, 45.6 (2C), 43.3 (2C), 39.4, 33.7, 26.1, 24.8, 20.0 ppm; HRMS (TF, EI+): m/z: calcd for C 36 H S: ; found: Dyad 4-SP H 2 A solution of the succinimidyl ester of 1-SP (50 mg, 0.1 mmol) and 3- (aminomethyl)perylene (30 mg, 0.1 mmol) in THF/DCM (1/2, 15 ml) and DMF (1 ml) was stirred at room temperature for 7.5 h. The resulting mixture was diluted with DCM and washed with brine and water. The organic phase was dried over a 2 S 4. Removal of the solvent with a rotary evaporator yielded the crude product, which was purified by 5

7 flash chromatography (Si 2 ) with a mixture of MeH/DCM (2/98) as eluent. This procedure yielded 45 mg of 4-SP (68% yield). 1 H MR (400 MHz, CDCl 3, 25 ºC) δ = (m, 3H; Ar-H), 8.13 (d, J = 7.2 Hz, 1H; Ar-H), 7.96 (dd, J = 8.4, 2.8 Hz, 1H; Ar-H), 7.93 (d, J = 2.4 Hz, 1H; Ar-H), 7.81 (d, J = 8.0 Hz, 1H; Ar-H), 7.72 (d, J = 8.4 Hz, 2H; Ar-H), (m, 3H; Ar-H), 7.39 (d, J = 7.6 Hz, 1H; Ar-H), 7.15 (dt, J = 7.6, 1.2 Hz, 1H; Ar-H), 7.07 (dd, J = 7.2, 0.8 Hz, 1H; Ar-H), 6.86 (dt, J = 7.6, 0.4 Hz, 1H; Ar-H), 6.78 (d, J = 10.8 Hz, 1H; vinyl-h), 6.70 (d, J = 9.2 Hz, 1H; Ar-H), 6.63 (d, J = 7.6 Hz, 1H; Ar-H), 5.82 (d, J = 10.4 Hz, 1H; vinyl-h), 5.58 (t, J = 5.2 Hz, 1H; H), (m, 2H; CH 2 ), (m, 2H; CH 2 ), (m, 2H; CH 2 ), (m, 2H; CH 2 ), 1.25 (s, 3H; CH 3 ), 1.15 ppm (s, 3H; CH 3 ); 13 C MR (100.6 MHz, CDCl 3, 25 ºC) δ = 171.9, 159.7, 147.2, 141.0, 136.0, 134.7, 133.0, 132.7, 132.0, 131.7, 131.1, 130.9, 129.2, 128.5, 128.3, (2C), 128.0, 127.7, 127.3, 126.8, 126.7, 126.0, 123.3, 122.8, 122.0, 121.9, 120.6, 120.5, (2C), 118.6, 115.6, 115.1, 107.0, 106.8, 53.6, 52.9, 43.3, 42.1, 33.9, 26.1, 25.0, 20.0 ppm; HRMS (TF, EI+): m/z: calcd for C 43 H : ; found: Model compound 2-M H 2 Scheme 6 H 2 + Cl CHCl 3 Et 3 reflux H 2 H A mixture of -(2-aminoethyl)-4-amino-1,8-naphthalimide (95 mg, 0.37 mmol), acetylchloride (53 µl, 0.74 mmol), and triethylamine (52 µl, 0.37 mmol) in 5 ml dry chloroform was refluxed under nitrogen atmosphere for 24 h. In the course of the reaction a precipitate was formed, which was filtered, washed with cold chloroform and water and dried. The crude product was purified by flash chromatography (Si 2 ) with a mixture of DCM/MeH (90/10). 47 mg (42% yield) of product were obtained. 1 H MR (400 MHz, [D 6 ]DMS, 25 ºC) δ = 8.61 (dd, J = 8.5, 1.1 Hz, 1H; Ar-H), 8.42 (dd, J = 7.3, 1.1 Hz, 1H; Ar-H), 8.19 (d, J = 8.4 Hz, 1H; Ar-H), 7.94 (t, J = 5.8 Hz, 1H; CH), 7.65 (dd, J = 8.4, 7.3 Hz, 1H; Ar-H), 7.43 (s, 2H; Ar-H 2 ), 6.84 (d, J = 8.4 Hz, 1H; Ar-H), 4.08 (t, J = 6.4 Hz, 2H; CH 2 ), 3.31 (t, 2H; partially hidden under the water signal; CH 2 ), 1.71 ppm (s, 3H; CH 3 ); HRMS (TF, EI+): m/z: calcd for C 16 H : ; found: Model compound 3-M Scheme 7 S H H 2 + CHCl 3 Cl Et 3 reflux S H H A mixture of -(2-aminoethyl)dansylamide (139 mg, 0.47 mmol), acetylchloride (67 µl, 0.95 mmol), and triethylamine (66 µl, 0.47 mmol) in 4 ml dry chloroform was refluxed under nitrogen atmosphere for 24 h. Thereafter the solvent was evaporated and 6

