Enabling light work in helical self-assembly for dynamic amplification of chirality with photoreversibility

Transcription

1 Supporting Information Enabling light work in helical self-assembly for dynamic amplification of chirality with photoreversibility Yunsong Cai,, Zhiqian Guo,, Jianmei Chen, Wenlong Li, Liubiao Zhong, Ya Gao, # Lin Jiang, Lifeng Chi,*,, He Tian, and Wei-Hong Zhu*, Key Laboratory for Advanced Materials and Institute of Fine Chemicals, Shanghai Key Laboratory of Functional Materials Chemistry, East China University of Science and Technology, Shanghai , P. R. China. whzhu@ecust.edu.cn Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou , P. R. China. Physikalisches Institut and Center for Nanotechnology (CeNTech), Universität Münster, Münster 48149, Germany. chi@uni-muenster.de # College of Fundamental Studies, Shanghai University of Engineering Science, Shanghai , P. R. China. Y.S.C. and Z.Q.G. contributed equally. S1

2 Contents 1. General... S3 2. UV and fluorescent spectra of 3, S-2 o and S-1 o... S4 3. Changes of UV and CD spectra upon light irradiation.... S5 4. Comparison of 1 H NMR spectra of S-2 c and S-2 o, S-1 c and S-1 o... S6 5. Supporting CD spectra... S7 6. SEM and AFM images of 3 and S-2 o... S8 7. Optical properties of 3, S-2 o and S-1 o... S9 8. Molecular modeling calculation... S11 9. Synthetic details... S Characterization... S19 S2

3 1. General All starting reagents were commercially available and of analytical purity, which were used without further treatment. 4-Bromo-1,8-naphthalic anhydride and (L-/D-) phenylalanine methyl ester hydrochloride were purchased from Adamas Reagent Co., Ltd., [1,1 -bis(diphenylphosphino)ferrocene]dichloropalladium and (Pd(PPh 3 ) 4 were purchased from Aladdin Reagent Co., Ltd, perfluorocyclopentene was purchased from J&K Scientific Ltd. Solvents used were analytical grade without further treatment, except those for recrystallization and optical tests, which were purified by distillation. TLC analysis was performed on silica-gel plates, and column chromatography was conducted using silica-gel column packages purchased from Qingdao Haiyang Chemical (China). NMR spectra were recorded on Bruker AM-400 spectrometers with tetramethylsilane (TMS) as an internal reference, CDCl 3 and DMSO-d 6 as solvents. High resolution mass (HRMS) spectra were recorded on a Waters LCT Premier XE spectrometer with methanol or acetonitrile as solvents. UV/Vis spectra were recorded on Varian Cary 500 (1 cm quartz cell) at 25 ºC. CD spectra were recorded on a JASCO J-810 spectropolarimeter at 25 ºC (1 cm quartz cell). The temperature-dependent CD spectra were recorded using JASCO J-810 spectropolarimeter connecting a thermostatic bath. All spectra were obtained with scanning rate of 100 nm/min, band width of 2 nm, and response time of 1 s. Continual three scans were averaged and blank-subtracted to give spectra. The photochromic reaction was induced in situ by continuous irradiation using an Hg/Xe lamp (Hamamatsu, LC8 Lightningcure, 200 W) equipped with a narrow band interference filter (Shenyang HB optical Technology) for λ irr = 313 nm and λ irr = 365 nm, a broad band interference filters (Shenyang HB optical Technology) for λ irr > 510 nm. The photochromic reaction quantum yields were evaluated by the standard procedures using BTF 6 as the reference for photocyclization. The rate of isomerization in the initial stage of the reaction (0-3%) were 3% uncertainties in the calculation. SEM. SEM images were acquired on ZEISS SUPRA The samples were prepared by spin-coating of CCl 4 solution ( M) after aging for 24 h with a rotation of 500 rpm on silicon wafer. AFM. AFM images were acquired under ambient conditions using Dimension Icon Nanoscope V (Veeco instrument, US) in Peak Force tapping mode. Silicon cantilevers with a nominal spring constant of 0.4 N/m and a nominal resonance frequency of 70 KHz (SCANASYST-AIR, Bruker, US) were used. The scan rate was 1 Hz. The samples were the same as SEM. Molecular modeling calculation. B3LYP/6-31G* was utilized to optimize the geometries and calculate the energy of parallel, anti-parallel and closed configurations of S-1 o. The solvation effect was considered using the conductor-polarizable continuum model (CPCM). A dielectric constant of was used for CCl 4. All calculations were carried out with Gaussian 09. Molecular modeling calculation of helixes was performed utilizing AMBER03 force field in gas phase. The repeating configuration of parallel form was first optimized using quantum chemistry method at B3LYP/6-31G* level in CCl 4 solvent, and then placed to allow DA-DA-DA hydrogen bonding interactions. Finally, it was further minimized using AMBER03 force field. S3

