Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2015 Supporting Information Synthesis and optical properties of covalently bound Nile Red in mesoporous silica hybrids - Comparison of dye distribution of materials prepared by facile grafting and by co-condensation routes. Markus Börgardts, a Kathrin Verlinden, b Manuel Neidhardt, c Tobias Wöhrle, c Annika Herbst, b Sabine Laschat, c Christoph Janiak, b and Thomas J.J. Müller*,a a b c Institut für Organische Chemie und Makromolekulare Chemie, Heinrich-Heine- Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany. Institut für Anorganische Chemie und Strukturchemie, Abteilung für Metallorganische Chemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany. Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany. Table of Contents 1. Structural characterization of grafted and cocondensed materials 6 and 7... 2 1.1. Nitrogen sorption measurements... 2 1.2. Small angle x-ray scattering (SAXS)... 4 1.3. Transmission electron microscopy (TEM)... 6 2. Spectroscopic properties of precursor 5, and hybrid materials 6 and 7... 15 2.1. Solvatochromism of precursor 5... 15 2.2. Determination of dye concentration inside materials 6 and 7... 16 2.3. Solvatochromism of hybrid materials 6 and 7... 17 2.4. Excitation and emission spectra of hybrid materials 6 and 7 in the solid state... 19 2.5. Red-edge excitation shift (REES) of hybrid materials 6b and 7e... 23 2.6. Fluorescence quenching of hybrid materials 6b and 7e... 24
1. Structural characterization of grafted and cocondensed materials 6 and 7 1.1. Nitrogen sorption measurements 700 600 500 volume / cm³g -1 400 300 200 100 0 1,0 relative pressure / p/p 0 6a 6b 6c 6d 6e 6f 6g 6h 6i Figure S 1: Nitrogen sorption isotherms of grafted samples 6. The deep adsorption increase of hybrid 6h at relative pressures close to the saturation pressure is attributed to nitrogen condensation in interparticle voids. 700 600 500 volume / cm³g -1 400 300 200 100 0 1,0 relative pressure / p/p 0 7a 7b 7c 7d 7e 7f 7g 7h Figure S 2: Nitrogen sorption isotherms of co-condensed samples 7.
dv(r) / cm³g -1 nm -1 0,14 0,13 0,12 0,11 0,10 9 8 7 6 5 4 3 2 1 0 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 pore diameter / nm 6a 6b 6c 6d 6e 6f 6g 6h 6i Figure S 3: pore size distribution curves of grafted samples 6. 0,18 0,16 0,14 dv(r) / cm³g -1 nm -1 0,12 0,10 8 6 4 2 0 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 pore diameter / nm 7a 7b 7c 7d 7e 7f 7g 7h Figure S 4: pore size distribution curves of co-condensed samples 7.
1.2. Small angle x-ray scattering (SAXS) 100 110 200 210 6i 6h 6g log intensity / a.u. 6f 6e 6d 6c 6b 6a 2 3 4 5 6 7 8 9 2 / Figure S 5: SAXS pattern of grafted samples 6.
100 110 200 210 7h 7g 7f log intensity / a.u. 7e 7d 7c 7b 7a 2 3 4 5 6 7 8 9 2 / Figure S 6: SAXS pattern of co-condensed samples 7.
1.3. Transmission electron microscopy (TEM) Figure S 7: TEM images of 6a a) along the channel direction and b) perpendicular to the channel direction. Figure S 8: : TEM images of 6b a) along the channel direction and b) perpendicular to the channel direction.
Figure S 9: TEM images of 6c a) along the channel direction, b) perpendicular to the channel direction and c) large scale. Figure S 10: TEM images of 6d a) along the channel direction and b) perpendicular to the channel direction.
Figure S 11: TEM images of 6e a) along the channel direction and b) perpendicular to the channel direction. Figure S 12: TEM images of 6f a) along the channel direction and b) perpendicular to the channel direction.
Figure S 13: TEM images of 6g a) along the channel direction, b) perpendicular to the channel direction and c) mixed phase. Figure S 14: TEM images of 6h a) along the channel direction and b) perpendicular to the channel direction.
Figure S 15: TEM images of 6i a) along the channel direction and b) perpendicular to the channel direction. Figure S 16: TEM images of 7a a) along the channel direction and b) perpendicular to the channel direction.
