Multicolour Self-Assembled Particles from Fluorene Based Bolaamphiphiles

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1 Supporting Information for Multicolour Self-Assembled Particles from Fluorene Based Bolaamphiphiles Robert Abbel, Rob van der Weegen, E. W. Meijer and Albertus P. H. J. Schenning Materials and Instruments All chemicals were purchased from Acros, Belgium unless stated otherwise. Concentrated hydrochloric acid was delivered by VWR International, Belgium. Na 2 SO was obtained from Merck, Germany, silicagel ( 6 µm, 6 Å) from Screening Devices, the Netherlands and Fluka, Germany. Gelatine was purchased from Dr. Oetker. Non-deuterated solvents were purchased from Biosolve, the Netherlands. All solvents and chemicals were used as received. Deuterated solvents were bought from Cambridge Isotope Laboratories, United States. NMR spectra were recorded using a Varian Mercury NMR Spectrometer at MHz for H and MHz for C or on a Varian Gemini NMR Spectrometer at MHz for H and 75 MHz for C. IR, UV-vis, CD and PL spectra were measured on a Perkin Elmer 6 FT-IR, a Perkin Elmer Lambda 9 UV/VIS/NIR spectrometer, a JASCO J- 85 CD Spectrometer and an Edinburgh Instruments FS92 spectrophotometer, respectively. Elemental analysis was performed using a Perkin Elmer 2 Series II CHNS/O Analyzer. MALDI-TOF-MS spectra were measured on a Perseptive DE Voyager Mass Spectrometer with a-cyano--hydroxycinnamic acid as a matrix. Analytical Size Exclusion chromatography was done on an apparatus consisting of a Shimadzu SIL-AD VP Auto Injector, a Shimadzu LC-AD VP Liquid Chromatograph, a PLgel µm Å column set, and a SPD-MA VP Diode Array Detector, using HPLC grade THF as the eluent. For recycling GPC, an apparatus consisting of a Shimadzu LC-AD VP Liquid Chromatograph, a Shimadzu SPD-AV VP UV-vis detector, and two JAIGEL columns (2.5 H and 2 H) from Japan Analytical Industry was used with HPLC grade THF as the eluent. Samples for fluorescence microscopy were prepared by injection of µl of a THF stock solution (total chromophore concentration mm) into ml of a freshly prepared gelatine ( g/l) solution, transferred to a glass slide and covered with a cover slip. Gelation took place overnight at a temperature of 7 o C. The images were taken on a Zeiss LSM 5 META

