Proton-conductive materials formed by coumarin photocrosslinked ionic liquid crystal dendrimers

Transcription

1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is The Royal Society of Chemistry 207 Supporting Information Proton-conductive materials formed by coumarin photocrosslinked ionic liquid crystal dendrimers Alberto Concellón, a Ting Liang, b Albertus P.. J. Schenning, b,c José Luis Serrano, d Pilar Romero,*,a and Mercedes Marcos,*,a a Instituto de Ciencia de Materiales de Aragón, Departamento de Química rgánica, Universidad de Zaragoza-CSIC, 50009, Zaragoza, Spain. b Department of Functional rganic Materials and Devices, Chemical Engineering and Chemistry, Eindhoven University of Technology, De Rondom 70, 562 AP, Eindhoven, The Netherlands c Institute for Complex Molecular Systems (ICMS), Eindhoven University of Technology, P.. Box 53, 5600 MB, Eindhoven, The Netherlands. d Instituto de Nanociencia de Aragón, Departamento de Química rgánica, Universidad de Zaragoza, 50009, Zaragoza, Spain. S

2 Table of Contents. Materials and methods S3 2. Experimental Procedures 2.. Synthesis of the coumarin functional units S Synthesis of the bifunctional dendron Ac-ChCou S Synthesis of the ionic hybrid dendrimers S8 3. Supplementary Material 3.. FTIR and NMR characterization S 3.2. PM textures S3 3.3 Nyquist plots S ptical and fluorescent properties S4 S2

3 . MATERIALS AND METDS Poly(amidoamine) dendrimers (PAMAM) were purchased from Dendritech, Inc. Cholesteryl hemisuccinate and the rest of reagents were purchased from Sigma-Aldrich and used as received without further purification. Anhydrous TF and DCM were purchased from Scharlab and dried using a solvent purification system. Benzyl 2,2 -bis(hydroxymethyl)propanoate was prepared following a previously reported procedure. The chemical structures of all the compunds were confirmed FTIR spectroscopy, one dimensional and 3 C NMR spectroscopy and two dimensional - CSY, - 3 C SQC and - 3 C MBC experiments, MALDI-TF mass spectroscopy and elemental analysis. FTIR spectra were obtained on a Bruker Vertex 70 FT-IR spectrophotometer using KBr pellets. Solution NMR experiments were carried out on Bruker Avance spectrometers operating at 400 Mz for and 00 Mz for 3 C, using standard pulse sequences. Chemical shifts are given in ppm relative to TMS and this was used as internal reference. Elemental analysis was performed using a Perkin-Elmer 2400 microanalyzer. MALDI-TF MS was performed on an Autoflex mass spectrometer (Bruker Daltonics) using dithranol as matrix. Solid-state NMR experiments were performed in a Bruker Avance III WB400 spectrometer using a double resonance ( -X) probe with a rotor of 4 mm or 2.5 mm diameter, and the spinning frequency was set to 2 kz or 20 kz, respectively. For the former, the and 3 C π/2 pulse length were 3 and 4.3 μs, respectively, the CP contact time was 3 ms and the recycle delay was 7 s. For the latter, the and 3 C pulse length were 8 and 5.7 μs, respectively, the CP contact time was.5 ms and the recycle delay was 5 s. The pulse sequence employed consisted of ramped cross-polarization with spinal-64 decoupling. Data were acquired at 298 K and chemical shifts are referenced to TMS using adamantane ( 3 C: δ = ppm) as secondary standard. Mesogenic behavior was investigated by polarized-light optical microscopy (PM) using an lympus B-2 polarizing microscope fitted with a Linkam TMS600 hot stage. Thermogravimetric analysis (TGA) was performed using a Q5000IR from TA instruments at heating rate of 0 ᵒC min - under a nitrogen atmosphere. Thermal transitions were determined by differential scanning calorimetry (DSC) using a DSC Q2000 from TA instruments with powdered samples (2 5 mg) sealed in aluminum pans. Glass transition temperatures (T g ) were determined at the half height of the baseline jump, and first order transition temperatures were read at the maximum of the corresponding peak.. Ihre, A. ult, J. M. J. Fréchet and I. Gitsov, Macromolecules 998, 3, S3

