Glassy Poly(methacrylate) Terpolymers with Covalently Attached Emitters
and Sensitizers for Low-Power Light Upconversion
Soo Hyon Lee, David C. Thévenaz, Christoph Weder*, and Yoan C. Simon*
Adolphe Merkle Institute, University of Fribourg, Chemin des Verdiers 4, CH-1700 Fribourg,
Switzerland
Correspondence to: Christoph Weder (E-mail: christoph.weder@unifr.ch), Yoan Simon (E-mail:
yoan.simon@unifr.ch)
Supporting Information
1H
NMR and 13CNMR spectra of porphyrin
S2-S3
Absorption spectra of porphyrin monomers
S4
1H
S5-S9
NMR spectra and GPC chromatogram of terpolymers
Thermal characterization of chromophores and terpolymers
S10-S13
Absorption and emission spectra of terpolymers
S14-S16
S1
1H
NMR and 13CNMR spectra of porphyrin intermediates
Figure S1. 1H NMR spectrum (360 MHz, CD2Cl2) of mPH3POH.
Figure S2. 13C NMR spectrum (75.5 MHz, CD2Cl2) of mPH3POH.
S2
Figure S3. 1H NMR spectrum (360 MHz, CD2Cl2) of mPH3PMA.
Figure S4. 13C NMR spectrum (75.5 MHz, CD2Cl2) of mPH3PMA.
S3
Absorption spectra of porphyrin monomers
3
mPH3PMA
PdmPH3PMA
Absorption
420
2
1
518
552
530
560
563
655
0
400
500
600
700
Wavelength (nm)
Figure S5. Absorption spectra of solutions of mPH3PMA (24 µM) and PdmPH3PMA (11 µM) in toluene.
PdmPH3PMA
Soret
Absorption
3
PdOEP
2
1


0
350
400
450
500
550
600
Wavelength (nm)
Figure S6. Absorption spectra of solutions of PdmPH3PMA (red, 11 µM) and PdOEP (black, 10 µM) in toluene.
S4
1H
NMR spectra and GPC chromatograms of terpolymers
Figure S7. 1H NMR spectrum (360 MHz, CD2Cl2) of terpolymer A1.
Figure S8. 1H NMR spectrum (360 MHz, CD2Cl2) of terpolymer A2.
S5
Figure S9. 1H NMR spectrum (360 MHz, CD2Cl2) of terpolymer A3.
Figure S10. 1H NMR spectrum (360 MHz, CD2Cl2) of terpolymer A4.
S6
Figure S11. 1H NMR spectrum (360 MHz, CD2Cl2) of terpolymer A5.
Figure S12. Gel permeation chromatogram of terpolymer A1.
S7
1.2
Terpolymer A2
UV-370 nm
UV-420 nm
RI
1.0
R.I.
0.8
0.6
0.4
0.2
0.0
8
9
10 11 12 13 14 15 16 17 18 19 20
Time (min)
Figure S13. Gel permeation chromatogram of terpolymer A2.
1.2 Terpolymer A3
UV 370 nm
UV 420 nm
RI
1.0
R.I.
0.8
0.6
0.4
0.2
0.0
10.0
12.5
15.0
17.5
Time (min)
Figure S14. Gel permeation chromatogram of terpolymer A3.
S8
1.0
Terpolymer A4
UV 370 nm
UV 420 nm
RI
R.I.
0.8
0.6
0.4
0.2
0.0
10
12
14
16
18
20
Time (min)
Figure S15. Gel permeation chromatogram of terpolymer A4.
1.0
Terpolymer A5
370 nm
420 nm
RI
R.I.
0.8
0.6
0.4
0.2
0.0
10
12
14
16
18
20
Time (min)
Figure S16. Gel permeation chromatogram of terpolymer A5.
S9
Thermal characterization of chromophores and terpolymers
100
90
Weight (%)
80
70
60
50
40
30
20
10
0
100
200
300
400
500
Temperature (°C)
Figure S17. Thermogravimetric analysis (TGA) trace of terpolymer A1 containing 0.73 wt% of PdmPH3P, and 37
wt% DPA. The TGA experiment was conducted under N2.
0.8
st
Terpolymer A1
1 Heating
Cooling
nd
2 Heating
Exothermic
0.6
0.4
0.2
138 °C
0.0
50
100
150
200
Temperature (°C)
Figure S18. Differential scanning calorimetry (DSC) traces of terpolymer A1, recorded under nitrogen. The
polymer was first heated from 25 °C to 200 °C, cooled from 200 °C to 0 °C, and heated again from 0 °C to 250 °C.
All heating and cooling rates were 10 °C/min.
S10
2.0
st
Terpolymer A2
1 Heating
Cooling
nd
2 Heating
Exothermic
1.8
1.6
1.4
140.5 °C
1.2
1.0
50
100
150
200
Temperature (°C)
Figure S19. Differential scanning calorimetry (DSC) traces of terpolymer A2, recorded under nitrogen. The
polymer was first heated from 25 °C to 200 °C, cooled from 200 °C to 0 °C, and heated again from 0 °C to 250 °C.