2 fluorescence microscope with a Plan-Apochromat 6x objective using immersion oil. The samples were excited with laser light of 58 nm or 5 nm. Synthesis The synthesis of the aromatic diamines by Suzuki coupling is described elsewhere.,2 General procedure for the synthesis of 5:,,5-tris(methyltetraethyleneoxy)benzoic acid chloride was prepared according to a literature procedure from its corresponding acid and oxalyl chloride. Aromatic diamine and triethyl amine were dissolved in dry chloroform and an excess of acid chloride was added as a solution in dry chloroform. After stirring at room temperature for several hours, water was added to the reaction mixture and the aqueous layer was extracted several times with chloroform. The combined organic layers were washed with water and dried over Na 2 SO. After evaporation, the crude products were purified by column chromatography and preparative recycling GPC. Bis(9,9,9,9 -tetra((s)-,7-dimethyloctyl)fluorenyl)naphthalene-2,7 -bis(,,5- tris(tetraethylene glycol)benzoic)amide (),,5-tris(methyltetraethyleneoxy)benzoic acid (6 mg,.85 mmol,.6 eq.), (9,9,9,9 -tetra((s)-,7-dimethyloctyl)fluorenyl)naphthalene-2,7 -diamine 2 (22 mg,.2 mmol,. eq.). Beige waxy solid, yield 5 mg (.75 mmol, 8 %). H-NMR (CDCl ): δ 8.52 (s, 2 H), 8. (dd,.5 Hz, 6.5 Hz, 2 H), (m, H), 7.75 (d, 8. Hz, 2 H), 7.65 (dd, 8. Hz,.5 Hz, 2 H), 7.57 (s, 2 H), (m, H), 7.2 (dd, 6.5 Hz,.5 Hz, 2 H), 7. (s, H),..2 (m, 2 H),.88 (tr, 5. Hz, 8 H),.82 (tr, 5. Hz, H), (m, 6 H),.59.5 (m, 2 H),.8 (s, 6 H),. (s, 2 H), (m, 8 H),.7.6 (m, H), (m, 2 H),.96.5 (m, 8 H). C- NMR (CDCl ) δ 65.22, 52.58, 52.5, 5.57,.92,.,.5, 9.8, 7.8, 7.2, 2.2,., 28.76, 26.57, 26.6, 25.7, 2.9, 2.5, 9.2, 9.,.9, 7., 72.2, 7.95, 7.9, (mult. C), 69.8, 69.27, 59., 58.98, 55.9, 9.22, 7., 6.78,.,., 27.89, 2.76, (mult. C), 22.58, 22.55, 9.75, 9.2. MALDI TOF MS: calc. [M + ] 29.58, found 26.7, 2. (fragmentation), 29.55, 2. (M-Na + ), 25. (M-K + ). IR (cm - ): ν = 522 (w), (w), 292 (s), 2868 (s), 6 (m), 58 (m), 58 (s), 5 (s), 72 (s), 55 (s), 27 (m), 9 (s), 29 (s), 2 (m), 2 (m), (vs), (m), 96 (m), 888 (w), 852 (m), 82 (s), 76 (m), 7 (w). UV-vis (CHCl ) λ max (logε) nm (5.). PL max (CHCl ) 2 nm, φ 7 % (quinine bisulfate). EA calc. for C H 222 N 2 O 2 : 69. % C, 9. % H,. % N; found 69. % C, 8.9 % H,.8 % N.

