This journal is The Royal Society of Chemistry 213 Electronic Supplementary Information for Zinc(II) tetraphenyltetrabenzoporphyrin complex as triplet photosensitizer for triplet-triplet annihilation upconversion Xiaoneng Cui, Jianzhang Zhao,* Pei Yang and Jifu Sun State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-28 West Campus, 2 Ling-Gong Road, Dalian 11624, P. R. China. E-mail : zhaojzh@dlut.edu.cn Web : http://finechem.dlut.edu.cn/photochem General information. S2 Synthesis of compound Zn TPTBP, H 2 TPTBP, Pd TPTBP and A-1... S3 Fig. S1-S2 NMR spectra of ZnTPTBP and MS of ZnTPTBP.. S5 Fig. S3-S4 NMR spectra of H 2 TPTBP and MS of H 2 TPTBP.. S6 Fig. S5-S6 NMR spectra of PdTPTBP and MS of PdTPTBP S7 Fig. S7-S8 NMR and MS spectra of A-1 S8 Fig. S9-S12 77 K emission spectra and Luminescence spectra in N 2 S1 Fig. S13-S16 Transient absorption spectra...... S11 Fig. S17-S22 Delayed fluorescence S13 Fig. S23-S24 Upconversion details of H 2 TPTBP and PdTPTBP..... S15 Fig. S25 Stern Volmer Plot for the quenching of the lifetime... S17 Fig. S26 Time-resolved emission spectra (TRES) of H 2 TPTBP. S18 Fig. S27 Time-resolved emission spectra (TRES) of PdTPTBP... S19 S1
This journal is The Royal Society of Chemistry 213 1. Experimental Section General information All the chemicals used in synthesis are analytical pure and were used as received. Solvents were dried and distilled before used for synthesis. 1 H and 13 C NMR spectra were recorded on a 4 MHz Varian Unity Inova spectrometer (TMS as the standard of the chemical shifts). The mass spectra were measured by a MALDI and ESI Micro MS spectrometer. UV-vis absorption spectra were taken on a HP8453 UV-visible spectrophotometer. Photoluminescence spectra were recorded on a Shimadzu RF 531PC spectrofluorometer. Luminescence lifetimes were measured on a OB 92 fluorescence/phosphorescence lifetime instrument. The nanosecond time-resolved transient difference absorption spectra were detected by Edinburgh LP92 instruments (Edinburgh Instruments, UK). The signal was buffered on a Tektronix TDS 312B oscilloscope and was analyzed by the LP9 software. Fluorescence quantum yields were measured with DCM (4-dicyanomethylene-6-(p-dimethylaminostyryl)-2-methyl- 4H-pyran) as the standard (Φ F =.1 in CH 2 Cl 2 ). A laser diode (continuous laser, 654 nm,12 mw, 95.5 mw cm -2 ) was used as the excitation source for the upconversion. The power of the laser beam was measured with VLP-2 pyroelectric laser power meter. For the upconversion experiments, the mixed solution of the compound (triplet photosensitizers) and the triplet acceptors was degassed with N 2 for at least 15 min. The steady state upconverted fluorescence was recorded with a RF 531PC spectrofluorometer. In order to repress the laser scattering, a small black box was put behind the fluorescent cuvette as beam dump to trap the laser. The upconversion quantum yields (Φ UC ) of ZnTPTBP, H 2 