4 2. UV and fluorescent spectra of 3, S-2 o and S-1 o Figure S1. Photoswitching behaviors and fluorescent regulations of reference compounds: Changes in absorbance for (a) 3 and (b) S-2 o, and changes in fluorescence for (d) 3 and (e) S-2 o upon irradiation with 365 nm (c = M). Time-dependent (c) absorbance and (f) fluorescence spectra of S-1 o in CCl 4. Note: the fluorescence of S-1 o is photoreversibly modulated by isomerization rather than self-assembly (Figure 1d). As we can see in Figure S1c and S1d, the aging absorbance and fluorescence spectra of S-1 o showed no differences during self-assembling, which can be attributed to S-1 o self-assemble into helixes through intermolecular hydrogen bonding rather than π-π stacking. Here the UV-Vis and fluorescent spectra at different time of self-assembling (Figure S1c and S1f), they showed no changes upon aging, indicating no π-π stacking occurs. S4

5 3. Changes of UV and CD spectra upon light irradiation Figure S2. (a) Absorbance and (b) CD changes of S-1 o upon irradiation with UV light (365 nm) and visible light (> 510 nm), alternatively. S5

6 4. Comparison of 1 H NMR spectra of S-2 c and S-2 o, S-1 c and S-1 o Figure S3. 1 H NMR spectral contrasts of S-2 c and S-2 o, S-1 c and S-1 o. In contrast of 1 H NMR spectra of S-1 o and S-1 c, the resonance signal of methyl proton H a is shifted downfield by 0.19 ppm upon irradiation with UV light (from 2.27 ppm to 2.46 ppm), meanwhile a prominent upfield-shift is observed for the signal of thiophene proton H b (from 7.56 ppm to 6.85 ppm), and the five aromatic protons in naphthalimide group are shifted downfield due to the extended π-conjugation of closed form S-1 c. Upon irradiation with UV light, 1 H NMR spectra of S-2 o showed the same shifting trend. S6

7 5. Supporting CD spectra The stabilization behavior of this hydrogen-bonded self-assembly was investigated through temperature-dependent CD spectra. No distinct decline of CD signal was observed in temperature-dependent CD spectra (Figure S4c), suggesting that the hydrogen-bond-induced self-assembly is fairly stable. Furthermore, we chose four different solvents (sequence of polarity: acetone > THF > CH 2 Cl 2 > CCl 4 ) to detect the self-assembly behavior of S-1 o (Figure S4b). CD signals of S-1 o in the polar solvents (acetone, THF, CH 2 Cl 2 ) are rather weak, whereas it is dramatically high in low-polarity solvent CCl 4. The self-assembly, especially those based on hydrogen bonding, is usually critical about solvent polarity. This preference may be due to that in non-competitive solvent CCl 4, intermolecular hydrogen bonding interaction are stronger compared to the more competitive solvents. Majority rules effect, where a slight excess of enantiomers can induce the overall helical sense, is absent in this helical self-assembly system. The CD signal of mixture solution (0.1 equivalent excess of S-1 o : S-1 o = M and R-1 o = M, Figure S4e) is rather weaker than pure solution of S-1 o, and 1:1 mixture solution is almost CD silent (Figure S4f). The phenomena suggests that the self-assembly of the enantiomers occurs separately, or even if they co-assemble, they obey their own preferable helicities. Figure S4. (a) CD spectral changes of S-1 o in MeOH-CCl 4 (1%-16%, v/v). (b) CD spectra of S-1 o in different solvents (acetonitrile, DCM, THF, CCl 4, M). (c) Temperature-dependent CD spectral changes of S-1 o in CCl 4 ( M). (d) CD spectra of S-2 o in open form and in PSS upon irradiation with 365 nm in CCl 4 ( M). (e) CD spectra of S-1 o ( M), R-1 o ( M) and mixture of S-1 o ( M) and R-1 o ( M). (f) CD spectra of S-1 o ( M), R-1 o ( M) and mixture of S-1 o ( M) and R-1 o ( M). S7