4 X-ray diffraction (XRD) was performed with a Ganesha lab instrument equipped with a GeniX-Cu ultralow divergence source producing X-ray photons with a wavelength of.54 Å and a flux of 0 8 ph s. Scattering patterns were collected using a Pilatus 300 K silicon pixel detector. The beam center and the q range were calibrated using the diffraction peaks of silver behenate. Powdered samples were placed in Lindemann glass capillaries ( mm diameter). UV-Vis absorption spectra were recorded on an ATI-Unicam UV4-200 spectrophotometer. Fluorescence measurements were performed using a Perkin-Elmer LS 50B fluorescence spectrophotometer. Electrochemical impedance spectroscopy was recorded on an Autolab potentiostat equipped with a temperature controller in the frequency range from z to Mz (applied voltage: 0 mv). The conductivities were studied as a function of temperature between 30 ºC and 50 ºC with 5 ºC intervals. For the preparation of the cells for ionic conductivities, the appropriate amount of the ionic dendrimer was placed on an IT electrode that was sandwiched with another IT electrode controlling the thickness by using glass spacers (20μm). The cell was heated up to a few degrees above the melting point of the liquid crystal and the cell was pressed to obtain the thin film. After the preparation of the cell, a random orientation of the layers (SmA) or columns (Col h ) was observed between electrodes. Smectic samples were mechanically sheared within the cell in order to obtain a planar alignment of the layers (smectic layers aligned perpendicular to the electrodes). n the other hand, homeotropic alignment of the columnar mesophase was attainable after slow cooling down to room temperature (0.05 ºC min - ) from the isotropic liquid. The impedance spectrum can be modeled as an equivalent circuit and divided into imaginary (Z ) and real (Z ) components. The resistance (R b ) was estimated from the intersection of the real axis (Z ) and the semicircle of the impedance spectrum. The proton conductivities σ (S cm - ) were calculated with the formula: σ = d (R b A) where d (cm) is the thickness of the film, A (cm 2 ) is the area of the film and R b (Ω) is the resistance of the sample. Photocrosslinking of coumarin units (photodimerization) was carried out by exposing the aligned LC system to 365 nm LED light (ThorsLab) for 30 min. S4

5 2. EXPERIMENTAL PRCEDURES 2.. Synthesis of the coumarin functional unit Methyl -Bromodecanoate K 2 C 3, KI, acetone (C 2 ) 0 C 2 Me K Me-TF (C 2 ) 0 C 2 2 Methyl -[(2-oxo-2-chromen-7-yl)oxy] undecanoate (). A mixture of 7- hydroxy-2-chromen-2-one (3 g, 8.5 mmol), methyl -bromoundecanoate (5.68 g, mmol), anhydrous potassium carbonate (5. g, mmol) and a teaspoon of KI in acetone (75 ml) was stirred and heated to reflux for 2 h. The reaction was allowed to cool down to room temperature and the solvent was evaporated under reduced pressure. The residue was dissolved in dichloromethane and washed with water and brine. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated. The crude product was recrystallized with ethanol. Yield: 93%. IR (KBr, ν, cm - ): 2923 (C- ), 744 (C=), 62, 463 (Ar), 232, 26 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): 7.63 (d, J= 9.4 z, ), 7.6 (d, J= 8.5 z, ), (m, 2), 6.24 (d, J= 9.5 z, ), 4.00 (t, J= 6.5 z, 2), 3.66 (s, 3), 2.30 (t, J= 7.5 z, 2), (m, 2), (m, 2),.5-.2 (m, 2). 3 C NMR (CDCl 3, 00 Mz, δ, ppm): 76.53, 62.58, 6.47, 56.07, 43.6, 28.83, 3.6, 3.05, 2.50, 0.46, 68.79, 5.60, 34.24, 29.58, 29.47, 29.43, 29.35, 29.26, 29.0, 26.07, [(2-xo-2-chromen-7-yl)oxy] undecanoic acid (2). An aqueous solution of potassium hydroxide (5.45 g, 0 ml) was added to a solution of methyl - [(2-oxo-2-chromen-7-yl)oxy] undecanoate () (4.5 g, 2.48 mmol) in methanol and tetrahydrofuran (50 ml and 5 ml, respectively). The mixture was stirred and heated under reflux for 2 h. Then the crude product was precipitated by addition of concentrated hydrochloric acid until p 2 and it was filtered. The product was recrystallized in ethanol. Yield: 9%. IR (KBr, ν, cm - ): 333 (-), 79, 699 (C=), , 466 (Ar), 205, 39 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): 7.63 (d, J= 9.5 z, ), 7.35 (d, J= 8.4 z, ), (m, 2), 6.24 (d, J= 9.4 z, ), 4.00 (t, J= 7.0 z, 2), 2.34 (t, J= 7.5 z, 2), (m, 2), (m, 2), (m, 2). 3 C NMR (CDCl 3, 00 Mz, δ, ppm): 79.23, 62.59, 6.55, 56.06, 43.65, 28.83, 3.9, 3.03, 2.5, 0.47, 68.80, 34.05, 29.55, 29.43, 29.39, 29.32, 29.6, 29.08, 26.05, S5

