Supporting Information UV-Irradiation-Enhanced Photoluminescence ...
Supporting Information UV-Irradiation-Enhanced Photoluminescence Emission of Polyfluorenes Containing Heterocyclic Benzo[c]cinnoline Moieties
Hsin-Chung Wu, Jyh-Chien Chen,* Hong-Ze Lin, Department of Materials Science and Engineering, National Taiwan University of Science and Technology, No. 43 Sec. 4 Keelung Rd., Taipei, 10607, Taiwan
Corresponding Author: Jyh-Chien Chen Department of Materials Science and Engineering, National Taiwan University of Science and Technology, No. 43 Sec. 4 Keelung Rd., Taipei, 106 , Taiwan TEL:+886-2-27376526 FAX:+886-2-27376544 E-mail: [email protected]
Measurements Proton (1H NMR) nuclear magnetic resonance spectra were measured at 600 MHz on a Bruker Avance-500 spectrometer. Molecular weights were measured on an ACQUITY Advanced Polymer ChromatographyTM (APCTM) System equipped with an RI detector (ACQ-RI), a ACQUITY APC XT 200 and 450 column (150 mm × 4.6 mm and 30 mm × 4.6 mm), using tetrahydrofuran (THF) as the eluent and calibrated with polystyrene standards. ACQUITY APCTM System contains smaller and higher pore volume hybrid particles in column, which provides significant gains in stability, flexibility and faster separations. Infrared spectra were obtained with a Digilab-FTS1000 FTIR. Thermal gravimetric analyses (TGA) were performed in nitrogen with a TA TGA Q500 thermogravimetric analyzer using a heating rate of 20 °C min-1. Differential scanning calorimetry (DSC) measurements were carried out under N2 atmosphere using a Perkin-Elmer DSC 4000 analyzer at a heating rate of 10 °C min-1. Cyclic voltammetric (CV) measurements were carried out on a CH Instrument 611C electrochemical analyzer at room temperature in a three-electrode electrochemical cell with a working electrode (polymer films coated on ITO glass), a reference electrode (Ag/Ag+, referenced against ferrocene/ferrocium (Fc/Fc+), 0.09 V), and a counter electrode (Pt gauze) at a scan rate of 100 mV s-1. CV measurements for polymer films were performed in an electrolyte solution of 0.1 M tetrabutylammonium perchlorate (TBAP) in acetonitrile. The potential window at oxidative and reductive scans were 0 to 1.7 V and 0 to -2.5 V, respectively. UV-vis spectrometry was carried out on a Cary-100 UV-vis spectrometer. Photoluminescence (PL) measurements were carried out on a Jasco (FP-8500) spectrofluorometer. PL quantum yield (ΦPL) of the polymer in THF was measured by using 2 × 10-5 M quinine sulfate in 1 N H2SO4 as reference standard (ΦPL = 0.546). The UV oven equipped with eight mercury lamps (352 nm, 8 W) was used for UV-irradiation. UV light with a wavelength of 365 nm was used for the investigation on the relationship between UV 1
doses and PL quantum yield. The intensity of UV light was manipulated by PINTEK PW-3033R power supply, and measured by Lutron UV-340A UV light meter. UV doses were calculated by UV intensity (µW cm-2) and irradiation time.
2
1
H NMR of monomers and polymers.
Figure S1. 1H NMR spectra of 3,8-dibromobenzo[c]cinnoline (1) in DMSO-d6.
Figure S2. 1H NMR spectra of 2,7-dibromo-9,9-dioctylfluorene (2) in DMSO-d6.
3
Figure S3. 1H NMR spectra of 2,7-di(9,9-dioctyl-9H-fluoren-2yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (3) in CDCl3.
Figure S4. 1H NMR spectra of PFO in CDCl3.
4
Figure S5. 1H NMR spectra of BF10 in CDCl3.
Figure S6. 1H NMR spectra of BF25 in CDCl3.