8 6. SEM and AFM images of 3 and S-2 o Figure S5. (a) and (c): SEM and AFM images of 3; (b) and (d): SEM and AFM images of S-2 o. S8

9 7. Optical properties of 3, S-2 o and S-1 o Table S1. Conversion ratios (CR), ring-closed quantum yields (Φ o-c ), ring-open quantum yields (Φ c-o ) and fluorescence quantum yields (Φ f ) of 3, S-2 o and S-1 o in CCl 4 solution. CR (365 nm) Φ o-c (365 nm) Φ c-o (570 nm) Φ f (356 nm) S-2 o S-1 o The conversion yield of photocyclization reaction is defined as the maximal ratio of the ring-open isomer that can convert to the ring-closed isomer, upon the irradiation at certain wavelength (e.g. 365 nm). C c = αo cctotal ( 1 ) C = C C = C α o total c total o c α c : C c : C o : C c : conversion yield at the irradiation wavelength (e.g. 365 nm); concentration of ring-closed isomer; concentration of ring-open isomer; total concentration of photochromic molecules (equals to initial charge of ring-open isomer). At photo-stationary state (PSS), there exists the equilibrium of the photocyclization reaction between the ring-open and ring-closed isomers. ε φ C = ε φ C c c o c o o c o ( 1 ) ε φ C α = ε φ C α c c o total o c o o c total o c α o c 1 = ε φ 1+ ε φ c c o o o c ε c : molar extinction coefficient of ring-closed isomer at the irradiation wavelength (e.g. 365 nm); ε o : molar extinction coefficient of ring-open isomer at the irradiation wavelength (e.g. 365 nm); φ o c : photocyclization quantum yield of ring-open isomer at the irradiation wavelength (e.g. 365 nm); φ c o : photocycloreversion quantum yield of ring-closed isomer at the irradiation wavelength (e.g. 365 nm). From the equation above, the increase of φ c o induces the decrease of α c. It should be noted that φ c o does endow some wavelength-dependence, as the Referee suggested. The dependence is attributed to the existence of an energy barrier on the potential energy surface in the excited singlet state, but the variation of photocycloreversion quantum yield (φ c o ) at different S9

10 wavelength (e.g. UV & Vis) is commonly very limited (keeping the same order of magnitudes, See Irie et al. Chem. Rev. 2014, 114, 12174). Meanwhile, it is very hard to obtain accurate value of φ c o at the wavelength for photocyclization (e.g. UV region, 365 nm), compared to that at the wavelength for photocycloreversion (e.g. visible region, 570 nm), because the absorption spectra of the photo-generated open-ring isomers and those of the closed-ring isomers overlap in the UV region. Therefore, we can confidentially use φ c o (570 nm) to evaluate φ c o (365 nm). As can be seen from Table S1, φ c o of S-1 o (570 nm) is as large as 0.136, quite different from those of 3 (0.043) and S-2 o (0.023). Thus, it can be concluded that the photocyclization conversion yield of S-1 o is the lowest, under the condition that those 3 photochromic system endow similar molar extinction coefficient (ε) and close photocyclization quantum yield (φ o c ). S10

11 8. Molecular modeling calculation Figure S6. Open form S-1 o exits in two interchangeable conformations: parallel form P-S-1 o and anti-parallel form AP-S-1 o in rapid equilibrium. Upon irradiation with UV light, only AP-S-1 o can be converted to closed form S-1 c. Figure S7. Geometry-optimized configuration of P-S-1 o, AP-S-1 o and S-1 c. Table S2. Energy data of P-S-1 o and AP-S-1 o obtained by B3LYP/6-31G* method in CCl4 and gas phase. Compound Solvation Gas phase E (Kcal/mol) E a (Kcal/mol) E (Kcal/mol) E a (Kcal/mol) P-S-1 o / / AP-S-1 o a E is calculated for anti-parallel configurations, in which the energy of parallel configuration is taken as a reference value. Figure S8. Molecular model of AP-S-1 o that cannot form helix. S11