3 Bis(9,9,9,9 -tetra((s)-,7-dimethyloctyl)fluorenyl)quinoxaline-2,7 -bis(,,5- tris(tetraethylene glycol)benzoic)amide (2),,5-tris(methyltetraethyleneoxy)benzoic acid (77 mg,. mmol,.2 eq.), (9,9,9,9 -tetra((s)-,7-dimethyloctyl)fluorenyl)quinoxaline-2,7 -diamine 2 (265 mg,.25 mmol,. eq.). Yellow-green waxy solid, yield 75 mg (.9 mmol, 76 %). H-NMR (CDCl ): δ 8.88 (s, 2 H), 8.5 (br s, 2 H), 7.95 (s, 2 H), 7.8 (d,.5 Hz, 2 H), 7.8 (d, 8. Hz, 2 H), (m, H), 7.67 (s, 2 H), 7.6 (dd, 8.5 Hz, 2. Hz, 2 H), 7. (s, H),..2 (m, 2 H),.88 (tr, 5. Hz, 8 H),.82 (tr, 5. Hz, H),.76.6 (m, 6 H),.58.5 (m, 2 H),.8 (s, 6 H),. (s, 2 H), (m, 8 H),.5. (m, H), (m, 2 H),.96.6 (8 H). C-NMR (CDCl ) δ 65.22, 52.58, 52., 5.2,.6,.9,.6,.8,.9, 7.77, 7.9, 6.7,.6,.2, 29.55, 25.5, 2., 9., 8.89,.97, 7.88, 72., 7.95, 7.9, 7.68, (mult, C), 69.8, 69.27, 59., 58.98, 55.6, 9.2, 9.2, 7.6, 6.96, 6.6,.,.5,.9,.87, 27.9 (mult. C), 2.8, 2.66, 22.68, 22.57, 22.5, 9.7, 9.. MALDI TOF MS: calc. [M + ], 29.57, found 25.7 (fragmentation), 29.55, (M-Na + ), 252,7 (M-K + ). IR (cm - ): ν = 522 (w), (w), 295 (m), 292 (s), 2868 (s), 6 (m), 58 (m), 58 (s), 5 (s), 65 (s), 27 (m), 7 (s), 29 (s), 25 (m), 29 (m), (vs), (w), 95 (m), 889 (m), 85 (s), 88 (s), 756 (w), 76 (w). UV-vis (CHCl ) λ max (logε) nm (.86), 86 nm (.5). PL max (CHCl ) 59 nm, φ 5 % (quinine bisulfate). EA calc. for C 2 H 22 N O 2 : 68. % C, 8.9 % H, 2.2 % N; found 68. % C, 8.8 % H, 2. % N. Bis(9,9,9,9 -tetra((s)-,7-dimethyloctyl)fluorenyl)benzothiadiazole-2,7 -bis(,,5- tris(tetraethylene glycol)benzoic)amide (),,5-tris(methyltetraethyleneoxy)benzoic acid (72 mg,.97 mmol,.2 eq.), (9,9,9,9 -tetra((s)-,7-dimethyloctyl)fluorenyl)benzothiadiazole-2,7 -diamine 2 (25 mg,.2 mmol,. eq.). Yellow-orange waxy solid, yield 525 mg (.2 mmol, 92 %). H- NMR (CDCl ): δ 8.6 (br s, 2 H), 8. (dd,.5 Hz, 8. Hz, 2 H), 7.9 (d,.5 Hz, 2 H), (m, H), 7.75 (d, 8.5 Hz, 2 H), 7.6 (dd, 8. Hz,.5 Hz, 2 H), 7. (s, H),.2.22 (m, 2 H),.9.8 (m, 2 H),.76.6 (m, 6 H),.58.5 (m, 2 H),.8 (s, 6 H),. (s, 2 H), (m, 8 H),.5. (m, H), (m, 2 H), (m, 8 H). C-NMR (CDCl ) δ 65.2, 5.9, 52.6, 52.68, 5.97,.96,., 7.9, 7., 5.77,.59,., 28.2, 27.77, 2.8, 2.26, 9., 9.,.9, 7.9, 72.9, 7.96, 7.92, (mult. C), 69.82, 69., 59., 58.98, 55.26, 9.25, 7.8, 7.6, 6.87, 6.62,.7, 2.98,.8, 27.9, 27.9, 2.8, 2.6, 22.67, 22.66, 22.57, 22.5, 9.7, 9.2. MALDI TOF MS: calc. [M + ] 299.5, found , (M-Na + ), (M-K + ). IR (cm - ): ν = 522 (w), (w), 295 (m), 292 (s), 2868 (s), 6 (m), 58 (m), 58 (s), 5 (s),