All heating and cooling rates were 10 °C/min.
1.0
st
Terpolymer A3
1 Heating
Cooling
nd
2 Heating
Exothermic
0.8
0.6
0.4
0.2
144 °C
0.0
50
75
100
125
150
175
200
Temperature (°C)
Figure S20. Differential scanning calorimetry (DSC) traces of terpolymer A3, recorded under nitrogen. The
polymer was first heated from 25 °C to 200 °C, cooled from 200 °C to 0 °C, and heated again from 0 °C to 250 °C.
All heating and cooling rates were 10 °C/min.
S11
1.0
st
Terpolymer A4
1 Heating
Cooling
nd
2 Heating
Exothermic
0.8
0.6
0.4
0.2
142 °C
0.0
50
75
100
125
150
175
200
Temperature (°C)
Figure S21. Differential scanning calorimetry (DSC) traces of terpolymer A4, recorded under nitrogen. The
polymer was first heated from 25 °C to 200 °C, cooled from 200 °C to 0 °C, and heated again from 0 °C to 250 °C.
All heating and cooling rates were 10 °C/min.
1.0
st
Polymer B5
1 Heating
Cooling
nd
2 Heating
Exothermic
0.8
0.6
0.4
0.2
138 °C
0.0
50
75
100
125
150
175
200
Temperature (°C)
Figure S22. Differential scanning calorimetry (DSC) traces of terpolymer A5, recorded under nitrogen. The
polymer was first heated from 25 °C to 200 °C, cooled from 200 °C to 0 °C, and heated again from 0 °C to 250 °C.
All heating and cooling rates were 10 °C/min.
S12
100
Weight (%)
75
50
25
0
50
100
150
200
250
300
350
400
450
500
Temperature (°C)
Figure S23. Thermogravimetric analyses (TGA) trace of mPH3POH. The TGA experiment was conducted under N2.
100
Weight (%)
75
50
25
0
100
200
300
400
500
Temperature (°C)
Figure S24. Thermogravimetric analyses (TGA) trace of mPH3PMA. TGA experiment was conducted under N2.
S13
Absorption and emission spectra of terpolymers
0.5
PdmPH3PMA
A1
A2
A3
A4
A5
Absorption
0.4
0.3
0.2
0.1
0.0
400
425
450
475
500
525
550
575
600
Wavelength (nm)
Figure S25. Absorption spectra of solutions of PdmPH3PMA (9.7 µM) and terpolymers Series A (0.496 g/L, 1.21
g/L, 1.991 g/L, 2.230 g/L, and 3.172 g/L, respectively) in toluene. The PdmPH3PMA content in the terpolymers was
determined from the absorption at 530 nm, the concentration of the solution, and ε of PdmPH3PMA (28890
mol/L/cm at 530 nm in THF) and approximately equal to 0.73 wt%, 0.11 wt%, 0.05 wt%, 0.45 wt%, and 0.12 wt%.
Normalized Absorption
1.0
Series A
A1
A2
A3
A4
A5
0.8
0.6
0.4
0.2
0.0
300
400
500
600
Wavelength (nm)
Figure S26. Normalized absorption spectra of terpolymers Series A (0.12 mg/mL in toluene). No baseline
correction was applied.
S14
Emission Intensity (count/s)
2.5x10
6
2.0x10
6
1.5x10
6
1.0x10
6
5.0x10
5
A1
A2
A3
A4
A5
0.0
400
420
440
460
480
500
520
540
Wavelength (nm)
Figure S27. Emission intensity of solution-cast films of terpolymer Series A as function of PdmPH3P content. The
films had a thickness of ca. 80 m and the samples were excited at 375 nm.
1.0
A1
A2
A3
A4
A5
Absorption
0.8
0.6
0.4
(b)
0.35
0.30
Absorption
(a)
0.25
0.20
0.15
0.10
0.2
0.05
0.0
450
500
550
Wavelength (nm)
600
650
0.00
0.02
0.04
0.06
0.08
0.10
0.12
PdmPH3P content (wt%)
Figure S28. (a) Absorption spectra of solution-cast films of terpolymer Series A. The films had a thickness of ca.
80 m. (b) Absorbance of the β Q-band of Series A as a function of PdmPH3P content.
S15
Emission Intensity (count/s)
4x10
5
3x10
5
2x10
5
1x10
5
0
550
600
650
700
750
Wavelength (nm)
Figure S29. Phosphorescence spectrum of PdmPH3PMA crystals recorded upon excitation at 532 nm. The spectrum
shows two phosphorescence bands with maxima at 630 and 740 nm.
A1
A2
A3
A4
A5
Absorption
0.8
0.6
0.4
(b)
0.7
0.6
Absorption
1.0
(a)
0.5
0.4
0.3
0.2
0.2
0.1
0.0
425 450 475 500 525 550 575 600 625 650
Wavelength (nm)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
PdmPH3P content (wt%)
Figure S30. (a) Absorption spectra of solution-cast films of terpolymer Series B. The films had a thickness of ca. 80
m. (b) Absorbance of the β Q-band of Series B as a function of PdmPH3P content.
S16