12 9. Synthetic details Scheme S1. Synthetic routes of building block S-1 o and R-1 o, and reference compound S-2 o, R-2 o and 3. (a) Dioxane, triethylamine, 90 ºC, L-phenylalanine methyl ester hydrochloride for S-1 o, D-Phenylalanine methyl ester hydrochloride for R-1 o ; acetic acid, n-butylamine, reflux for 3. (b) Potassium acetate, dry dioxane, bis(pinacolato)diboron, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium, 85 ºC. (c) aq. 2 M Na 2 CO 3, THF, (Pd(PPh 3 ) 4 ), 60 ºC. (d) Concentrated HCl, acetic acid, 90 ºC. For S-1 o or S-2 o, its chiral carbon has a S conformation, and R-1 o or R-2 o has a R conformation. Synthesis of 4-bromo-N-butyl-1, 8-naphthalimide 1 A mixture of 4-bromo-1,8-naphthalic anhydride (4.00 g, mmol) and n-butylamine (10.60 g, 0.14 mol) in acetic acid (40 ml) was refluxed under argon for 8 h. After cooling, the mixture was poured into water, resulting in yellow precipitate. It was filtered and recrystallized from acetic acid to afford pale yellow crystal in yield 91.7% (4.40 g). 1 H NMR (400 MHz, CDCl 3, ppm): δ 0.98 (t, J = 7.6 Hz, 3H, -CH 3 ), (m, 2H, -CH 2 CH 3 -), (m, 2H, -NCH 2 CH 2 -), 4.18 (t, J = 7.6 Hz, 2H, -NCH 2 -), 7.85 (t, J = 8.0 Hz, 1H, naphthalene-h ), 8.04 (d, J = 8.0 Hz, 1H, naphthalene-h), 8.42 (d, J = 8.0 Hz, 1H, naphthalene-h ), 8.57 (d, J = 8.0 Hz, 1H, naphthalene-h), 8.66 (d, J = 8.0 Hz, 1H, naphthalene-h). Synthesis of N-butyl-1, 8-naphthalimide borate S12

13 A stirred solution of 4-bromo-N-butyl-1,8-naphthalimide (500 mg, 1.51 mmol) and bis(pinacolato)diboron (1.10 g, 4.33 mmol) in dry dioxane (40 ml) was charged with potassium acetate (443 mg, 4.52 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (50 mg, 0.07 mmol), and the mixture was heated to 85 ºC under argon atmosphere. After 12 h stirring at this temperature, it was cooled and poured into water (100 ml), then extracted with dichloromethane (50 ml 3), the organic layer was separated and concentrated in vacuum. The residue was purified by column chromatography on silica gel (petroleum ether: dichloromethane = 1:1) to afford white powder in 87.6% yield (500 mg). 1 H NMR (400 MHz, CDCl 3, ppm): δ 0.98 (t, J = 7.6 Hz, 3H, -CH 3 ), (m, 2H, -CH 2 CH 3 ), 1.45 (s, 12H, -(CH 3 ) 4 ), (m, 2H, -NCH 2 CH 2 -), 4.19 (t, J = 7.6 Hz, 2H, -NCH 2 -), 7.78 (t, J = 7.6 Hz, 1H, naphthalene-h ), 8.29 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.56 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.60 (d, J = 7.6 Hz, 1H, naphthalene-h), 9.10 (d, J = 7.6 Hz, 1H, naphthalene-h). Synthesis of 3: A stirred solution of N-butyl-1,8-naphthalimide borate (433 mg, 1.14 mmol) and 1,2-bis(2-methxyl-5-bromo-thien-3-yl)perfluorocyclopentene 2 (150 mg, 0.28 mmol) in THF (20 ml) was charged with 2 M Na 2 SO 4 aqueous solution (5 ml), tetrakis(triphenylphosphine) palladium (Pd(PPh 3 ) 4, 50 mg, 0.04 mmol), and the mixture was heated to 70 ºC under argon atmosphere. After 36 h stirring at this temperature, it was cooled and poured into water (30 ml), then extracted with dichloromethane (30 ml 3), the organic layer was separated, washed with saturated brine solution and dried over MgSO 4, then concentrated in vacuum. The residue was purified by column chromatography on silica gel (petroleum ether: ethyl acetic =10:1) to afford pale yellow solid in 20.1% yield (50 mg). 1 H NMR (400 MHz, CDCl 3, ppm): δ 0.99 (t, J = 7.6 Hz, 3H, -CH 2 CH 3 ), (m, 2H, -CH 2 CH 3 ), (m, 2H, -NCH 2 CH 2 -), 2.24 (s, 3H, thiophene-ch 3 ), 4.20 (t, J = 7.6 Hz, 2H, -NCH 2 -), 7.33 (s, 1H, thiophene-h), 7.73 (t, J = 7.2 Hz, 1H, naphthalene-h ), 7.78 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.47 (d, J = 8.0 Hz, 1H, S13