4 65 (s), 27 (m), 7 (s), 29 (s), 25 (w), 29 (w), (vs), (w), 95 (m), 889 (m), 85 (m), 88 (s), 756 (w), 76 (w). UV-vis (CHCl ) λ max (logε) 9 nm (.9), 28 nm (.5). PL max (CHCl ) 569 nm, φ 8 % (N,N -pentylhexyl perylene bisimide). EA calc. for C H 28 N O 2 S: 67.2 % C, 8.8 % H, 2.2 % N; found 66.8 % C, 8.7 % H, 2. % N. Bis(9,9,9,9 -tetra((s)-,7-dimethyloctyl)fluorenyl)thienopyrazine-2,7 -bis(,,5- tris(tetraethylene glycol)benzoic)amide (),,5-tris(methyltetraethyleneoxy)benzoic acid (5 mg,.69 mmol,. eq.), (9,9,9,9 -tetra((s)-,7-dimethyloctyl)fluorenyl)thienopyrazine-2,7 -diamine 2 (7 mg,.6 mmol,. eq.). Viscous dark purple oil, yield 256 mg (. mmol, 6 %). H-NMR (CDCl ): δ 8.55 (s, 2 H), 8. (br s, 2 H), 8.22 (dd, 8. Hz,. Hz, 2 H), 8. (s, 2 H), 7.82 (s, 2 H), 7.76 (d, 8. Hz, 2 H), 7.72 (d,.5 Hz, 2 H), 7.6 (dd, 8.5 Hz,. Hz, 2 H), 7.2 (s, H),..2 (m, 2 H),.88 (tr, 5. Hz, 8 H),.82 (tr, 5. Hz, H),.77.6 (m, 6 H),.58.5 (m, 2 H),.8 (s, 6 H),. (s, 2 H), (m, 8 H),..2 (m, H),.2.96 (m, 2 H),.96.8 (m, H),.8.67 (m, H),.67.5 (m, H). C-NMR (CDCl ) δ.65.7, 52.6, 52.25, 5.,.97,.96,.9,.27, 7.92, 7., 2.78,.6,., 27.7, 22.52, 2.22, 9.7, 9.9,.8, 7.9, 7.96, 7.9, (mult. C), 69.8, 69.2, 59., 58.99, 55., 9.22, 7.8, 7.6, 6.8, 6.59,., 2.9,.7, 27.9, 2.76, 2.5, 22.66, 22.56, 22.5, 9.62, 9.2. MALDI TOF MS: calc. [M + ] 299.5, found 22., 2.5, 257. (fragmentation), 299.6, (M-Na + ), (M-K + ). IR (cm - ): ν = 522 (w), (w), 292 (s), 2868 (s), 6 (m), 58 (m), 58 (s), 5 (m), 66 (s), 28 (m), 8 (s), 29 (s), 5 (w), 25 (w), 29 (w), 2 (vs), 29 (w), 97 (m), 85 (m), 87 (s), 755 (m), 668 (w). UV-vis (CHCl ) λ max (logε) 66 nm (.88), 52 nm (.). PL max (CHCl ) 679 nm, φ % (Rhodamine ). EA calc. for C H 28 N O 2 S: 67.2 % C, 8.8 % H, 2.2 % N; found 66. % C, 8.7 % H, 2. % N. 9,9,9,9,9,9 -hexa((s)-,7-dimethyloctyl)fluorene-2,7 -bis(,,5-tris(tetraethylene glycol)benzoic)amide (5),,5-tris(methyltetraethyleneoxy)benzoic acid (75 mg,.5 mmol, 6.92 eq.), 9,9,9 9,9,9 -hexa((s)-,7-dimethyloctyl)terfluorene-2,7 -diamine ( mg,.7 mmol,. eq.). Yield 92 mg of a yellow solid (5 %). H-NMR (THF-d 8, 5 o C): δ 9.9 (s, 2 H), 7.82 (s, 2 H), 7.7 (d, 7.5 Hz, 2 H), (m, H), 7.2 (s, H),..9 (m, 2 H),.7 (tr, 5. Hz, 8 H),.67 (tr, 5. Hz, H),.58. (m, 6 H),.6.2 (m, 2 H),.8 (s, 6 H),.7 (s, 2 H), (m, 2 H),.9.27 (m, 6 H),.6.9 (m, 6 H),.9.78 (m, 6 H),.76.8 (m, 66 H). C-NMR (THF-d 8, 5 o C) δ 6.2, 52.6, 5.28, 5.9, 5.9,.75,.5,.6,.6, 9.62,

5 9.2, 6.22,.7, 25.8 (mult. C), 2.9, 2.82, 9.69, 9.9, 9.9, 8.57,., 7.5, 72.28, 7.88, (mult. C), 69.59, 57.89, 5.85, 9., 9., 7.7, 7.6, 7.8, 6.7, 6.59, 6.56, 2.99, 2.92, 2.88,.6, 27.78, 2.79, 2.65, 2.6, 2.58, 2.52, 2.6, 2.26, 2.6, 2.86, 22., 2.9, 2.92, 8.99, 8.9, 8.8. MALDI TOF MS: calc. [M + ] 289.9, found 28., (M-Na + ). IR (cm - ): ν = 5 (w), 22 (w), 295 (m), 2925 (s), 2868 (s), 67 (w), 67 (w), 58 (m), 57 (m), 9 (m), 59 (s), 29 (s), (s), 2 (m), 26 (m), 29 (m), (vs), 96 (m), 852 (m), 86 (s), 75 (s), 665 (w). UV-vis (CHCl ) λ max (logε) 65 nm (5.7). PL max (CHCl ) 5 nm, 25 nm, φ 5 % (quinine bisulfate). EA calc. for C 67 H 26 N 2 O 2 : 7. % C, 9.5 % H,. % N; found 7. % C, 9. % H,.6 % N. Supplementary measurements ε (M - cm - ).x x PL intensity Fig. S UV-vis absorption and fluorescence spectra of in chloroform. Fluorescence samples have been diluted to an OD below. prior to the measurements. The fluorescence spectra are weighted according to the respective quantum yields. Excitation at the absorption maximum.

