Supporting nformation for: Organic Triplet Sensitizer Library Derived rom a Single Chromophore (ODPY) with Long-lived Triplet Excited State for Triplet-Triplet-Annihilation ased Upconversion Wanhua Wu, Huimin Guo, Wenting Wu, Shaomin Ji, Jianzhang Zhao* State Key Laboratory of ine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-28 Western Campus, 2 Ling Gong Road, Dalian 11624, P. R. China. Phone/ax: +86 411 8498 6236 *E-mail: zhaojzh@dlut.edu.cn Table of Contents 1. General..S2 2. Synthesis and molecular structure characterization data...s4 3. MR and HRMS spectra......s5 4. Up-conversion details.... S18 5. Transient absorption details...s2 6. Calculation details.s24 7. 77 K emission spectra.s43 8. Stability of the iodinated compounds with irradiation by the sun light.s48 9. Photophysics of the Acceptors.S49 S1
1. General. All the chemicals used in synthesis are analytical pure and were used as received. Solvents were dried and distilled before used for synthesis. luorescence quantum yields were measured with quinine sulfate as the standard (Φ =.547 in.5 M sulfuric acid). All the data were independently measured for three times (with different solutions samples). luorescence lifetimes were measured on a Horiba Jobin Yvon luoro Max-4 (TCSPC) instrument. The nanosecond time-resolved transient absorption spectra were detected by Edinburgh analytical instruments (LP9, Edinburgh nstruments, U.K.) and recorded on a Tektronix TDS 312 oscilloscope. The lifetime values (by monitoring the decay trace of the transients) were obtained with the LP9 software. All samples in flash photolysis experiments were deaerated with argon for ca. 15 min before measurement and the gas flow is kept during the measurement. The upconversion quantum yields (ΦUC) of -1, -2 and -4 were determined with the prompt fluorescence of the sensitizer as the inner standard, e.g. Φ UC of -2 was determined by comparing the upconverted fluorescence and its prompt fluorescence. or -5, -6 and -7, Φ UC was determined with the prompt fluorescence of -5 as the standard. The upconversion quantum yields were calculated with the following equation, where Φ UC, A unk, unk and η unk represents the quantum yield, absorbance, integrated photoluminescence intensity and the refractive index of the samples and the solvents (Eq. 1). The equation is multiplied by factor 2 in order to make the maximum quantum yield to be unity. [1] All these data were independently measured for three times (with different solutions samples). Φ = Φ A η std unk unk UC 2 std Aunk std ηstd 2 (Eq. 1) or the measurement of the TTET efficiency, i.e. the Stern-Volmer quenching constants, the concentration of the sensitizer was fixed at 1. 1-5 M, the lifetime of the sensitizer was measured with increasing the perylene concentration in the solution. The diameter of the 532 nm laser spot is ca. 3 mm and for 635 nm laser, it is ca. 6 mm. or the upconversion experiments, the mixed solution of the complex (triplet sensitizer) and perylene or 1-chloro-bis-phenylethynylanthracene (1CPEA) (triplet acceptor) was degassed for at least 15 min with 2 or Ar. Then the solution was excited with laser. The upconverted fluorescence of perylene or 1CPEA was observed with fluorospectrometer. n order to repress the scattered laser, a black box with a small hole on it was put behind the fluorescent cell to trap the laser beam behind the vial (the small hole as the entrance of the laser into the black box). The polymer used for the upconversion is PEG-15 (molecular weight: 15). The film was obtained by casting a 1.5 ml solution of PEG15 (11 % in CH 2 Cl 2 ), in which 6 μl of sensitizer solution (1. 