Supporting Information

Transcription

1 Supporting Information Size Selective Adsorption in Nanoporous Polymers from Coumarin Photo-Cross-Linked Columnar Liquid Crystals Alberto Concellón, Albertus P. H. J. Schenning,, Pilar Romero, Mercedes Marcos, and José Luis Serrano*, Instituto de Ciencia de Materiales de Aragón, Departamento de Química Orgánica, Universidad de Zaragoza CSIC, Zaragoza, Spain. Department of Functional Organic Materials and Devices, Chemical Engineering and Chemistry, and Institute for Complex Molecular Systems (ICMS), Eindhoven University of Technology, P. O. Box 513, 5600 MB, Eindhoven, The Netherlands Instituto de Nanociencia de Aragón, Departamento de Química Orgánica, Universidad de Zaragoza, Zaragoza, Spain. * Corresponding Author: joseluis@unizar.es S1

2 1. SUPPLEMENTARY FIGURES 1695 cm 1 Absorbance 1670 cm cm Wavenumber (cm -1 ) Figure S1. FTIR spectra (C=O st. region) of dcou (black line), M dcou (blue line), and T dcou (red line). Figure S2. POM microphotographs for 1:3 supramolecular complexes: (a) M dcou taken at 75 ᵒC in the heating process, (b) M dcou taken at 86 ᵒC in the heating process (c) M dcou taken at RT in the cooling process, (d) T dcou taken at 40 ᵒC in the heating process, (e) T dcou taken at 77 ᵒC in the heating process, and (f) T dcou taken at RT in the cooling process. S2

3 T-dCou complex T-based polymer T-based nanoporous polymer Intensity (a.u.) 1 10 q (nm -1 ) Figure S3. 1D XRD profiles of T dcou complex, T based polymer (with template) and T based nanoporous polymer (after template removal). Figure S4. (a) Self standing T based nanoporous polymer, (b) FTIR spectra T based polymer and nanoporous polymer, and (c) Nitrogen to carbon ratio of the T based polymer and nanoporous polymer as function of the sputter time (depth) determined by XPS. S3

4 Figure S5. The MM2 energy minimized structure and the diameter of M and T central cores. Schematic illustration of the nanoporous polymers with different pore sizes. S4

5 COOH occupation (%) M-dCou T-dCou 0 1st adsorption 1st desorption 2nd adsorption 2nd desorption 3rd adsorption 3rd desorption Cycle Figure S6. Occupation degree of adsorption sites (COOH) with pna during three adsorption desorption cycles. S5

6 Preparation of anionic nanoporous polymers with different counter cations in the pore Nanoporous polymers with carboxylic acid functionalized pores were treated with 0.1M aqueous solutions of the hydroxide salts of Li +, Na +, K +, Cs + and NH 4 + ions for 5h. The formation of a porous polymers with COOLi, COONa, COOK, COOCs, and COONH 4 groups at the pore surface, was confirmed by FTIR. The COOH st. band was shifted from 1685 to 1560 and 1404 cm 1 (Figure S7). C=O st asym(coo ) C=O st (COOH) C=O st sym(coo ) NH 4 + Absorbance (a.u.) Cs + Li + K + Na + Initial Wavenumer (cm -1 ) Figure S7. FTIR spectra of the M based nanoporous polymer after exposure to different hydroxide salts. S6

7 6Å 9Å 4Å pna 8Å APy 18Å TAPP 12Å 6Å 5Å RhB 16Å MB 13Å 12Å MO Figure S8. The MM2 energy minimized structure and the size of p nitroaniline (pna), 1 aminopyrene (APy), meso tetra(p aminophenyl)porphine (TAPP), methylene blue (MB), methyl orange (MO) and rhodamine B (RhB). S7

8 M-dCou T-dCou COO - occupation (%) st adsorption 1st desorption 2nd adsorption Cycle Figure S9. Occupation degree of adsorption sites (COO ) with MB during three adsorption desorption cycles. 2nd desorption 3rd adsorption 3rd desorption S8

9 2. SUPPLEMENTARY TABLES α θ ζ η β δ ε T S Q P O R N M L K J F G H E D I C B A T S Q P O R N M L K J F G H E D I C B A κ M dcou T dcou Table S1. Main shifts in the 1 H NMR spectra (CD 2 Cl 2, 500 MHz) of the complexes (the changes in chemical shift are shown in brackets) Compound H T H P H α H ε H ζ H 3 H 5 H 6 M T dcou * 7.32 M-dCou (-0.02) 6.04 (+1.15) 6.30 (+1.32) 3.36 (+0.06) T-dCou * 7.30 (-0.02) 9.04 (+0.18) (+0.17) (+0.14) * Not detected S9

10 Table S2. Main shifts in the 13 C NMR spectra (CD 2 Cl 2, 500 MHz) of the complexes (the changes in chemical shift are shown in brakets) Compound C S C R C Q C P C O C δ,β C ζ C 1 C 2 C 3 C 4 C 5 C 6 C 7 M T dcou M-dCou (-0.62) (-0.48) (+1.20) (-0.14) (-0.05) (-2.66) (+0.20) T-dCou (-1.40) (-0.14) (+0.07) (-0.03) (+0.01) (+0.03) (+0.04) (+0.08) (+0.05) (+0.06) (+0.06) (+0.06) S10