5
Figure S7. 1H NMR spectra of BF50 in CDCl3.
6
Identification of FBF
Figure S8. 1H 1H COSY spectra of FBF. 7
Thermal properties of polymers
Figure S9. TGA thermograms and DSC curves (inset) of polymers.
8
Redox Behavior Characterized by Cyclic Voltammetry
Figure S10. Cyclic voltammograms of polymer films on ITO-coated glasses in CH3CN containing 0.1M TBAP.
9
Optical properties of solid state
Figure S11. UV-visible absorption spectra and PL emission spectra of films of polymers excited by λmaxUV.
10
PL spectra of polymer and FBF solutions with different UV irradiation time
Figure S12. PL emission spectra of FBF in THF at 2 × 10-5 M with different UV irradiation time.
11
Figure S13. PL emission spectra of (a) PFO in THF, (b) BF10 in THF, (c) BF25 in THF, (d) BF50 in NMP, (e) BF50 in CHCl3, and (f) BF50 in toluene (2 × 10-5 M) with different UV irradiation time. 12
PL spectra of polymer solutions at different concentrations with different UV irradiation time
Figure S14. PL emission spectra of BF50 in THF at 2 × 10-4 M with different UV irradiation time.
Figure S15. PL emission spectra of BF50 in THF 2 × 10-3 M with different UV irradiation time. 13
Comparison of the wavenumbers of carbonyl group in IR spectra Table S1. The Carbonyl Group Wavenumbers of Fluorene Analogs Chemical Structure
O
O
IR (cm-1)
Ref.
1660
1
1645
2
1663
2
1675
3
1721
4
O
O
O
O
References: 1.
Anastassiou, A. G.; Kasmai, H. S.; Saadein, M. R. Helv. Chim. Acta 1981, 64, 617.
2.
Nagasawa, H. T.; Gutmann, H. R. J. Med. Chem. 1966, 9, 719.
3.
Malthete, J.; Canceill, J.; Gabard, J.; Jacques, J. Tetrahedron 1981, 37, 2823.
4.
List, E. J. W.; Guentner, R.; Scanducci de Freitas, P.; Scherf, U. Adv. Mater. 2002, 14, 374.
14
Molecular weights of irradiated BF50 solution The molecular weights of pristine and UV-irradiated (30 and 60 min) BF50 were measured. The results are shown in the Table S2. The molecular weights barely change. It means that BF50 in solution are still intact and photo-oxidation by UV irradiation does not lead to chain scission.
Table S2. Molecular Weights of BF50 with Different UV Irradiation Time Time Mna Mwa PDIa -1 (min) g mol g mol-1 0 10,000 18,000 1.81 30 10,000 18,000 1.83 60 10,000 17,000 1.67 a TM Soluble part obtained from APC system using THF as solvent and calibrated with polystyrene standards.
15
UV irradiation under nitrogen condition BF50 in THF (2 × 10-5 M) was exposed to UV light under nitrogen condition. In order to exclude oxygen, the solvent, THF, was purged by nitrogen for 60 min before using. UV oven and cell holder of spectrometer were also purged by nitrogen for 60 min before using. The nitrogen gas was kept purging during irradiation or PL measurement. The PL spectra of BF50 solution
irradiated
under
nitrogen
is
shown
in
Figure
S16.
No
discernible
UV-irradiation-enhanced PL emission was observed when BF50 was UV-irradiated under nitrogen atmosphere, compared with the obvious PL enhancement when BF50 was irradiated in air.
Figure S16. PL emission spectra of BF50 in THF (2 × 10-5 M) and BF50 in THF (2 × 10-5 M) irradiated (30 min) under air and nitrogen conditions.
16
Additions of compounds with different pKa
Figure S17. PL emission spectra of UV-irradiated (30 min) BF50 in THF (2 × 10-5 M) with different amount of acetic acid.