1-3 M) and.7 ml of acceptor solution (1. 1-3 M) had been added, or only.7 ml of acceptor solution (1. 1-3 M) perylene had been added, on a glass disk. Then after evaporation of the solvents, the films were study under air. The CE coordinates (x,y) of the emission of the sensitizers alone and the emission of the upconversion were derived from the emission spectra with the software of CE color Matching Linear Algebra. The density functional theory (DT) calculations were used for optimization of the ground state geometries, for both singlet states and triplet states. The energy level of the T 1 state (energy gap between S state and T 1 state) were calculated with the time-dependent DT (TDDT), based on the optimized triplet state geometries. These TDDT calculations were used for the prediction of the UV-vis absorption of the T 1 state of the organic triplet sensitizers, in our case it is the transient absorption of the organic triplet sensitizers after the laser flash (the pulsed excitation of the organic triplet sensitizer solution). Please note that the bleaching bands in the time-resolved transient absorption spectra can not be predicted by the TDDT calculations. All the calculations S2
were performed with Gaussian 9. [2] [1] T.. Singh-Rachford,.. Castellano, Coord. Chem. Rev. 21, 254, 256 2573. [2] M. J. risch, G. W. Trucks, H.. Schlegel, et al. Gaussian 9 Revision A.1, Gaussian nc., Wallingford CT, 29. [3] L. Jiao, C. Yu, J. Li, Z. Wang, M. Wu, E. Hao, J. Org. Chem. 29, 74, 7525 7528. [4] C. Tahtaoui, C. Thomas,. Rohmer, P. Klotz, G. Duportail, Y. Me ly, D. onnet, M. Hibert, J. Org. Chem. 27, 72, 269-272. S3
2. Synthesis and molecular structure characterization data O C Cl H CH 2 Cl 2 - S (1eq) CH 2 Cl 2-1 - S(4eq) CH 2 Cl 2-2 5) 6) 4) -3-8 -4 Si -5 Perylene 1CPEA Cl -1 1) 2) 3) a-1 a-2 S(4eq) CH 2 Cl 2-6 -1 1) 2) 3) a-1 a-3 S (4eq) CH 2 Cl 2-7 1) Trimethylsilylacetylene, Pd(PPh 3 ) 2 Cl 2, PPh 3, Cu, Et 3, reflux, 8 h; 2) aoh(aq), TH/MeOH; 3) -1, Pd(PPh 3 ) 2 Cl 2, PPh 3, Cu, Et 3, reflux, 8 h; 4) 4-(dimethylamino)benzaldehyde, Piperidine, reflux; 5) Trimethylsilylacetylene, Pd(PPh 3 ) 2 Cl 2, PPh 3, Cu, TH/Et 3, r.t.; 6) 9-butyl-3-ethynylcarbazole, Pd(PPh 3 ) 2 Cl 2, PPh 3, Cu, TH/Et 3, r.t. Scheme S1. Synthesis of the ODPY based organic triplet sensitizers -1, -2, -3, -4, -5, -6 and -7. The known compound of - [3] and the -8 [4] were presented for comparison. ote the iodo atom is attached to the 4-position of the meso-phenyl in -8, this substitution profile is non-efficient to induce a SC (S 1 T 1 transition) because the heavy atom (iodine atom) is far away from the core of the fluorophore. S4