TPTBP and PdTPTBP were determined with the prompt fluorescence of the free porphyrin H 2 TPTBP as the inner standard, e.g. The upconversion quantum yields were calculated with the following equation (Eq. 1), where Φ UC, A sam and I sam represents the quantum yield, absorbance, integrated photoluminescence intensity and the refractive index of the samples. η sam represents the diffraction index used for the samples, symbols with std stand the corresponding parameter for the standard (Eq. 1) (Eq. 1) The delayed fluorescence of the upconversion was measured with a nanosecond pulsed laser (Opolette TM 355II+UV nanosecond pulsed laser, typical pulse length: 7 ns. Pulse repetition: 2 Hz. Peak OPO energy: 4 mj. The wavelength is tunable in the range of 21 355 nm and 41 22 nm. OPOTEK, USA), which is synchronized to FLS 92 spectrofluorometer (Edinburgh Instruments, UK). The pulsed laser is sufficient to sensitize the TTA upconversion. The decay kinetics of the upconverted fluorescence (delayed fluorescence) was monitored with an FLS92 spectrofluorometer (synchronized to the OPO nanosecond pulse laser). The prompt fluorescence lifetime of the triplet acceptor A-1 was measured with EPL picosecond pulsed laser (45 nm, 45 ±1 nm, pulse width: 66.9 ps, maximum average power: 5 mw; Edinburgh Instrument Ltd., UK) which was synchronized to the FLS 92 spectrofluorometer. Φ 2 A std I sam η sam sam = 2Φstd Asam Istd ηstd S2
This journal is The Royal Society of Chemistry 213 Synthesis of compounds ZnTPTBP, H2TPTBP, PdTPTBP and A-1 O NH O COOH Zn(PhAcO) 2 36 C Zn CH 2 Cl 2 HCl NH N N HN Zn TPTBP H 2 TPTBP Pd(OAc) 2 CH 2 Cl 2 /DMF Pd Pd TPTBP B F F A-1 Scheme S1. Synthesis of meso-tetraphenyltetrabenzoporphyrin compounds of PdTPTBP, H 2 TPTBP, ZnTPTPB. The molecular structure of triplet acceptor A-1 used in the TTA upconversion studies is also presented. Zn TPTBP, H 2 TPTBP and Pd TPTBP were synthesized according to a modified literature method. 1 Synthesis of Zinc phenylacetate: Sodium hydroxide (2.32 g,.58 mol), phenylacetic acid (7.76 g,.58 mol) and 4 ml water were mixed together, the ph value was adjusted to 8.. Then ZnCl 2 (4.9 g,.3 mol) was dissolved in a small amount of water and the ph value was adjusted to 3.. With the exchange reaction between sodium phenylacetate and ZnCl 2, Zinc phenylacetate was obtained as a white precipitate. The product was isolated by filtration and the product was used without further purification. Yield: 8.59 g (89.8%). Synthesis of ZnTPTBP : The preparation followed a reported method. 1 Under N 2 atmosphere, phthalimide (1.47 g, 1. mmol), phenylacetic acid (1.8 g, 13.3 mmol) and Zinc phenylacetate (.84 g, 2.5 mmol) were ground in a mortar and loaded into a 5 ml round-bottom flask. The mixture was melted and stirred for 1 h at 36 C until the color turned dark green. The melt was collected and washed with water (2 1 ml) and dried over Na 2 SO 4. The product was dissolved in toluene and purified on column chromatography( Al 2 O 3 ). The column was elutated firstly with toluene/hexane (2:1, v/v) and then with toluene to remove the yellow and the red fractions. Finally, CH 2 Cl 2 containing 1.5% tetrahydrofuran was used to elute the desired product. Yield: 45. mg (18.5 %). 