8 water was added. A solid formed, which was washed with copious amounts of water. The crude product was purified by flash chromatography (Si 2 ) with a mixture of DCM/MeH (90/10). 68 mg (43% yield) of product were obtained. 1 H MR (400 MHz, [D 6 ]DMS, 25 ºC) δ = 8.46 (dt, J = 8.4, 1.0 Hz, 1H; Ar-H), 8.26 (dt, J = 8.6, 0.8 Hz, 1H Ar-H), 8.09 (dd, J = 7.3, 1.3 Hz, 1H; Ar-H), 7.98 (t, J = 5.7 Hz, 1H; H), 7.78 (t, J = 5.8 Hz, 1H; H), (m, 2H; Ar-H), 7.26 (dd, J = 7.6, 0.7 Hz, 1H; Ar-H), (m, 2H, CH 2 ), 2.83 (s, 6H; (CH 3 ) 2 ), (m, 2H; CH 2 ), 1.68 ppm (s, 3H; CH 3 ); HRMS (TF, EI+): m/z: calcd for C 16 H S: ; found: Model compound 4-M H 2 H Ac 2 MeC Scheme 8 3-(Aminomethyl)perylene (28 mg, 0.1 mmol) was reacted with excess acetic anhydride (5 ml) in dry MeC (5 ml) at room temperature for 20 h. Then EtH (20 ml) was added to the mixture and the solvents were removed under reduced pressure. The procedure of addition and removal of EtH was repeated two more times to afford the solid product (32 mg, quantitative yield). 1 H MR (400 MHz, CDCl 3, 25 ºC) δ = 1 H MR (400 MHz, CDCl 3 ) δ = 8.25 (d, J = 7.6 Hz, 1H; Ar-H), 8.21 (t, J = 7.8 Hz, 2H; Ar-H), 8.14 (d, J = 7.8 Hz, 1H; Ar-H), 7.84 (d, J = 8.4 Hz, 1H; Ar-H), 7.71 (d, J = 8.0 Hz, 2H; Ar-H), 7.58 (t, J = 8.0 Hz, 1H; Ar-H), 7.50 (dt, J = 7.6, 1.6 Hz, 2H; Ar-H), 7.45 (d, J = 7.6 Hz, 1H; Ar-H), 5.69 (br. s, 1H; H), 4.83 (d, J = 5.2 Hz, 2H; CH 2 ), 2.05 ppm (s, 3H; CH 3 ); HRMS (TF, EI+): m/z: calcd for C 23 H 17 : ; found:

9 3) Comparison of Absorption and Fluorescence Spectra Dyads (3-SP, 4-SP) and Model Compounds (1-SP, 3-M, 4-M) Figure S1. Absorption spectra (three spectra on the left) of 3-M (solid line), 1-SP (dashed line), and 3-SP (dotted line) in acetonitrile. n the right the fluorescence spectra of optically matched solutions of 3-M (solid line) and 3-SP (dotted line) in acetonitrile are shown. The fluorescence of 3-SP is corrected for the absorption of SP at the excitation wavelength of 341 nm. Figure S2. Absorption spectra (three spectra on the left) of 4-M (solid line), 1-SP (dashed line), and 4-SP (dotted line) in acetonitrile. n the right the fluorescence spectra of optically matched solutions of 4-M (solid line) and 4-SP (dotted line) in acetonitrile are shown. 8

10 4) Sequential Logic with 3-MEH + and 4-MEH + Figure S3. Sequential logic with 3-MEH + as initial state and In 1 (phosphazene base) and In 2 (irradiation at λ > 530 nm) as inputs. The horizontal line shows the threshold value. Fluorescence signals above the threshold are considered as binary 1 and below as binary 0. Figure S4. Sequential logic with 4-MEH + as initial state and In 1 (phosphazene base) and In 2 (irradiation at λ > 530 nm) as inputs. The horizontal line shows the threshold value. Fluorescence signals above the threshold are considered as binary 1 and below as binary 0. 9

11 5) Cycling of the Dyads 3-SP and 4-SP Figure S5. Repeated switching cycles of 3-SP. The application order of UV light (302 nm), acid (TFA), base (P 2 -Et), and light of λ > 530 nm is shown for the first cycle and identical for the following cycles. Figure S6. Repeated switching cycles of 4-SP. The application order of UV light (302 nm), acid (TFA), base (P 2 -Et), and light of λ > 530 nm is shown for the first cycle and identical for the following cycles. 10

12 6) Cycling of 5 Figure S7. Cycling of the fluorescence of 5/5H + upon alternating addition of acid (1 equiv TFA) and base (1 equiv P 2 -Et). 11

13 7) MR spectra 12

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20 References [1] U. Asseline, E. Cheng, Tetrahedron Lett. 2001, 42, [2] M. V. Skorobogatyi, A. A. Pchelintseva, A. L. Petrunina, I. A. Stepanova, V. L. Andronova, G. A. Galegov, A. D. Malakhova, V. A. Korshuna, Tetrahedron 2006, 62, [3] M. Printz, C. Richert, Chem. Eur. J. 2009, 15, [4] H. Qiu, C. Wang, J. Xu, G. Lai, Y. Shen, Monatsh. Chem. 2008, 139, [5] A. A. García, S. Cherian, J. Park, D. Gust, F. Jahnke, R. Rosario, J. Phys. Chem. A 2000, 104, [6] A. García, M. Marquéz, T. Cai, R. Rosario, Z. Hu, D. Gust, M. Hayes, S. A. Vail, C.-D. Park, Langmuir 2007, 23, [7] L. Songa, E. A. Jares-Erijman, T. M. Jovin, J. Photochem. Photobiol. A: Chem. 2002,