1, 3, 5, 7-tetramethyl-8-phenyl-4, 4-difluoroboradiazaindacene (-) Under nitrogen atmosphere, benzoyl chloride (2.8 g,.21mol ) and 2, 4-dimethylpyrrole (4 ml, 3.7 g,.4 mol ) were added to 15 ml anhydrous CH 2 Cl 2 via syringe, the mixture was stirred at room temperature over night, then Et 3 (2 ml) and 3 Et 2 O (2 ml) were added under ice-cold condition, and reaction mixture was stirred for additional 1 h. After the reaction, the mixture was poured into water (2 ml), the organic layer was collected and dried over anhydrous MgSO 4 and evaporated under reduced pressure. The crude product was further - purified using column chromatography (CH 2 Cl 2 :hexane = 1:1) to give - as green power. 2.3 g, Yield: 33.3 %. 1 H MR (4 MHz, CDCl 3 ): 7.49 7.47 (m, 3H), 7.29 7.26 (m, 2H), 5.98 (s, 2H), 2.56 (s, 6H), 1.37 (s, 6H). 3. MR and HR-MS spectra - igure S1. 1 H MR of - (4 MHz, CDCl 3 ). 7.51 7.51 7.5 7.49 7.48 7.27 7.27 7.26 7.25 7.51 7.51 7.5 7.49 7.48 7.27 7.26 7.25 6.4 2.63 2.57 1.38 3. 2.61 7.5 7.4 7.3 7.2 3..95 3.5 6.8 8 7 6 5 4 3 2 1 igure S2. 1 H MR of -1 (4 MHz, CDCl 3 ). S5
igure S3. 13 C MR of -1 (1 MHz, CDCl 3 ). 111152 25 (.831) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:29) TO LD+ 1 45.535 449.639 1.69e4 % 451.569 448.785 481.3112 59.2488 44 45 46 47 48 49 5 51 52 53 54 55 56 57 m/z igure S4. MALD-HRMS of -1. S6
7.54 7.53 7.52 7.51 7.51 7.26 7.25 7.24 7.54 7.53 7.52 7.51 7.51 7.26 7.25 7.24 2.65 1.38 3. 2.49 7.6 7.5 7.4 7.3 7.2 3. 5.98 5.97 8 7 6 5 4 3 2 1 igure S5. 1 H MR of -2 (4 MHz, CDCl 3 ). igure S6. 13 C MR of -2 (1 MHz, CDCl 3 ). S7
111172 12 (.399) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:26) TO LD- 575.9528 1 2.65e3 % 574.9576 576.956 5 52 54 56 58 6 62 64 66 68 m/z igure S7. MALD-HRMS of -2. 8.21 8.17 7.59 7.56 7.54 7.52 7.52 7.51 7.5 7.28 7.28 7.27 6.81 8.17 7.59 7.56 7.52 7.52 7.51 7.5 7.28 7.28 7.27 6.81 3.6 2.68 1.44 1.38.97 6.1 1.9 1.8 8. 7.5 7..97 6.1 1.8 5.99 3.11 8 7 6 5 4 3 2 1 igure S8. 1 H MR of -3 (4 MHz, CDCl 3 ). S8
igure S9. 13 C MR of -3 (1 MHz, CDCl 3 ). 111157 5 (.167) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:11) TO LD+ 77.286 1 1.1e4 76.229 % 78.32 75.23 m/z 6 65 7 75 8 85 9 95 1 igure S1. MALD-HRMS of -3. S9
7.51 7.51 7.26 7.25 7.24 7.51 7.51 7.26 7.25 7.24 2.65 2.64 1.44 1.39.2 3. 2.33 7.5 7.4 7.3 7.2-4 Si 3. 5.89 3.5 8.9 8 7 6 5 4 3 2 1 igure S11. 1 H MR of -4 (4 MHz, CDCl 3 ) Si igure S12. 13 C MR of -4 (1 MHz, CDCl 3 ). S1
111151 33 (1.98) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (33:38) TO LD+ 546.938 1 2.8e3 % 547.96 681.269 873.197 5 6 7 8 9 1 11 12 13 14 m/z igure S13. MALD-HRMS of -4. 8.21 8.8 8.6 7.56 7.54 7.54 7.53 7.48 7.42 7.4 7.35 7.33 7.31 7.3 7.29 7.28 7.25 8.21 8.8 8.6 7.56 7.54 7.54 7.53 7.46 7.42 7.35 7.3 5.3 4.32 4.3 4.28 2.77 2.67 1.87 1.85 1.83 1.56 1.54 1.41 1.4 1.38.96.94.93 1. 1.2 4.1 1.4 2.8 8. 7.5 1.2 4.1 2.2 3.4 3.383.19 9 8 7 6 5 4 3 2 1 igure S14. 1 H MR of -5(4 MHz, CDCl 3 ). S11
igure S15. 13 C MR of -5 (1 MHz, CDCl 3 ). 111154 21 (.698) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (18:22) TO LD+ 695.1746 1 75 % 696.1759 694.1752 m/z 5 55 6 65 7 75 8 85 9 95 1 igure S16. MALD-HRMS of -5 S12
7.52 7.51 7.5 7.5 7.49 7.28 7.27 7.26 7.25 7.51 7.5 7.49 7.28 7.27 7.26 7.25 6.4 3.28 2.64 2.57 1.44 1.39 3. 2.37 7.5 7.4 7.3 3..94.89 3.9 3.16 8 7 6 5 4 3 2 1 igure S17. 1 H MR of a1 (4 MHz, CDCl 3 ) igure S18. 13 C MR of a1 (1 MHz, CDCl 3 ) S13