6 2.2. Synthesis of the bifunctional dendron Ac-ChCou Bn Cholesteryl hemisuccinate DCC, DPTS, DCM Bn 3 2 DCC, DPTS, DCM Bn Bn-ChCou Pd() 2 Cyclohexene/TF Ac-ChCou Monofunctionalized dendron (3). Benzyl 2,2 -bis(hydroxymethyl)propanoate (.00 g, 4.46 mmol), cholesteryl hemisuccinate (2.7 g, 4.46 mmol) and (N,N - dimethylamino)pyridinium p-toluenesulfonate (0.70 g, 2.23 mmol) were dissolved in dry dichloromethane (00 ml). The reaction flask was cooled in an ice bath and flushed with argon, then N,N -dicyclohexylcarbodiimide (.0 g, 4.9 mmol) was added dropwise. The mixture was stirred at RT for 24 h under argon atmosphere. The white precipitate was filtered off and washed with dichloromethane. The solvent was evaporated and the crude product was purified by flash column chromatography on silica gel using dichloromethane as eluent and gradually changing the composition of the eluent to dichloromethane/ethyl acetate (9:). Yield: 66%. IR (KBr, ν, cm - ): 356 (), 2954 (C-), 722 (C=), 254, 055 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): (m, 5), 5.36 (d, J= 3.6 z, ), 5.20 (d, J= 2.4 z, ), 5.6 (d, J= 2.4 z, ), (m, ), 4.39 (d, J=.2 z, ), 4.25 (d, J=.2 z, ), (m, 2), (m, 4), 2.3 (d, J= 7.7 z, 2), (m, 4), 0.68 (s, 3). 3 C NMR (CDCl 3, 00 Mz, δ, ppm): 74.3, 72.63, 7.72, 39.64, 35.78, 28.75, 28.47, 28.5, 22.9, 74.64, 66.83, 66.05, 65.00, 56.82, 56.26, 50.4, 48.43, 42.44, 39.86, 39.65, 38.8, 37.08, 36.7, 36.32, 35.93, 32.03, 3.98, 29.49, 29.8, 28.37, 28.5, 27.85, 24.42, 23.96, 22.96, 22.7, 2.6, 9.44, 8.85, 7.7,.99. S6