6 ε (M - cm - ) 6.x 2.x 2.x PL intensity Fig. S2 UV-vis absorption and fluorescence spectra of in water. Injected as mm THF stock solution. Fluorescence samples have been diluted to an OD below. prior to the measurements. The fluorescence spectra are weighted according to the respective quantum yields. Excitation at the absorption maximum CD (mdeg) - CD (mdeg) CD (mdeg) - Cd (mdeg) Fig. S CD spectra of in chloroform (grey) and in water (black). Concentration 5 µm. Injected as mm THF stock solution.

7 Tab. S UV-vis and PL characteristics of two aqueous solutions of, prepared by injection of concentrated ( mm) and diluted (.2 mm) THF stock solutions into water. UV-vis absorption photoluminescence λ max (nm) ε (M - cm - ) λ max (nm) φ PL * (%) stock sol..2 mm stock sol. mm * Reference compound: quinine bisulfate in N H 2 SO x 6 x 6 2x 6 x 6 mixture of pure particles 5 6 Fig. S PL spectra of mixtures of pure nanoparticles of and in aqueous solution. Arrows indicate spectral changes with decreasing donor to acceptor ratio from : to :. Excitation wavelength λ exc = 2 nm. Total chromophore concentration.5-6 M.

8 a norm. PL int b PL(donor)/PL(acceptor) c tot (M) Fig. S5 (a) Concentration dependent fluorescence spectra of mixed aggregates of and with a composition of 95 : 5 in water, normalised to the acceptor concentration. The arrow indicates spectral changes upon dilution. The sharp peak at 8 nm is due to Raman scattering of the solvent. Excitation wavelength λ exc = nm. (b) Concentration dependence of the ratio of donor to acceptor emission in these mixed aggregates. a 6 donor emission acceptor emission 2 2 t (h) b x 6 x 6 2x 6 x 6 x 5 2x 5 x 5 acceptor emission donor emission T ( o C) Fig. S6 Stability of aggregates of and in aqueous solution. (a) Time dependence of a 75 : 25 mixture of separate aggregates at 25 o C, followed at 2 nm (donor emission) and 56 nm (acceptor emission). (b) Temperature dependence of the PL emission maxima of mixed aggregates of and with a composition of 95 : 5. Total chromophore concentration.5-6 M. Excitation wavelength λ exc = nm.

9 5 6 7 Fig. S8 Simultaneous emission of in a mixture of pure nanoparticles. Excitation wavelength λ exc = 6 nm. Molar ratio of : 2 : : = : 7.9 : 6.7 : 5.. Total chromophore concentration.5-6 M. References Abbel, R.; Grenier, C.; Pouderoijen, M. J.; Stouwdam, J. W.; Leclère, P. E. L. G.; Sijbesma, R. P.; Meijer, E. W.; Schenning, A. P. H. J. J. Am. Chem. Soc., 29,, 8. 2 Abbel, R.; van der Weegen, R.; Pisula, W.; Surin, M.; Lazzaroni, R.; Leclère, P. E. L. G.; Meijer, E. W.; Schenning, A. P. H. J., manuscript in preparation. Brunsveld, L.; Zhang, H.; Glasbeek, M.; Vekemans, J. A. J. M.; Meijer, E. W. J. Am. Chem. Soc. 2, 22, 675.