7.51 7.5 7.49 7.26 7.25 7.24 7.51 7.5 7.49 7.26 7.25 7.24 6.5 2.65 2.57 1.44 1.39 6. 4.25 7.6 7.5 7.4 7.3 7.2 7.1 6. 1.86 5.91 5.98 8 7 6 5 4 3 2 1 igure S19. 1 H MR of a2 (4 MHz, CDCl 3 ). igure S2. 13 C MR of a2 (1 MHz, CDCl 3 ). S14
7.53 7.52 7.51 7.26 7.25 7.24 7.23 7.53 7.52 7.51 7.26 7.25 7.24 7.23 2.66 1.44 1.4 6. 4.38 7.6 7.55 7.5 7.45 7.4 7.35 7.3 7.25 7.2 6. 12.7 6.38 8 7 6 5 4 3 2 1 igure S21. 1 H MR of -6 (4 MHz, CDCl 3 ). igure S22. 13 C MR of -6 (1 MHz, CDCl 3 ). S15
111228 3 (.99) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:1) TO LD+ 946.137 1 8.3e3 945.161 % 927.1144 947.182 82.2169 948.1159 5 6 7 8 9 1 11 12 13 14 m/z igure S23. MALD-HRMS of -6 7.59 7.54 7.5 7.33 7.26 6.2 2.63 2.57 1.44 1.39 3.55.98 6.13 6.4 8 7 6 5 4 3 2 1 igure S24. 1 H MR of a3 (4 MHz, CDCl 3 ). S16
igure S25. 13 C MR of a3 (1 MHz, CDCl 3 ). 111183 75 (2.5) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (61:77) TO LD+ 67.341 1 2.74e3 % 669.368 671.362 651.354 672.367 711.1389 786.696 813.77 855.476 927.4242 943.4174 988.744 65 7 75 8 85 9 95 1 m/z igure S26. MALD-HRMS of a3. S17
7.54 7.52 7.51 7.5 7.26 7.54 7.52 7.51 7.5 7.26 2.65 2.64 1.44 1.4 3. 1.69 7.6 7.5 7.4 7.3 7.2 3. 6.1 3.35 7 6 5 4 3 2 1 igure S27. 1 H MR of -7 (4 MHz, CDCl 3 ). igure S28. 13 C MR of -7 (1 MHz, CDCl 3 ). S18
111227 1 (.31) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:19) TO LD+ 922.933 1 1.84e3 921.943 % 846.641 845.659 923.964 5 6 7 8 9 1 11 12 13 14 m/z igure S29. MALD-HRMS of -7 4. Up-conversion details. Luminescent intensity / a.u. 9 upconverted Laser Power (mw) emission 13.3 11.6 8.4 6 7.7 5.7 3.7 3 2. 1. 4 5 6 7 ormalized PL intensity / a.u..9.6.3...3.6.9 ormalized Power Density igure S3. (a) Emission intensity of upconverted fluorescence of perylene and the prompt fluorescence intensity of -1 following selective excitation at 532 nm in a deaerated MeC. (b) ormalized integrated emission intensity from panel (a) plotted as a function of ormalized incident light power. S19
Luminescent intensity / a.u. 9 6 3 Laser Power at 532nm 17.6 mw 15.1 9.5 8.7 7.5 6.9 3.6 1.8.9 mw 4 5 6 7 ormalized PL intensity / a.u..9.6.3...3.6.9 ormalized Power Density igure S31. (a) Emission intensity profile of upconverted fluorescence of Perylene and the prompt fluorescence of -4 following selective excitation at 532 nm in a deaerated MeC (b) ormalized integrated emission intensity from panel (a) plotted as a function of ormalized incident light Power. Luminescent intensity / a.u. 9 6 3 upconverted fluorescence -1 scattered laser emission of -1 4 5 6 7 Luminescent intensity / a.u. 12 9 6 3 upconverted scattered fluorescence laser -2 emission of -2 4 5 6 7 igure S32. Unconverted fluorescence of perylene and fluorescence of -1 and -2 measured in the PEG15 polymer film. λ ex = 532 nm, 5 mw. Luminescent intensity / a.u. 9 6 3-3 + 1CPEA 1CPEA 5 55 6 65 igure S33. Emission intensity profile of upconverted fluorescent of 1CPEA in a deaerated toluene mixture of 1. 1-5 M -3 and 1.8 1-2 M 1CPEA. λ ex = 635 nm, 4 mw. S2