7 Bifunctionalized dendron Bn-ChCou. -[(2-xo-2-chromen-7-yl)oxy] undecanoic acid (2) (0.96 g, 2.77 mmol), the monofunctional dendron (3) (.75 g, 2.53 mmol) and (N,N -dimethylamino)pyridinium p-toluenesulfonate (0.39 g,.26 mmol) were dissolved in dry dichloromethane (75 ml). The reaction flask was cooled in an ice bath and flushed with argon, then N,N - dicyclohexylcarbodiimide (0.63 g, 3.03 mmol) was added dropwise. The mixture was stirred at RT for 24 h under argon atmosphere. The white precipitate was filtered off and washed with dichloromethane. The solvent was evaporated and the crude product was purified by flash column chromatography on silica gel using dichloromethane as eluent and gradually changing the composition of the eluent to dichloromethane/ethyl acetate (9:). Yield: 90%. IR (KBr, ν, cm - ): 2934 (C-), 74 (C=), 63, 467 (Ar), 23, 56 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): 7.63 (d, J= 9.4 z, ), (m, 6), (m, 2), 6.24 (d, J= 9.5 z, ), (m, ), 5.6 (s, 2), (m, ), (m, 4), 4.00 (t, J= 6.5 z, 2), (m, 4), 2.30 (d, J= 7.7 z, 2), 2.22 (t, J= 7.6 z, 2), (m, 54), 0.67 (s, 3). 3 C NMR (CDCl 3, 00 Mz, δ, ppm): 73.35, 72.69, 7.94, 7.56, 62.59, 6.4, 56.0, 43.57, 39.7, 35.76, 28.82, 28.72, 28.47, 28.27, 22.86, 3.5, 3.08, 2.5, 0.49, 74.55, 68.8, 66.94, 65.77, 65.43, 56.84, 56.29, 50.7, 46.55, 42.46, 39.88, 39.66, 38.20, 37.0, 36.72, 36.33, 35.93, 34.8, 32.04, 32.00, 29.62, 29.5, 29.46, 29.36, 29.24, 29.3, 28.37, 28.6, 27.88, 26.0, 24.94, 24.42, 23.98, 22.96, 22.70, 2.7, 9.45, 8.86, 7.9, Bifunctionalized dendron Ac-ChCou. The dendron with benzyl ester group (Bn-ChCou) and Pd() 2 /C (20% wt.) were dissolved in a mixture of TFcyclohexene (:3) under reflux. After 2 h, the catalyst was filtered off using Celite and carefully washed with dichloromethane. The solvent was evaporated and the crude product was purified by flash column chromatography on silica gel using dichloromethane as eluent and gradually changing the composition of the eluent to ethyl acetate. Yield: quantitative. IR (KBr, ν, cm - ): 3228 (), 3044 (=C-), 2932 (C-), 74, 730, 683 (C=), 604, 507, 466 (Ar), 252, 65 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): 7.63 (d, J= 9.5 z, ), 7.36 (d, J= 8.5 z, ), (m, 2), 6.24 (d, J= 9.5 z, ), (m, ), (m, ), (m, 4), 4.0 (t, J= 6.5 z, 2), (m, 4), (m, 4), (m, 54), 0.67 (s, 3). 3 C NMR (CDCl 3, 00 Mz, δ, ppm): 76.98, 73.40, 7.97, 7.65, 62.6, 6.57, 56.07, 43.65, 39.70, 28.84, 22.87, 3.20, 3.05, 2.53, 0.50, 74.62, 68.82, 65.50, 65.2, 56.83, 56.30, 50.6, 46.2, 42.46, 39.87, 39.66, 38.9, 37.0, 36.72, 36.33, 35.94, 34.22, 32.04, 32.00, 29.58, 29.48, 29.40, 29.33, 29.23, 29.9, 29.09, 28.37, 28.6, 27.87, 26.07, 24.96, 24.43, 23.99, 22.96, 22.70, 2.7, 9.45, 8.86, 7.89, MS (MALDI +, dithranol, m/z): calcd. for C 56 82, 930.6; found, [M+Na] +, [M-+2Na] +. Anal. calcd. for C : C, 72.23%;, 8.88%. Found: C, 72.00%;, 8.94%. S7