Figure S 17: TEM images of 7b a) along the channel direction and b) perpendicular to the channel direction. Figure S 18: TEM images of 7c a) along the channel direction and b) perpendicular to the channel direction.
Figure S 19: TEM images of 7d a) along the channel direction and b) perpendicular to the channel direction. Figure S 20: TEM images of 7e a) along the channel direction and b) perpendicular to the channel direction.
Figure S 21: TEM images of 7f a) along the channel direction and b) perpendicular to the channel direction. Figure S 22: TEM images of 7g a) along the channel direction and b) perpendicular to the channel direction.
Figure S 23: TEM images of 7h a) along the channel direction and b) perpendicular to the channel direction.
2. Spectroscopic properties of precursor 5, and hybrid materials 6 and 7 2.1. Solvatochromism of precursor 5 1,0 normalized absorption 425 450 475 500 525 550 575 600 625 Hexane CHCl 3 1,4-Dioxane ipr 2 O DCM Et 2 O DCE THF EtOH EtOAc MeOH DMSO MeCN Acetone Figure S 24: Absorption spectra of 5 in different solvents. 1,0 normalized emission 500 550 600 650 700 750 800 Hexane CHCl 3 1,4-Dioxane ipr 2 O DCM Et 2 O DCE THF EtOH EtOAc MeOH DMSO MeCN Acetone Figure S 25: Emission spectra of 5 in different solvents. The molar extinction coefficient of precursor 5 in DMSO was determined to be 539nm = 21000 M -1 cm -1.
2.2. Determination of dye concentration inside materials 6 and 7 0,14 0,12 0,10 absorption 8 6 4 2 0 400 450 500 550 600 650 700 750 800 6a 6b 6c 6d 6e 6f 6g 6h 6i Figure S 26: UV/Vis-spectra of grafted hybrid materials suspended in DMSO with c(6a) = 3.0 g/l, c(6b-6g) = 0.3 g/l, c(6h) = 0.15 g/l, c(6i) = 0.12 g/l. 0,12 0,10 8 absorption 6 4 2 0 400 450 500 550 600 650 700 750 800 7a 7b 7c 7d 7e 7f 7h 7g Figure S 27: UV/Vis-spectra of co-condensed hybrid materials suspended in DMSO with c(7a) = 10 g/l, c(7b - 7e) = 3.0 g/l, c(7f) = 0.30 g/l, c(7g) = 0.075 g/l, c(7h) = 0.060 g/l.
2.3. Solvatochromism of hybrid materials 6 and 7 1,0 normalized emission 600 625 650 675 700 725 750 775 800 Et 2 O 1,4-Dioxane Hexane H 2 O Figure S 28: normalized emission spectra of 6b in different solvents. 1,0 normalized emission intensity 400 425 450 475 500 525 550 575 600 625 650 Et 2 O 1,4-Dioxane Hexane H 2 O Figure S 29: normalized excitation spectra of 6b in different solvents ( emission = 660 nm).
1,0 normalized emission 600 650 700 750 800 Hexane CHCl 3 1,4-Dioxane ipr 2 O DCM Et 2 O DCE THF EtOH EtOAc MeOH H 2 O DMSO MeCN Acetone Figure S 30: normalized emission spectra of 7e in different solvents. 1,0 normalized intensity 420 440 460 480 500 520 540 560 580 600 Hexane CHCl 3 1,4-Dioxane ipr 2 O DCM Et 2 O DCE THF EtOH EtOAc MeOH H 2 O DMSO MeCN Acetone Figure S 31: normalized excitation spectra of 7e in different solvents ( emission = 650 nm).
2.4. Excitation and emission spectra of hybrid materials 6 and 7 in the solid state 1,0 wavenumber / cm -1 24000 22000 20000 18000 16000 1,0 normalized intensity normalized intensity 400 450 500 550 600 650 6a 6b 6c 6d 6e 6f 6g 6h 6i Figure S 32: normalized excitation spectra of grafted hybrid materials 6 ( emission = 700 nm). wavenumber / cm -1 24000 22000 20000 18000 16000 intensity 280 260 240 220 200 180 160 140 120 100 80 60 40 20 400 450 500 550 600 650 6b 6c 6d 6e 6f 6h 6i 280 260 240 220 200 180 160 140 120 100 80 60 40 20 intensity Figure S 33: excitation spectra of grafted hybrid materials 6 ( emission = 700 nm). (Hybrid materials 6a and 6g not shown as they were measured in another setup.)