1 H NMR (DMSO-d 6, 4 MHz): δ 8.27 (d, 8H, J = 7.2 Hz), 8.3 (d, 4H, J = 8. Hz), 7.96 (t, 8H, J = 16. Hz), 7.28 7.24 (m, 8H), 1. S. M. Borisov, I. Klimant, Dyes and Pigm. 29, 83, 312 316. S3
This journal is The Royal Society of Chemistry 213 7.8 7.5 (m, 8H). MALDI-HRMS: Calcd ([C 6 H 36 N 4 Zn] + ) m/z 876.22314, found m/z 876.2222. Other peaks: m/z 966.278(ZnTPTBP+C 7 H 7 )) and m/z 156.365 (ZnTPTBP+2(C 7 H 7 )). 1 Synthesis of H 2 TPTBP: The preparation followed a reported method. 1 ZnTPTBP (5. mg,.57 mmol) was dissolved in CH 2 Cl 2 (2 ml) and then 15 ml of hydrochloride acid (HCl:H 2 O = 1:2, v/v) was added. The solution was stirred for 3 min. Water (1 ml) was added in the mixture. The mixture was extracted with CH 2 Cl 2 (3 3 ml). The solvent was evaporated under reduced pressure, the solid was washed thoroughly with water and dried under vacuum. The crude product was purified with column chromatography (silica gel, CH 2 Cl 2 ) to give dark-green powder. Yield: 22.3 mg (48. %). 1 H NMR (4 MHz, DMSO-d 6, ): δ 8.33 (d, 8H, J = 5.6 Hz ), 8.5 (t, 4H, J = 16. Hz ), 7.97 (t, 8H, J = 16. Hz), 7.33 7. (m, 16H), 1.7 (s, 2H). MALDI-HRMS: Calcd ([C 6 H 38 N 4 +H + ] + ), m/z 814.397, found, m/z 815.3129. Other peaks: m/z 95.3795(TPTBP+C 7 H 7 ) and m/z 995.4377 (TPTBP+(C 7 H 7 ) 2 ). 1 Synthesis of PdTPTBP: The preparation followed a reported method. 1 Under nitrogen atmosphere, H 2 TPTBP (3.3 mg,.37 mmol) was dissolved in 2 ml solution ( CH 2 Cl 2 :DMF = 1:3, v/v). Then Pd(OAc) 2 (24.8 mg,.11 mmol) was added. The reaction mixture was refluxed at 15 C and stirred for 45 min until the UV-Vis absorption spectrum indicated the reaction was finished. The weak absorption at 633 nm disappeared and a new strong absorption at 628 nm emerged. In toluene). After completion of the reaction, the mixture was cooled to r. t. The mixture was evaporated to dryness under reduced pressure, then washed with hot water. The solid was dried under vacuum. The product was dissolved in toluene and purified by column chromatography (Al 2 O 3, toluene/hexane, 1:1, v/v). Yield: 16.3 mg (47.9 %). 1 H NMR ( 4 MHz. DMSO-d 6 ): δ 8.25 (d, 8 H, J = 7.2 Hz), 8.4 (d, 4 H, J = 7.2 Hz), 7.97 (t, 8 H, J = 14. Hz), 7.3 7.28 (m, 8 H), 7.6 7.3 (m, 8 H). MALDI-HRMS: Calcd ([C 6 H 36 N 4 Pd] + ), m/z 918.1975, found, m/z 918.238. Other peaks: m/z 18.281 (ZnTPTBP+C 7 H 7 ) and m/z 111.2496(ZnTPTBP+(C 7 H 7 ) 2 ). 1 Synthesis of A-1 : A-1 were synthesized by a modified literature method. 2 Orange power was obtained. Yield (28. mg, 51.2%). 1 H NMR (CDCl 3, 4 MHz): δ 8.28 (d, 2H, J = 7.6 Hz), 8.24 (d, 2H, J = 6.8 Hz), 7.73 (d, 3H, J = 7.6 Hz), 7.66 (d, 2H, J = 7.6 Hz), 7.53 7.42(m, 6H), 2.57 (s, 6H), 2.38 (q, 4H, J = 6.8 Hz), 1.48 (s, 6H), 1.4 (t, 6H, J = 14.4 Hz). EI-HRMS: Calcd ([C 43 H 37 BN 2 F 2 ] + ), m/z 63.318, found, m/z 63.326. 2 A. Turshatov, D. Busko, Y. Avlasevich, T. Miteva, K. Landfester, S. Baluschev, ChemPhysChem. 212, 13, 3112 3115. S4