8 2.3. Synthesis of the ionic hybrid dendrimers Ionic dendrimers were prepared following the previously described methodology. 2,3 A solution of Ac-ChCou in dry tetrahydrofuran was added to a solution of the corresponding generation of PAMAM dendrimer, in approximately : (primary amine groups:carboxylic acid groups) stoichiometry. The mixture was ultrasonicated for 5 min, and then it was slowly evaporated at room temperature and dried in vacuum at 40ᵒC until the weight remained constant. PAMAM4-ChCou. IR (KBr, ν, cm - ): 3258 (N-), 3069 (=C-), 2930 (C-), 729, 645 (C=), 6 (Ar), 555 (C asym), 406 (C sym), 58 (C-). NMR (CDCl3, 400 Mz, δ, ppm): (m, 4), 7.63 (d, J= 9.5 z, 4), 7.35 (d, J= 8.6 z, 4), (m, 8), 6.23 (d, J= 9.5 z, 4), (m, 4), (m, 4), (m, 6), 4.00 (t, J= 6.5 z, 8), (m, 4), (m, 4), (m, 52), (m, 26), 0.66 (s, 2). 3 C NMR (CDCl3, 00 Mz, δ, ppm): 78.40, 73.80, 72.3, 72.02, 62.60, 6.49, 56.08, 43.65, 39.7, 28.86, 22.87, 3.6, 3.04, 2.52, 0.49, 74.62, 68.8, 68.2, 66.80, 66.5, 56.83, 56.32, (detected by - 3 C SQC, ζ -C ζ ), 50.5, (detected by - 3 C SQC, ε - C ε ), 46.59, 42.46, 39.87, 39.66, (detected by - 3 C SQC, η -C η ), 39.0 (detected by - 3 C SQC, α -C α ), 38.20, (detected by - 3 C SQC, β -C β ), 37.0, 36.73, 36.34, 35.95, 34.38, (detected by - 3 C SQC, δ - C δ ), 32.05, 3.99, 29.65, 29.56, 29.47, 29.44, 29.34, 29.22, 29.3, 28.38, 28.6, 27.87, 26.0, 25.76, 25.06, 24.43, 24.02, 22.97, 22.7, 2.8, 9.45, 8.86, 8.64, PAMAM8-ChCou. IR (KBr, ν, cm - ): 3260 (N-), 3070 (=C-), 2928 (C-), 728, 644 (C=), 60 (Ar), 555 (C asym), 406 (C sym), 58 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): (m, 8), (m, 4), 7.63 (d, J= 9.5 z, 8), 7.36 (d, J= 8.6 z, 8), (m, 6), 6.24 (d, J= 9.5 z, 8), (m, 8), (m, 8), (m, 32), 4.00 (t, J= 6.5 z, 6), (m, 6), (m, 24), (m, 20), (m, 432), 0.66 (s, 24). 3 C NMR (CDCl 3, 00 Mz, δ, ppm):78.02, 73.74, 72.25, 7.90, 62.59, 6.5, 56.06, 43.66, 39.70, 28.85, 22.86, 3.6, 3.03, 2.5, 0.48, 74.59, 68.80, 56.82, 56.30, (detected by - 3 C SQC, ζ -C ζ ), 50.8 (detected by - 3 C SQC, ε -C ε ), 50.4, 42.45, 39.86, 39.65, (detected by - 3 C SQC, α -C α ), 38.8, (detected by - 3 C SQC, η -C η ), (detected by - 3 C SQC, β - C β ), 37.09, 36.72, 36.33, 35.94, 34.35, 34.0 (detected by - 3 C SQC, δ - C δ ), 32.04, 3.98, 29.63, 29.55, 29.5, 29.45, 29.42, 29.32, 29., 28.37, 28.5, 2 V. Chechik, M. Zhao, R. M. Crooks,. J. Am. Chem. Soc. 999, 2, R. Martín-Rapún, M. Marcos, A. menat, J. Barberá, P. Romero, J. L. Serrano, J. Am. Chem. Soc. 2005, 27, S8