Figure S18. PL emission spectra of UV-irradiated (30 min) BF50 in THF (2 × 10-5 M) with different amount of TEA. 17
Hsin-Chung Wu, Jyh-Chien Chen,* Hong-Ze Lin, Department of Materials Science and Engineering, National Taiwan University of Science and Technology, No. 43 Sec. 4 Keelung Rd., Taipei, 10607, Taiwan
Corresponding Author: Jyh-Chien Chen Department of Materials Science and Engineering, National Taiwan University of Science and Technology, No. 43 Sec. 4 Keelung Rd., Taipei, 106 , Taiwan TEL:+886-2-27376526 FAX:+886-2-27376544 E-mail: [email protected]
Measurements Proton (1H NMR) nuclear magnetic resonance spectra were measured at 600 MHz on a Bruker Avance-500 spectrometer. Molecular weights were measured on an ACQUITY Advanced Polymer ChromatographyTM (APCTM) System equipped with an RI detector (ACQ-RI), a ACQUITY APC XT 200 and 450 column (150 mm × 4.6 mm and 30 mm × 4.6 mm), using tetrahydrofuran (THF) as the eluent and calibrated with polystyrene standards. ACQUITY APCTM System contains smaller and higher pore volume hybrid particles in column, which provides significant gains in stability, flexibility and faster separations. Infrared spectra were obtained with a Digilab-FTS1000 FTIR. Thermal gravimetric analyses (TGA) were performed in nitrogen with a TA TGA Q500 thermogravimetric analyzer using a heating rate of 20 °C min-1. Differential scanning calorimetry (DSC) measurements were carried out under N2 atmosphere using a Perkin-Elmer DSC 4000 analyzer at a heating rate of 10 °C min-1. Cyclic voltammetric (CV) measurements were carried out on a CH Instrument 611C electrochemical analyzer at room temperature in a three-electrode electrochemical cell with a working electrode (polymer films coated on ITO glass), a reference electrode (Ag/Ag+, referenced against ferrocene/ferrocium (Fc/Fc+), 0.09 V), and a counter electrode (Pt gauze) at a scan rate of 100 mV s-1. CV measurements for polymer films were performed in an electrolyte solution of 0.1 M tetrabutylammonium perchlorate (TBAP) in acetonitrile. The potential window at oxidative and reductive scans were 0 to 1.7 V and 0 to -2.5 V, respectively. UV-vis spectrometry was carried out on a Cary-100 UV-vis spectrometer. Photoluminescence (PL) measurements were carried out on a Jasco (FP-8500) spectrofluorometer. PL quantum yield (ΦPL) of the polymer in THF was measured by using 2 × 10-5 M quinine sulfate in 1 N H2SO4 as reference standard (ΦPL = 0.546). The UV oven equipped with eight mercury lamps (352 nm, 8 W) was used for UV-irradiation. UV light with a wavelength of 365 nm was used for the investigation on the relationship between UV 1
doses and PL quantum yield. The intensity of UV light was manipulated by PINTEK PW-3033R power supply, and measured by Lutron UV-340A UV light meter. UV doses were calculated by UV intensity (µW cm-2) and irradiation time.
2
1
H NMR of monomers and polymers.
Figure S1. 1H NMR spectra of 3,8-dibromobenzo[c]cinnoline (1) in DMSO-d6.
Figure S2. 1H NMR spectra of 2,7-dibromo-9,9-dioctylfluorene (2) in DMSO-d6.
3
Figure S3. 1H NMR spectra of 2,7-di(9,9-dioctyl-9H-fluoren-2yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (3) in CDCl3.
Figure S4. 1H NMR spectra of PFO in CDCl3.
4
Figure S5. 1H NMR spectra of BF10 in CDCl3.
Figure S6. 1H NMR spectra of BF25 in CDCl3.
5
Figure S7. 1H NMR spectra of BF50 in CDCl3.