ntensity / a.u. 9 16.8 mw a 13.3... 6... 2. 1. 3 4 5 6 7 ntensity / a.u. b 16.8 mw 8 13.2 mw 11.6 mw 6 8.8 mw 7.6 mw 4 5.6 mw 3.6 mw 2 2. mw 1.2 mw 4 5 6 7 8 ntensity / a.u. 4 b 2 45 5 55 6 65 igure S34. (a) Excitation power dependency of the upconverted perylene emission with -2 as sensitizer (λ ex = 532 nm) in CH 3 C. (b) Control experiment with only the acceptor was added. 4 ntensity / a.u. 3 2 1 h.5 h 1. h 1.5 h 2. h 3. h 4 5 6 7 igure S35. The variety of the upconverted fluorescence intensity of -2 under illumination. Excited with 532 nm laser (5 mw). c[sensitizer] = 1. 1-5 M. c[perylene] = 1.1 1-4 M. n deaerated CH 3 C. 2 C. The mixed solution was illuminated by a 35W Xe lamp, the power density of the facula on the sample is 22 mw cm -2 5. Transient absorption details.1 Δ O.D.. 7 -.1 6 5 -.2 4 3 2 -.3 1 Delayed time (ns) -.4 4 5 6 7 8 - igure S36. Transient absorption difference spectra of - in deaerated MeC at room temperature after pulsed laser excitation (λ ex = 532 nm). 1.5 1-5 M. 2 C. S21
.2.6 Δ O.D.. -.2 15 11 8 6 4 2 1 Delayed time (μs) 4 5 6 7 8 Δ O.D. Residules.4.2..5. -.5 5 1 15 2 Time / μs 5 1 15 2 Time / μs igure S37. Transient absorption difference spectra of -1 in deaerated MeC at room temperature after pulsed laser excitation (λ ex = 532 nm). 1.5 1-5 M. 2 C..2 Δ O.D.. -.2 48.8 μs 26.92 μs 16.83 μs 13.46 μs 11.78 μs 8.41 μs 5.5 μs 3.37 μs 4 5 6 7 igure S38. anosecond time-resolved transient absorption difference spectra of -1 with 2. 1-5 of perylene was added, in deaerated CH 3 C after pulsed laser excitation (λ ex = 532 nm), 1. 1-5 M. 2 C. The transient absorption at 479 nm is due to perylene. The transient absorption at 428 nm is due to -1. Δ O.D..6.3. Delayed time (μs).67 1.33 2. 2.67 3.33 4. 5.33 8.67 Delta OD/1-2 5. 4. 3. 2. 1.. -1. -.3 4 5 6 7 8 Residuals 5 1 15 2 25 3 Time/ 祍 3.4. -3.4 igure S39. Transient absorption difference spectra of -3 in deaerated CH 3 C at room temperature after pulsed laser excitation (λ ex = 532 nm). 1.5 1-5 M. 2 C. S22
.3.12 Δ O.D.. 192 128 96 -.3 64 32 16 Delayed time (μs) -.6 4 5 6 7 8 Δ O.D. Residules.6..2. -.2 1 2 3 Time / μs 1 2 3 Time / μs igure S4. Transient absorption difference spectra of -4 in deaerated MeC at room temperature after pulsed excitation (λ ex = 532 nm). 1.5 1-5 M. 2 C..2 Δ O.D.. -.2 47.6 μs 34.47 μs 26.26 μs 19.7 μs 9.85 μs 6.57 μs 4.92 μs -.4 4 5 6 7 Si igure S41. anosecond time-resolved transient absorption difference spectra of -4 with 2. 1-5 of perylene was added, in deaerated CH 3 C after pulsed laser excitation (λ ex = 532 nm), 1. 1-5 M. 2 C..5.2 Δ O.D.. 28μs 144μs -.5 112μs 8μs 32μs -.1 48μs 16μs μs Delayed time (μs) -.15 4 5 6 7 8 Δ O.D. Residules.1..5. -.5 1 2 3 Time / μ s 1 2 3 Time / μ s igure S42. Transient absorption difference spectra of -5 in deaerated toluene at room temperature after pulsed excitation (λ ex = 532 nm). 1.5 1-5 M. 2 C. S23
.5 Δ O.D.. -.5 76.6 μs 58.1 μs 42.3 μs 31.7 μs 23.8 μs 15.8 μs 1.6 μs 5.3 μs -.1 4 5 6 7 8 igure S43. anosecond time-resolved transient absorption difference spectra of -5 with 2. 1-5 of 1CPEA was added, in deaerated CH 3 C after pulsed laser excitation (λ ex = 532 nm), 1. 1-5 M. 2 C. Δ O.D. 2-2 -4 Delayed time (μs) 94.5 μs 72. μs 53.5 μs 36. μs 27.5 μs 18. μs 13.5 μs 9. μs 4.5 μs μs 4 5 6 7 8 Δ O.D. Residules.4.3.2.1..2. -.2 5 1 15 2 Time / μs 5 1 15 2 Time / μs igure S44. Transient absorption difference spectra of -6 in deaerated toluene at room temperature after pulsed excitation (λ ex = 532 nm). 1.5 1-5 M. 2 C..3.4.3 Δ O.D.. 21 μs 12 μs -.3 9 μs 7 μs 5 μs 4 μs -.6 3 μs 2 μs 1 μs -.9 4 5 6 7 8 Δ O.D. Residuals.2.1..4. -.4 5 1 15 Time / μs 5 1 15 Time / μs igure S45. Transient absorption difference spectra of -7 in deaerated toluene at room temperature after pulsed excitation (λ ex = 532 nm). 1.5 1-5 M. 2 C. S24