14 naphthalene-h), 8.61 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.63 (d, J = 7.2 Hz, 1H, naphthalene-h). 13 C NMR (100 MHz, CDCl 3, ppm): δ , , , , , , , , , , , , , , , , 40.40, 30.21, 20.40, 14.62, HRMS-ESI (m/z): [M+H] + Calcd. for (C 47 H 36 F 6 N 2 O 4 S 2 ), , found: [M+Na] + Calcd. for (C 47 H 36 F 6 N 2 O 4 S 2 ), , found: Synthesis of 4-bromo-N-L-phenylalanine-1, 8-naphthalimide 3 A mixture of 4-bromo-1,8-naphthalic anhydride (1.50 g, 5.41 mmol) and L-phenylalanine methyl ester hydrochloride (3.50 g, mmol) and triethylamine (8 ml) in dioxane (150 ml) was refluxed under argon for 10 h. After cooling, the mixture was poured into water (100 ml), the organic layer was separated and washed with saturated brine solution, and dried over Na 2 SO 4. The solvent was removed in vacuum, and the residue was purified by column chromatography on silica gel (petroleum ether: dichloromethane = 1:2) to afford white solid in 50.6 % yield (1.20 g). 1 H NMR (400 MHz, CDCl 3, ppm): δ 3.48 (dd, J 1 = 10.0 Hz, J 2 = 14.4 Hz, 1H, -Ph-CH 2 -), 3.71 (dd, J 1 = 5.6 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.75 (s, 3H, -COOCH 3 -), 6.01 (dd, J 1 = 5.6 Hz, J 2 = 10.0 Hz, 1H, -NCH 2 -), (m, 5H, phenyl-h), 7.82 (t, J = 8.0 Hz, 1H, naphthalene-h), 8.01 (d, J = 8.0 Hz, 1H, naphthalene-h), 8.33 (d, J = 8.0 Hz, 1H, naphthalene-h), 8.55 (m, 2H, naphthalene-h). HRMS-ESI (m/z): [M+H] + Calcd. for (C 22 H 16 BrNO 4 ), , found: Synthesis of N-L-phenylalanine-1,8-naphthalimide borate A stirred solution of 4-bromo-N-L-phenylalanine-1,8-naphthalimide (1.30 g, 2.97 mmol) and bis(pinacolato)diboron (2.26 g, 8.90 mmol) in dry dioxane (70 ml) was charged with potassium acetic (883 mg, 8.99 mmol), [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (100 mg, S14