6
Identification of FBF
Figure S8. 1H 1H COSY spectra of FBF. 7
Thermal properties of polymers
Figure S9. TGA thermograms and DSC curves (inset) of polymers.
8
Redox Behavior Characterized by Cyclic Voltammetry
Figure S10. Cyclic voltammograms of polymer films on ITO-coated glasses in CH3CN containing 0.1M TBAP.
9
Optical properties of solid state
Figure S11. UV-visible absorption spectra and PL emission spectra of films of polymers excited by λmaxUV.
10
PL spectra of polymer and FBF solutions with different UV irradiation time
Figure S12. PL emission spectra of FBF in THF at 2 × 10-5 M with different UV irradiation time.
11
Figure S13. PL emission spectra of (a) PFO in THF, (b) BF10 in THF, (c) BF25 in THF, (d) BF50 in NMP, (e) BF50 in CHCl3, and (f) BF50 in toluene (2 × 10-5 M) with different UV irradiation time. 12
PL spectra of polymer solutions at different concentrations with different UV irradiation time
Figure S14. PL emission spectra of BF50 in THF at 2 × 10-4 M with different UV irradiation time.
Figure S15. PL emission spectra of BF50 in THF 2 × 10-3 M with different UV irradiation time. 13
Comparison of the wavenumbers of carbonyl group in IR spectra Table S1. The Carbonyl Group Wavenumbers of Fluorene Analogs Chemical Structure
O
O
IR (cm-1)
Ref.
1660
1
1645
2
1663
2
1675
3
1721
4
O
O
O
O
References: 1.
Anastassiou, A. G.; Kasmai, H. S.; Saadein, M. R. Helv. Chim. Acta 1981, 64, 617.
2.
Nagasawa, H. T.; Gutmann, H. R. J. Med. Chem. 1966, 9, 719.
3.
Malthete, J.; Canceill, J.; Gabard, J.; Jacques, J. Tetrahedron 1981, 37, 2823.
4.
List, E. J. W.; Guentner, R.; Scanducci de Freitas, P.; Scherf, U. Adv. Mater. 2002, 14, 374.
14
Molecular weights of irradiated BF50 solution The molecular weights of pristine and UV-irradiated (30 and 60 min) BF50 were measured. The results are shown in the Table S2. The molecular weights barely change. It means that BF50 in solution are still intact and photo-oxidation by UV irradiation does not lead to chain scission.
Table S2. Molecular Weights of BF50 with Different UV Irradiation Time Time Mna Mwa PDIa -1 (min) g mol g mol-1 0 10,000 18,000 1.81 30 10,000 18,000 1.83 60 10,000 17,000 1.67 a TM Soluble part obtained from APC system using THF as solvent and calibrated with polystyrene standards.
15
UV irradiation under nitrogen condition BF50 in THF (2 × 10-5 M) was exposed to UV light under nitrogen condition. In order to exclude oxygen, the solvent, THF, was purged by nitrogen for 60 min before using. UV oven and cell holder of spectrometer were also purged by nitrogen for 60 min before using. The nitrogen gas was kept purging during irradiation or PL measurement. The PL spectra of BF50 solution
irradiated
under
nitrogen
is
shown
in
Figure
S16.
No
discernible
UV-irradiation-enhanced PL emission was observed when BF50 was UV-irradiated under nitrogen atmosphere, compared with the obvious PL enhancement when BF50 was irradiated in air.
Figure S16. PL emission spectra of BF50 in THF (2 × 10-5 M) and BF50 in THF (2 × 10-5 M) irradiated (30 min) under air and nitrogen conditions.
16
Additions of compounds with different pKa
Figure S17. PL emission spectra of UV-irradiated (30 min) BF50 in THF (2 × 10-5 M) with different amount of acetic acid.
Figure S18. PL emission spectra of UV-irradiated (30 min) BF50 in THF (2 × 10-5 M) with different amount of TEA. 17