This journal is The Royal Society of Chemistry 213 2. NMR and MS spectra Zn 8. 4.16 8.5 7.82 7.96 8. 7.5 7. 8.27 8.26 7.96 7.94 7.27 7.25 7.24 7.8 7.7 7.6 7.5 3.35 2.5. 8.27 8.26 8.3 8.1 7.96 7.94 7.92 7.28 7.27 7.25 7.24 7.8 7.7 7.6 7.5 8.5 7.96 8 7 6 5 4 3 2 1 Fig. S1 1 H NMR spectra of Zn TPTBP (4 MHz, DMSO-d 6 ). ppm 12121415 33 (1.1) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (32:33) 1 876.2222 1.25e3 878.2219 88.2179 Zn % 966.278 967.2727 97.2668 971.2658 856.6871 156.365 522.659 16.393 74.8444 787.1327 5 6 7 8 9 1 11 12 13 14 m/z Fig. S2 MALDI-HRMS of ZnTPTBP. S5
This journal is The Royal Society of Chemistry 213 NH N N HN 8. 4.7 8.3 8.9 7.97 8. 7.5 7. 8.33 8.31 8.3 7.97 7.95 7.93 7.33 7.21 7.14 7.7 3.31 2.51-1.7 8.33 8.31 8.5 8.3 8.1 7.97 7.95 7.93 7.33 7.21 7.14 7.7 7. 8.3 8.9 1.98 8 7 6 5 4 3 2 1-1 ppm Fig. S3 1 H NMR spectra of H 2 TPTBP (4 MHz, DMSO-d 6 ) 12121416 61 (2.33) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (61:63) 815.3129 1 1.2e3 816.3195 814.385 NH N % N HN 95.3795 512.795 96.391 586.1387 813.371 995.4377 613.1314 996.4348 186.5464 1286.7171326.3225 5 6 7 8 9 1 11 12 13 14 m/z Fig. S4 MALDI-HRMS of H 2 TPTBP. S6
This journal is The Royal Society of Chemistry 213 Pd 8. 3.99 7.8 7.9 7.91 8. 7.5 7. 8.25 8.23 7.95 7.3 7.29 7.28 7.28 7.6 7.5 7.4 3.33 2.5. 8.25 8.23 8.4 8.2 7.97 7.95 7.93 7.3 7.29 7.28 7.28 7.6 7.5 7.4 7.3 8. 7.91 8 7 6 5 4 3 2 1 ppm Fig. S5 1 H NMR spectra of Pd TPTBP (4 MHz, DMSO-d 6 ). 1212214 14 (.465) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (14:16) 918.238 1 1.4e3 92.2122 917.278 % 921.2146 922.2195 Pd 829.1613 828.1548 916.2133 923.2191 18.281 11.2919 111.36 827.1326 113.332 543.9929 748.153 111.2496 5 6 7 8 9 1 11 12 13 14 m/z Fig. S6 MALDI-HRMS of Pd TPTBP. S7
This journal is The Royal Society of Chemistry 213 8.28 8.26 8.24 8.23 7.73 7.71 7.66 7.64 7.53 7.51 7.49 7.47 7.44 7.42 7.26 4. 3.1 2.14 6.8 N B N 8. 7.5 F F 8.26 8.24 7.73 7.71 7.66 7.64 7.51 7.49 7.44 7.26 2.57 2.38 2.36 2.34 2.32 1.48 1.4 1.2 1.1. 4. 6.8 5.96 6.2 6.4 8 7 6 5 4 3 2 1 ppm Fig. S7 1 H NMR spectra of A-1 (4 MHz, CDCl 3 ). zjz121215-1 424 (7.67) Cm (424-77:85) 1 615.289 63.326 TOF MS EI+ 2.93e3 % N B N 631.355 F F 68.2815 632.365 37.6398 94.9979 163.672 282.113 385.899 595.2746 461.26 634.311 716.7413 5 1 15 2 25 3 35 4 45 5 55 6 65 7 75 8 m/z Fig. S8 EI-HRMS of A-1. S8
This journal is The Royal Society of Chemistry 213 12 Intensity / a.u. 8 4 Pd TPTBP H 2 TPTBP Zn TPTBP 6 65 7 75 8 85 Fig. S9 Emission spectra of ZnTPTBP, H 2 TPTBP and Pd TPTBP in ethanol-methanol (4:1, V/V) glass at 77 K. Excitation wavelength: 441 nm. c = 1. 1-5 M. 12 Intensity / a.u. 8 4 77 K 293 K 65 7 75 8 85 * Fig. S1 Emission spectra of ZnTPTBP in ethanol-methanol (4:1, v/v) glass at 77 K and in solution at 293 K. Excitation wavelength was 441 nm. c = 1. 1-5 M. The asterisk indicated the phosphorescence. S9