9 27.86, 26.09, 25.03, 24.42, 24.0, 22.96, 22.7, 2.7, 9.45, 8.86, 8.54,.99. PAMAM6-ChCou. IR (KBr, ν, cm - ): 326 (N-), 3069 (=C-), 2929 (C-), 729, 645 (C=), 60 (Ar), 555 (C asym), 406 (C sym), 58 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): (m, 6), (m, 2), 7.63 (d, J= 9.5 z, 7), 7.35 (d, J= 8.6 z, 6), (m, 32), 6.23 (d, J= 9.5 z, 6), (m, 6), (m, 6), (m, 64), 3.99 (t, J= 6.5 z, 32), (m, 32), (m, 56), (m, 264), (m, 864), 0.66 (s, 48). 3 C NMR (CDCl 3, 00 Mz, δ, ppm): 73.73, 72.26, 7.86, 62.59, 6.48, 56.05, 43.66, 39.70, 28.86, 22.84, 3.4, 3.02, 2.5, 0.48, 74.55, 68.80, 68.0, 66.64, 66.05, 56.82, 56.3, (detected by - 3 C SQC, ζ -C ζ ), (detected by - 3 C SQC, ε -C ε ), 50.4, 46.5, 42.44, 39.86, 39.64, (detected by - 3 C SQC, α -C α ), 38.9, (detected by - 3 C SQC, η -C η ), (detected by - 3 C SQC, β -C β ), 37.09, 36.7, 36.33, 35.93, 34.35, 34.7 (detected by - 3 C SQC, δ -C δ ), 3.98, 29.65, 29.56, 29.47, 29.33, 29.2, 28.36, 28.5, 27.86, 26.0, 25.74, 25.04, 24.42, 24.0, 22.96, 22.70, 2.6, 9.45, 8.86, 8.65,.99. PAMAM32-ChCou. IR (KBr, ν, cm - ): 3260 (N-), 3069 (=C-), 2929 (C-), 729, 645 (C=), 60 (Ar), 554 (C asym), 405 (C sym), 60 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): (m, 32), (m, 28), 7.63 (d, J= 9.5 z, 32), 7.35 (d, J= 8.6 z, 32), (m, 64), 6.22 (d, J= 9.5, 32), (m, 32), (m, 32), (m, 28), 3.99 (t, J= 6.5 z, 64), (m, 64), (m, 20), (m, 552), (m, 728), 0.66 (s, 96). 3 C NMR (CDCl 3, 00 Mz, δ, ppm): 78.59, 73.82, 72.35, 7.93, 62.6, 6.48, 56.08, 43.66, 39.73, 28.88, 22.85, 3.5, 3.04, 2.54, 0.52, 74.58, 68.82, 66.49, 66.26, 56.85, 56.37, (detected by - 3 C SQC, ζ -C ζ ), (detected by - 3 C SQC, ε -C ε ), 50.8, 46.60, 42.47, 39.89, (detected by - 3 C SQC, α -C α ), 39.67, 38.2, (detected by - 3 C SQC, η -C η ), (detected by - 3 C SQC, β -C β ), 37.2, 36.74, 36.36, 35.96, 34.38, (detected by - 3 C SQC, δ -C δ ), 32.05, 29.85, 29.67, 29.59, 29.49, 29.36, 29.27, 29.5, 28.38, 28.6, 27.88, 26.2, 25.06, 24.44, 24.05, 22.96, 22.7, 2.9, 9.46, 8.88, 8.63, 2.0. PAMAM64-ChCou. IR (KBr, ν, cm - ): 3260 (N-), 3069 (=C-), 2929 (C-), 729, 645 (C=), 60 (Ar), 555 (C asym), 406 (C sym), 58 (C-). NMR (CDCl 3, 400 Mz, δ, ppm): (m, 64), (m, 60), 7.63 (d, J= 9.5 z, 64), 7.35 (d, J= 8.6 z, 64), (m, 28), 6.23 (d, J= 9.5 z, 64), (m, 64), (m, 64), (m, 256), 3.97 (t, J= 6.5 z, 28), (m, 376), (m, 28), (m, 3456), 0.70 (s, 92). 3 C NMR (CDCl 3, 00 Mz, δ, ppm): 78.08, 73.70, 72.23, 7.82, 62.59, 6.49, 56.05, 43.68, 39.69, 28.87, S9