6. Calculation details Table S1. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizers, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Ground State Geometries Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C d - S T 1 1.52 ev 816 nm. -1 S T 1 1.51 ev 82 nm. -2 S T 1 1.5 ev 827 nm. -3 S T 1 1.15 ev 175 nm. -4 S T 1 1.5 ev 829 nm. -5 S T 1 1.41 ev 878 nm. -6 S T 1 1.39 ev 893 nm. -7 S T 1 1.43 ev 866 nm. HOMO-1 LUMO.151 HOMO LUMO.8287 HOMO-1 LUMO.1256 HOMO LUMO.727 HOMO LUMO.1128 HOMO-1 LUMO.29 HOMO LUMO.847 HOMO-2 LUMO.1293 HOMO-1 LUMO.2616 HOMO LUMO.7756 HOMO-1 LUMO.1675 HOMO LUMO.6861 HOMO-2 LUMO.121 HOMO-1 LUMO.3724 HOMO LUMO.595 HOMO-2 LUMO.1668 HOMO-2 LUMO+1.3582 HOMO LUMO.584 HOMO-2 LUMO.134 HOMO-1 LUMO.3522 HOMO LUMO.5979 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. S25
LUMO LUMO LUMO LUMO HOMO HOMO HOMO HOMO - -1-2 -4 igure S46. rontier molecular orbitals of the ODPY based organic triplet sensitizers of -1, -2, -4. Calculated by DT at the 3LYP/6-31G(d)/ LanL2DZ level using Gaussian 9. The known compound - were presented for comparison, the orbitals of others were displayed in the main text. The molecular orbitals (MOs) show that the iodo-substitution on the core of the ODPY (-1, -2, -3, -4, -5, -6 and -7) is necessary to exert the heavy atom effect. odo substitution at the peripheral phenyl moiety at the meso position of the ODPY (e.g. -8) is a non-effective method to induce the heavy atom effect because the iodo atom is far away from the frontier orbitals of the ODPY organic triplet sensitizers. S26
-1-2 -4 igure S47. Spin density surfaces of the ODPY based triplet sensitizers of -1, -2 and -4(the iodine atoms are in pink color). Calculated by DT at the 3LYP/6-31G(d)/ LanL2DZ level using Gaussian 9, the surfaces of other sensitizers were displayed in the main text. The spin density surface distributions show that only the iodo-substitution on the core of the ODPY fluorophore will be efficient to induce the heavy atom effect before the iodine atom is close to the spin density distribution. or -8, however, the iodine atom at the 4-position of the meso phenyl moiety at the ODPY fluorophore is unable to induce any significant heavy atom effect because it is far way from the spin density distribution. t is known that the heavy atom effect is strongly dependent on the distance between the heavy atom and the chromophore. 4 - Absorption 2 4 6 8 igure S48. Transient absorption difference spectra of -. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S27
89A 88A 86A 85 84 8 igure S49. Selected frontier molecular orbitals of - Table S2. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -, Calculated by TDDT//3LYP/6-31G(d), based on the DT//3LYP/6-31G(d) Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 3 1.5 ev.187 84 -> 85.9588 825 nm 8 -> 85.1932 T 1 T 4 2.21 ev.583 8 -> 85.9339 561 nm 86A -> 89A.2295 T 1 T 8 2.87 ev.414 86A -> 88A.9796 433 nm 8 -> 85.151 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. S28