This journal is The Royal Society of Chemistry 213 4 Intensity / a.u. 3 2 1 Air N 2 6 66 72 78 84 Fig. S11 Luminescence spectrum of the compounds H 2 TPTBP in N 2 or air-saturated solutions. λ ex = 441 nm. c = 1. 1-5 M, in deaerated toluene. 2 C. Intensity 8. 6. 4. 2. air N 2 a Intensity 12. 9. 6. 3. b air N 2. 65 7 75 8 85. 6 7 8 9 Fig. S12 Luminescence spectra of (a) ZnTPTBP and (b) PdTPTBP λ ex = 441 nm. in N 2 or air-saturated toluene (1. 1-5 M; 2 C). The emission band in (b) at 638 nm is known. S1
This journal is The Royal Society of Chemistry 213 Δ O. D..5. -.5 -.1 24 ns 2266 ns...... 133 ns ns -.15 4 5 6 7 a Δ O. D..5. -.5 -.1 -.15 -.2 b τ T = 55 ns 25 5 75 1 Time / ns Fig. S13 (a) Nanosecond time-resolved transient difference absorption spectra of ZnTPTBP, (b) decay trace at 47 nm. Excited with 532 nm nanosecond pulsed laser excitation. In aerated toluene (c = 1. 1-5 M, 2 C)..1.5. -.5 -.1 475 ns 45 ns...... 25 ns ns a 4 5 6 7.12.9.6.3. b τ = 873 ns 2 4 6 81 Time / ns Fig. S14 (a) Nanosecond time-resolved transient difference absorption spectra of PdTPTBP, (b) decay trace at 51 nm; Excited with 532 nm nanosecond pulsed laser excitation. In aerated toluene (c = 1. 1-5 M, 2 C). S11
This journal is The Royal Society of Chemistry 213 Δ O. D..1 a. -.1 -.2 294 μs 288 μs...... 6 μs μs -.3 4 5 6 7 Δ O. D..12.8.4. b τ T = 137 μs 2 4 6 8 1 Time / μs Fig. S15 (a) Nanosecond time-resolved transient difference absorption spectra of H 2 TPTBP, (b) decay trace at 51 nm; With 532 nm nanosecond pulsed laser excitation. In deaerated toluene (c = 1. 1-5 M, 2 C). Δ O. D..1. -.1 -.2 15 ns 144ns...... 6 ns ns a Δ O. D. 4 5 6 7.12.8.4. 15 3 45 6 Time / ns b τ T = 236 ns Fig. S16 (a) Nanosecond time-resolved transient difference absorption spectra of H 2 TPTBP, (b) decay trace at 51 nm; With 532 nm nanosecond pulsed laser excitation. In toluene (c = 1. 1-5 M, 2 C). S12
This journal is The Royal Society of Chemistry 213 1 1 1 a τ DF = 159.7 μs 1 5 1 15 2 Time / μs 1 1 Fig. S17 (a) Delayed fluorescence observed in the TTA upconversion with ZnTPTBP as the triplet photosensitizer and A-2 as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser, synchronized with FLS 92 spectrofluorometer) and the emission was monitored at 45 nm. Under the circumstances, compound ZnTPTBP is selectively excited and the emission is due to the upconverted emission of the triplet acceptor A-2. (b) The decay trace of the prompt fluorescence of A-2 determined in a different experiment (excited with picosecond 45 nm laser; the decay of the emission was monitored at 45 nm). In deaerated toluene; c [Photosensitizer]= 2. 1 6 M; c [Triplet energy acceptor A-2]= 4. 