10 22.84, 3.4, 3.0, 2.5, 0.48, 74.54, 68.80, 68.0, 66.53, 56.8, 56.32, 52.4 (detected by - 3 C SQC, ζ -C ζ ), (detected by - 3 C SQC, ε -C ε ), 50.4, 46.49, 42.44, 39.86, 39.64, 39.4 (detected by - 3 C SQC, α -C α ), 38.9, (detected by - 3 C SQC, η -C η ), (detected by - 3 C SQC, β -C β ), 37.09, 36.7, 36.33, 35.94, 34.34, 3.98, 29.65, 29.57, 29.47, 29.33, 29.3, 28.37, 28.5, 27.86, 26.0, 25.74, 25.04, 24.42, 24.02, 22.96, 22.70, 2.7, 9.45, 8.86, 8.59,.99. S0

11 3. SUPPLEMENTARY MATERIAL 3.. FTIR and NMR characterization Absorbance (a.u.) Wavenumber (cm - ) Figure S. FTIR spectra (C= st. region) of PAMAM6 (black line), Ac-ChCou (blue line), and PAMAM6-ChCou (red line) 9 N 3 + P, P J β η α U, V, ζ ε M, 4 δ 2 K, M J P, P N 3 + U, V, ζ M, 4 β η α ε δ 2 9 Figure S2. - NESY spectrum of PAMAM32-ChCou (CDCl 3, 298 K, t mix = 200 ms). S

12 P, P J β η α U, V, ζ M, 4 ε δ 2 K, M Figure S C SQC spectrum of PAMAM32-ChCou (CDCl 3, 298 K). S2

13 3.2. PM textures (a) (b) (c) (d) (e) (f) Figure S4. PM microphotographs observed in the cooling process at room temperature for: (a) Ac-ChCou, (b) PAMAM4-ChCou, (c) PAMAM8-ChCou, (d) PAMAM6-ChCou, (e) PAMAM32-ChCou, and (f) PAMAM64-ChCou Nyquist plots -Z'' (imaginary) ( ) 2,0x0 6,6x0 6,2x0 6 8,0x0 5 4,0x0 5 5x0 3 50ᵒC 00ᵒC 50ᵒC 0,0 0 x0 6 2x0 6 3x0 6 4x0 6 5x0 6 Z' (real) ( ) -Z'' (imaginary) ( ) 4x0 3 3x0 3 2x0 3 x ,0 2,0x0 3 4,0x0 3 6,0x0 3 8,0x0 3,0x0 4 Z' (real) ( ) -Z'' (imaginary) ( ) 2,0x0 2,6x0 2,2x0 2 8,0x0 4,0x0 x0 2 2x0 2 3x0 2 4x0 2 5x0 2 Figure S5. Nyquist plots of PAMAM64-ChCou at 50ᵒC, 00ᵒC and 50ᵒC. Z' (real) ( ) S3

14 3.4. ptical and fluorescent properties The ionic dendrimers present identical absorption spectra in TF solution with a band at 323 nm related to the π π* transition of the coumarin units. The UV-Vis absorption spectra in solid thin films showed that the absorption band was broader respect to the corresponding TF solutions, due to aggregation of the ionic dendrimers. The fluorescence emission spectra in TF solution exhibit one band at 384 nm. The fluorescence quantum yields (Φ) of the ionic dendrimers were also measured with anthracene (Φ = 0.27 in ethanol) as standard, obtaining moderate quantum yield values in the range of In general, the quantum yields increase as the generation increases. The fluorescence emission in solid thin film was also recorded. Compared to the data from TF solutions, the emission peak appeared broader and red-shifted by ca. 50 nm. Absorbance (a.u.) Intensity (a.u.) Wavelength (nm) Figure S6. Absorption (red) and emission (blue) spectra of PAMAM64-ChCou in TF solution (solid line) and in thin film (dot line). Table S. Photophysical data λ TF abs (log ε) a λ film a abs λ TF b em Φ c Ac-ChCou 324 (4.3) PAMAM4-ChCou 323 (4.72) PAMAM8-ChCou 323 (5.03) PAMAM6-ChCou 324 (5.32) PAMAM32-ChCou 323 (5.6) PAMAM64-ChCou 323 (5.94) a Maximum of the absorption band in nm (ε: extinction coefficient in M - cm - ). b Maximum of the emission band in nm. c Quantum yields in TF relative to anthracene (Φ=0.27 in ethanol) S4