1,0 wavenumber / cm -1 17000 16000 15000 14000 13000 1,0 normalized intensity normalized intensity 600 650 700 750 800 6a 6b 6c 6d 6e 6f 6g 6h 6i Figure S 34: normalized emission spectra of grafted hybrid materials 6. 17000 16000 15000 14000 13000 140 140 120 120 fluorecence intensity 100 80 60 40 100 80 60 40 fluorecence intensity 20 20 0 0 600 650 700 750 800 6a 6b 6c 6d 6e 6f 6g 6h 6i Figure S 35: emission spectra of grafted hybrid materials 6.
1,0 wavenumber / cm -1 24000 22000 20000 18000 16000 1,0 normalized intensity normalized intensity 400 450 500 550 600 650 7a 7b 7c 7d 7e 7f 7g 7h Figure S 36: normalized excitation spectra of co-condensed hybrid materials 7 ( emission = 700 nm). wavenumber / cm -1 24000 22000 20000 18000 16000 intensity 90 80 70 60 50 40 30 20 10 90 80 70 60 50 40 30 20 10 intensity 350 400 450 500 550 600 650 700 7a 7b 7c 7d 7e 7f 7g 7h Figure S 37: excitation spectra of co-condensed hybrid materials 7 ( emission = 700 nm).
1,0 wavenumber / cm -1 17000 16000 15000 14000 13000 1,0 normalized intensity normalized intensity 600 650 700 750 800 7a 7b 7c 7d 7e 7f 7g 7h Figure S 38: normalized emission spectra of co-condensed hybrid materials 7. 140 wavenumber / cm -1 17000 16000 15000 14000 13000 140 120 120 fluorescence intensity 100 80 60 40 100 80 60 40 fluorescence intensity 20 20 0 0 600 650 700 750 800 7a 7b 7c 7d 7e 7f 7g 7h Figure S 39: emission spectra of co-condensed hybrid materials 7.
2.5. Red-edge excitation shift (REES) of hybrid materials 6b and 7e 1,0 normalized intensity 540 560 580 600 620 640 660 680 700 720 740 760 780 800 470 nm 500 nm 520 nm 530 nm 547 nm 570 nm 580 nm 590 nm 600 nm 610 nm 620 nm 630 nm 640 nm 650 nm Figure S 40: Fluorescence spectra of 6b at designated excitation wavelengths showing REES. 1,0 normalized intensity 540 560 580 600 620 640 660 680 700 720 740 760 780 800 450 nm 500 nm 520 nm 541 nm 560 nm 570 nm 580 nm 590 nm 600 nm 610 nm 620 nm Figure S 41: Fluorescence spectra of 7e at designated excitation wavelengths showing REES.
2.6. Fluorescence quenching of hybrid materials 6b and 7e fluorescence intensity c(hcl) / mmoll -1 0.00 1200 2.00 4.00 6.00 1000 16.0 24.0 800 40.0 56.0 72.0 600 88.0 104 120 400 136 152 200 168 184 200 0 625 650 675 700 725 750 775 800 825 Figure S 42: fluorescence quenching of 6b in water upon addition of designated amounts of HCl. fluorescence intensity c(hcl) / mmoll -1 700 0.00 2.00 4.00 600 6.00 16.0 500 24.0 40.0 400 56.0 72.0 88.0 300 104 120 200 136 152 168 100 184 200 0 450 475 500 525 550 575 600 625 650 675 700 Figure S 43: excitation spectra of fluorescence quenching of 6b in water upon addition of designated amounts of HCl ( emission = 720 nm).
fluorescence 1400 1200 1000 800 600 400 200 0 c(hcl) / mmoll -1 0.00 2.00 4.00 6.00 8.00 16.0 24.0 40.0 56.0 72.0 88.0 104 120 136 152 168 184 200 625 650 675 700 725 750 775 800 825 Figure S 44: fluorescence quenching of 7e in water upon addition of designated amounts of HCl. excitation intensity c(hcl) / mmoll -1 600 0.00 2.00 4.00 500 6.00 8.00 16.0 400 24.0 40.0 56.0 300 72.0 88.0 104 200 120 136 100 152 168 184 0 200 450 475 500 525 550 575 600 625 650 675 Figure S 45: excitation spectra of fluorescence quenching of 7e in water upon addition of designated amounts of HCl ( emission = 720 nm).