1 5 M; 2 C. 1 b τ PF = 4.3 ns 2 4 6 8 1 Time / ns 1 a τ DF = 184.4 μs 1 1 1 b τ PF = 5.8 ns 1 1 5 1 15 2 Time / μs 2 4 6 8 1 Time / ns Fig. S18 (a) Delayed fluorescence observed in the TTA upconversion with ZnTPTBP as the triplet photosensitizer and A-1 as the triplet energy acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with FLS 92 spectrofluorometer) and the emission was monitored at 545 nm. Under the circumstances, ZnTPTBP was selectively excited and the emission is due to the upconverted emission of the triplet acceptor A-1. (b) The decay trace of the prompt fluorescence of A-1 determined in a different experiment (excited with 45 nm picosecond pulsed laser; the decay of the emission was monitored at 545 nm). In deaerated toluene; c[triplet photosensitizers]= 2. 1 6 M; c [Acceptor A-1] = 4. 1 5 M; 2 C. S13
This journal is The Royal Society of Chemistry 213 1 1 1 a τ DF = 114.9 μs 1 1 1 b τ PF = 5.6 ns 1 5 1 15 2 Time / μs 2 4 6 8 1 Time / ns Fig. S19 (a) Delayed fluorescence observed in the TTA upconversion with ZnTPTBP as the triplet photosensitizer and PBI as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with FLS 92 spectrofluorometer) and the emission was monitored at 539 nm. Under the circumstances, ZnTPTBP is selectively excited and the emission is due to the upconverted emission of the triplet acceptor PBI. (b) The prompt fluorescence decay of PBI determined in a different experiment (excited with 45 nm picosecond pulsed laser; the decay of the emission was monitored at 539 nm). In deaerated toluene; c[triplet photosensitizers]= 2. 1 6 M; c [Triplet energy acceptor PBI]= 4. 1 5 M; 2 C. 1 τ DF = 211.4 μs 1 1 5 1 15 2 Time / μs Fig. S2 Delayed fluorescence observed in the TTA upconversion with PdTPTBP as the triplet photosensitizer and A-1 as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with spectrofluorometer) and the emission was monitored at 545nm. Under the circumstances, PdTPTBP is selectively excited and the emission is due to the upconverted emission of triplet acceptor. In deaerated toluene; c[sensitizers]=2. 1 6 M; c [Acceptor] = 4. 1 5 M; 2 C. S14
This journal is The Royal Society of Chemistry 213 1 τ DF = 165.5 μs 1 1 5 1 15 2 Time / μs Fig. S21 Delayed fluorescence observed in the TTA upconversion with PdTPTBP as the triplet photosensitizer and A-2 as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with FLS 92 spectrofluorometer) and the emission was monitored at 45 nm. Under the circumstances, Pd TPTBP is selectively excited and the emission is due to the upconverted emission of triplet acceptor. In deaerated toluene; c[sensitizers]=2. 1 6 M; c [Acceptor] = 4. 1 5 M; 2 C. 1 a 1 b 1 1 τ DF = 86.9 μs 1 1 τ DF = 118.2 μs 1 5 1 15 2 Time / μs 5 1 15 2 Time / μs Fig. S22 Delayed fluorescence observed in the TTA upconversion with compound (a)pd TPTBP and (b)h 2 TPTBP as the triplet photosensitizer and PBI as the triplet acceptor. Excited at 654 nm (nanosecond pulsed OPO laser synchronized with spectrofluorometer) and monitored at 539 nm. Under the circumstances, compound is selectively excited and the emission is due to the upconverted emission of triplet acceptor. In deaerated toluene; c[sensitizers]=2. 1 6 M; c [Acceptor]= 4. 1 5 M; 2 C. S15