15 0.14 mmol), and the mixture was heated to 85 ºC under argon atmosphere. After 12 h stirring at this temperature, it was cooled and poured into water (150 ml), then extracted with dichloromethane (50 ml 3), the organic layer was separated and concentrated in vacuum. The residue was purified by column chromatography on silica gel (petroleum ether: dichloromethane = 1:2) to afford white powder in 90.3% yield (1.30 g). 1 H NMR (400 MHz, CDCl 3, ppm): δ 1.44 (s, 12H, -(CH 3 ) 4 ), 3.48 (dd, J 1 = 9.6 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.71 (dd, J 1 = 5.6 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.75 (s, 3H, -COOCH 3 -), 6.02 (dd, J 1 = 5.6 Hz, J 2 = 9.6 Hz, 1H, -NCH 2 -), (m, 5H, phenyl-h), 7.76 (t, J = 7.6 Hz, 1H, naphthalene-h), 8.27 (d, J = 7.2 Hz, 1H, naphthalene-h), 8.48 (d, J = 7.2 Hz, 1H, naphthalene-h), 8.52 (d, J = 7.2 Hz, 1H, naphthalene-h), 9.11 (d, J = 8.0 Hz, 1H, naphthalene-h). HRMS-ESI (m/z): [M+H] + Calcd. for (C 28 H 28 BNO 6 ), , found: [M+Na] + Calcd. for (C 28 H 28 BNO 6 ), , found: Synthesis of S-2 o A stirred solution of N-L-phenylalanine-1,8-naphthalimide borate (973 mg, 2.00 mmol) and 1,2-bis(2-methxyl-5-bromo-thien-3-yl)perfluorocyclopentene (170 mg, 0.32 mmol) in THF (30 ml) was charged with 2 M Na 2 SO 4 aqueous solution (10 ml), tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (50 mg, 0.04 mmol), and the mixture was heated to 70 ºC under argon atmosphere. After 36 h stirring at this temperature, it was cooled and poured into water (50 ml), then extracted with dichloromethane (30 ml 3), the organic layer was separated, washed with saturated brine solution and dried over MgSO 4, then concentrated in vacuum. The residue was purified by column chromatography on silica gel (petroleum ether: ethyl acetic =1:5) to afford pale yellow solid in 28.6% yield (100 mg). 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.21 (s, 3H, thiophene-ch 3 ), 3.51 (dd, J 1 = 10.0 Hz, J 2 = 14.4 Hz, 1H, -Ph-CH 2 -), 3.73 (dd, J 1 = 5.6 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.76 (s, 3H, -COOCH3-), 6.04 (dd, J 1 = 5.6 Hz, J 2 = 9.6 Hz, 1H, -NCH 2 -), (m, 5H, phenyl-h), 7.30 (s, 1H, thiophene-h ), 7.71 (t, J = 8.0 Hz, 1H, naphthalene-h), 7.75 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.46 (d, J = 8.0 Hz, 1H, naphthalene-h), 8.52 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.55 (d, J = 7.2 Hz, 1H, naphthalene-h). 13 C NMR (100 MHz, CDCl 3, ppm): δ , , , , , , , , , , , , , , , , , S15

16 126.58, , , , 54.43, 52.58, 34.94, HRMS-ESI (m/z): [M+Na] + Calcd. for (C 59 H 40 F 6 N 2 O 8 S 2 ), , found: [M+K] + Calcd. for (C 47 H 36 F 6 N 2 O 4 S 2 ), , found: Synthesis of S-1 o : 4 F F F F F F F F F F F F O N MeOOC Ph O S S O O N COOMe Ph HCl/AcOH 90 O N HOOC Ph O S S O O N COOH Ph A 200 ml round flask charged with S-2 o (120 mg, 0.11 mmol), acetic acid 60 ml and 12 M HCl (60 ml) was refluxed for 36 h. It was cooled and poured into 200 ml ice water, extracted with dichloromethane (100 ml 3). The combined organic layer was washed with 200 ml water and dried over Na 2 SO 4. The solvent was removed in vacuum, and the residue was purified by column chromatography on silica gel (dichloromethane: acetic acid=30: 1) and recrystallized from ethanol to form pale yellow solid in 85.5 % yield (100 mg). 1 H NMR (400 MHz, DMSO-d 6, ppm): δ 2.27 (s, 3H, thiophene-ch 3 ), 3.38 (dd, J 1 = 10.0 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.56 (dd, J 1 = 5.2 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 5.90 (dd, J 1 = 5.2 Hz, J 2 = 10.0 Hz, 1H, -NCH 2 -), (m, 5H, phenyl-h), 7.56 (s, 1H, thiophene-h), 7.77 (t, J = 8.0 Hz, 1H, naphthalene-h), 7.93 (d, J = 7.6 Hz, 1H, naphthalene-h), (m, 3H, naphthalene-h), (s, 1H, -COOH). 13 C NMR (100 MHz, DMSO-d 6, ppm): δ , , , , , , , , , , , , , , , , , , , , , , 54.00, 34.11, HRMS-ESI (m/z): [M+H] + Calcd. for (C 57 H 36 F 6 N 2 O 8 S 2 ), , found: Synthesis of 4-bromo-N-D-Phenylalanine-1,8-naphthalimide A mixture of 4-bromo-1,8-naphthalic anhydride (4.50 g, mmol) and D-phenylalanine methyl ester hydrochloride (11.00 g, mmol) and triethylamine (30 ml) in dioxane (350 ml) was refluxed under argon for 10 h. After cooling, the mixture was poured into water (300 ml), the organic layer was separated and washed with saturated brine solution, and dried over Na 2 SO 4. The solvent was removed in vacuum, and the residue was purified by column chromatography on S16