This journal is The Royal Society of Chemistry 213 25 2 * Intesity (a.u.) 15 1 5 H2 TPTBP (+ A-1/ A-2) + PBI 5 6 7 8 N B N F F A-1 A-2 O O N O N O PBI Fig. S23 Upconversion of H 2 TPTBP with A-1, A-2 and PBI as the triplet acceptor. Excited with 654 nm laser diode (12 mw, 95.5 mw cm -2 ). In deaerated toluene. c [Sensitizer] = 2. 1-6 M, c [Acceptor] = 4. 1-5 M. 2 C. 4 Intensity / a.u. 3 2 1 (+ A-1) Pd TPTBP * 5 6 7 8 9 Fig. S24 Upconversions with triplet photosensitizer PdTPTBP. A-1 was used as triplet acceptor. Emission of the sensitizers in the presence of triplet acceptor A-1. Excited with 635 nm laser (4.8 mw). c [sensitizer] = 2. 1-6 M; c [A-1] = 4. 1-5 M; in deaerated Toluene, 2 C. S16
This journal is The Royal Society of Chemistry 213 1.2 a Pd TPTBP 6. b Zn TPTBP (τ /τ)-1.8.4 Zn TPTBP (τ /τ)-1 4. 2. Pd TPTBP H 2 TPTBP H 2 TPTBP.. 4.x1-6 8.x1-6 c[a-1] / M.. 5.x1-6 1.x1-5 c[pbi] / M Fig. S25 The Stern-Volmer plot of ZnTPTBP, H 2 TPTBP and PdTPTBP with (a) A-1 and (b) PBI as the triplet acceptor. c [Sensitizer] = 2. 1-6 M. In deaerated toluene. 2 C. Note the quenching was determined with A-1 at low concentration. S17
Electronic Supplementary Material (ESI) for Chemical Communications This journal is The Royal Society of Chemistry 213.).u PL Intensity (a m /n th av el en g 4 3 2 1 Tim e/μ s (b) 5 4 3 2 1 Tim e/μ s W th ng e el av m /n W 5 18 16 14 12 1 8 6 4 2 85 8 75 7 5 6 6 5 5 5.u.) PL Intensity (a (a) 85 8 75 7 65 6 35 3 25 2 15 1 5 Fig. S26 Time-resolved emission spectra (TRES) of the TTA upconversion with H2TPTBP as the triplet photosensitizer and PBI as the triplet acceptor. (a) H2TPTBP alone, τf= 1.6 μs (λem = 7 nm), which is the delayed fluorescence of H2TPTBP. (b) H2TPTBP/PBI upconversion mixture, τdf = 122.4 μs (λem= 54 nm). Time-resolved emission spectra and intensity decays were recorded using emission mode. The samples were excited using nanosecond pulsed OPO laser (654 nm) c [Photosensitizer] = 2. 1-6 M. c [PBI] = 4. 1-5 M. In deaerated toluene. 2 C. S18
Electronic Supplementary Material (ESI) for Chemical Communications This journal is The Royal Society of Chemistry 213 (a) 6 (b) 4 6 4 2 8 7 6 5 4 3 2 1 Time / μs /n m W av ele ng th 6 5 4 3 2 1 Time / μs 8 8 4 82 7 76 8 74 72 7 /n 2 W av el en gt h 8.u.) PL Intensity (a 1 8 85 8 5 7 7 5 6 6 55 5.u.) PL Intensity (a 12 Fig. S27 Time-resolved emission spectra (TRES) of the TTA UC with A-1 as triplet acceptor. (a) PdTPTBP alone. τp = 223.7 μs (λem= 79 nm). (b) PdTPTBP/A-1, τdf = 22.5 μs (λem= 55 nm). Excited using nanosecond pulsed OPO laser (654 nm). c [Photosensitizers] = 2. 1-6 M. c [A-1] = 4. 1-5 M in deaerated toluene; 2 C. S19