17 silica gel (petroleum ether: dichloromethane =1:2) to afford white solid in 70.3 % yield (5.0 g). 1 H NMR (400 MHz, CDCl 3, ppm): δ 3.48 (dd, J 1 = 10.0 Hz, J 2 = 14.0 Hz,1H, -Ph-CH 2 -), 3.71 (dd, J 1 = 6.0 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.75 (s, 3H, -COOCH 3 -), 6.01 (dd, J 1 = 6.0 Hz, J 2 = 10.0 Hz, 1H, -NCH 2 -), (m, 5H, phenyl-h), 7.82 (t, J = 8.0 Hz, 1H, naphthalene-h), 8.01 (d, J = 8.0 Hz, 1H, naphthalene-h), 8.32 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.55 (m, 2H, naphthalene-h). Synthesis of N-D-phenylalanine-1,8-naphthalimide borate: A stirred solution of 4-bromo-N-D-Phenylalanine-1,8-naphthalimide (3.00 g, 6.85 mmol) and bis(pinacolato)diboron (5.10 g, mmol) in dry dioxane (150 ml) was charged with potassium acetic (2.00 g, mmol), [1,1'-bis(diphenylphosphino) ferrocene] dichloropalladium (200 mg, 0.28 mmol), and the mixture was heated to 85 ºC under argon atmosphere. After 12 h stirring at this temperature, it was cooled and poured into water (300 ml), then extracted with dichloromethane (100 ml 3), the organic layer was separated and concentrated in vacuum. The residue was purified by column chromatography on silica gel (petroleum ether: dichloromethane =1:2) to afford white powder in 60.2 % yield (2.00 g). 1 H NMR (400 MHz, CDCl 3, ppm): δ 1.44 (s, 12H, -(CH 3 ) 4 ), 3.48 (dd, J 1 = 9.6 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH2-), 3.71 (dd, J 1 = 5.6 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.75 (s, 3H, -COOCH 3 -), 6.02 (dd, J 1 = 5.6 Hz, J 2 = 9.6 Hz, 1H, -NCH 2 -), (m, 5H, phenyl-h), 7.76 (t, J = 8.0 Hz, 1H, naphthalene-h), 8.27 (d, J = 6.8 Hz, 1H, naphthalene-h), 8.48 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.52 (d, J = 7.6 Hz, 1H, naphthalene-h), 9.11 (d, J = 8.0 Hz, 1H, naphthalene-h). Synthesis of R-2 o : S17

18 A stirred solution of N-D-phenylalanine-1,8-naphthalimide borate (973 mg, 2.0 mmol) and 1,2-bis(2-methxyl-5-bromo-thien-3-yl)perfluorocyclopentene (170 mg, 0.32 mmol) in THF (30 ml) was charged with 2 M Na 2 SO 4 aqueous solution (10 ml), tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (50 mg, 0.04 mmol), and the mixture was heated to 70 ºC under argon atmosphere. After 36 h stirring at this temperature, it was cooled and poured into water (50 ml), then extracted with dichloromethane (30 ml 3), the organic layer was separated, washed with saturated brine solution and dried over MgSO 4, then concentrated in vacuum. The residue was purified by column chromatography on silica gel (petroleum ether: ethyl acetic =1: 5) to afford pale yellow solid in 28.6% yield (100 mg). 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.21 (s, 3H, thiophene-ch 3 ), 3.51 (dd, J 1 = 10.0 Hz, J 2 = 14.4 Hz, 1H, -Ph-CH 2 -), 3.73 (dd, J 1 =5.6 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.76 (s, 3H, -COOCH 3 -), 6.04 (dd, J 1 = 5.6 Hz, J 2 = 9.6 Hz, 1H, -NCH 2 -), (m, 5H, phenyl-h), 7.31 (s, 1H, thiophene-h ), 7.71 (t, J = 8.0 Hz, 1H, naphthalene-h), 7.75 (d, J = 7.6 Hz, 1H, naphthalene-h), 8.47 (d, J = 8.0 Hz, 1H, naphthalene-h), 8.52 (d, 1H, J = 7.6 Hz, naphthalene-h) (d, J = 7.2 Hz, 1H, naphthalene-h). 13 C NMR (100 MHz, CDCl 3, ppm): δ , , , , , , , , , , , , , , , , , , , , , 54.40, 52.61, 34.89, HRMS-ESI (m/z): [M+Na] + Calcd. for (C 59 H 40 F 6 N 2 O 8 S 2 ), , found: [M+K] + Calcd. for (C 47 H 36 F 6 N 2 O 4 S 2 ), , found: Synthesis of R-1 o : A 200 ml round flask charged with R-2 o (40 mg, mmol), acetic acid 30 ml and 12 M HCl (30 ml) was refluxed for 36 h. It was cooled and poured into 100 ml ice water, extracted with dichloromethane (50 ml 3). The combined organic layer was washed with 100 ml water and dried over Na 2 SO 4. The solvent was removed in vacuum, and the residue was purified by column chromatography on silica gel (dichloromethane: acetic acid = 30: 1) and recrystallized from ethanol to form pale yellow solid in 76.9% yield (30 mg). 1 H NMR (400 MHz, DMSO-d 6, ppm): δ 2.27 (s, 3H, thiophene-ch 3 ), 3.39 (dd overlap with H 2 O, J 1 = 10.0 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 3.56 (dd, J 1 = 5.6 Hz, J 2 = 14.0 Hz, 1H, -Ph-CH 2 -), 5.88 (dd, J 1 = 5.6 Hz, J 2 = 9.2 Hz, S18

19 1H, -NCH 2 -), (m, 5H, phenyl-h), 7.55 (s, 1H, thiophene-h ), 7.77 (t, J = 8.0 Hz, 1H, naphthalene-h), 7.92 (d, J = 7.2 Hz, 1H, naphthalene-h), (m, 3H, naphthalene-h), (s, 1H, -COOH). 13 C NMR (100 MHz, DMSO-d 6, ppm): δ , , , , , , , , , , , , , , , , , , , , , 54.24, 34.19, HRMS-ESI (m/z): [M+Na] + Calcd. for (C 57 H 36 F 6 N 2 O 8 S 2 ), , found: [M+H] + Calcd. for (C 57 H 36 F 6 N 2 O 8 S 2 ), , found: Characterization Figure S9. 1 H NMR spectrum of 4-bromo-N-butyl-1, 8-naphthalimide. S19

20 Figure S10. 1 H NMR spectrum of N-butyl-1,8-naphthalimide borate. Figure S11. 1 H NMR spectrum of 3. S20

21 Figure S C NMR spectrum of 3. Figure S13. HRMS spectrum of 3. S21

22 Figure S14. 1 H NMR spectrum of 4-bromo-N-L-phenylalanine-1,8-naphthalimide. Figure S15. HRMS spectrum of 4-bromo-N-L-phenylalanine-1,8-naphthalimide. S22

23 Figure S16. 1 H NMR spectrum of N-L-phenylalanine-1,8-naphthalimide borate. Figure S17. HRMS spectrum of N-L-phenylalanine-1,8-naphthalimide borate. S23

24 Figure S18. 1 H NMR spectrum of S-2 o. Figure S19. HRMS spectrum of S-2 o. S24

25 Figure S C NMR spectrum of S-2 o. Figure S21. 1 H NMR spectrum of S-1 o. S25

26 Figure S C NMR spectrum of S-1 o. Figure S23. HRMS spectrum of S-1 o. S26

27 Figure S24. 1 H NMR spectrum of 4-bromo-N-D-phenylalanine-1,8-naphthalimide. Figure S25. 1 H NMR spectrum of N-D-phenylalanine-1,8-naphthalimide borate. S27

28 Figure S26. 1 H NMR spectrum of R-2 o. Figure S C NMR spectrum of R-2 o. S28

29 Figure S28. HRMS spectrum of R-2 o. Figure S29. 1 H NMR spectrum of R-1 o. S29

30 Figure S C NMR spectrum of R-1 o. Figure S31. HRMS spectrum of R-1 o. [1] Song, L. W.; Yang, Y.; Zhang, Q.; Tian, H.; Zhu, W.-H. J. Phys. Chem. B 2011, 115, [2] Chung, J. W.; Yoon, S. J.; Lim, S. J.; An, B. K.; Park, S. Y. Angew. Chem. Int. Ed. 2009, 48, [3] Huang, X.; Fang, Y.; Li, X.; Xie, Y.; Zhu, W.-H. Dye Pigm. 2011, 90, [4] Arnusch, C. J.; Pieters, R. J. Eur. J. Org. Chem. 2003, 3, S30