-1 6 Absorption 3 4 6 8 igure S5. Transient absorption difference spectra of -1. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. 93A 92A 89A 88 84 83 igure S51. Selected frontier molecular orbitals of -1 S29
Table S3. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -1, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 4 2.4 ev.991 84 -> 88.87664 68 nm 83 -> 88.2932 89A -> 93A.2222 T 1 T 1 2.93 ev 423 nm.586 89A -> 92A.98153 84 -> 88.12379 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. 15-2 Absorption 1 5 4 6 8 igure S52. Transient absorption difference spectra of -2. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S3
97A 96A 92A 91 89 88 igure S53. Selected frontier molecular orbitals of -2 Table S4. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -2, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 4 1.87 ev.1561 88 -> 91.93191 662 nm 92A -> 97A.22562 89 -> 91.22537 T 1 T 12 2.99 ev.848 92A -> 96A.97977 414 nm 88 -> 91.17124 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. S31
Absorption 6-3 3 4 6 8 igure S54. Transient absorption difference spectra of -3. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. 128A 127A 126A 127 126 125 122 igure S55. Selected frontier molecular orbitals of -3 S32
Table S5. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -3, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 5 2. ev.7675 127A ->128A.7484 62 nm 125 ->126.47979 122 ->126.37398 T 1 T 6 2.16eV 574 nm.2117 122 ->126.86517 127A ->128A.37427 T 1 T 2 3.21 ev 387 nm.2544 126A ->128A.73852 125 ->127.429 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. 18-4 Absorption 12 6 45 6 75 igure S56. Transient absorption difference spectra of -4. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S33
12A 119A 117A 115A 114 111 igure S57. Selected frontier molecular orbitals of -4 Table S6. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -4, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 4 1.86 ev.1951 111 114.93252 668 nm 115A ->12A.21485 T 1 T 12 2.96 ev.898 115A ->119A.94969 42 nm 115A ->117A.2718 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. S34
3-5 Absorption 2 1 4 6 8 igure S58. Transient absorption difference spectra of -5. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. 147A 144A 143A 142A 142 141 14 138 137 136 igure S59. Selected frontier molecular orbitals of -5 S35
Table S7. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -5, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 5 1.81 ev / 685 nm.212 137 141.6652 136 141.69 138 141.2917 T 1 T 14 2.2 ev / 564 nm.318 142A 144A.738 142A 143A.5984 T 1 T 17 2.89 ev / 429 nm.745 142A 147A.835 14 142.3242 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. 4-6 Absorption 2 4 6 8 igure S6. Transient absorption difference spectra of -6. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S36
189A 187A 186A 188 187 186 185 183 182 181 18 176 igure S61. Selected frontier molecular orbitals of -6 Table S8. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -6, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 5 1.83 ev.3455 181 187.62688 678 nm 182 187.55543 18 187.3594 T 1 T 8 2.22 ev.1786 187A 189A.53792 558 nm 183 187.52749 186 188.5638 T 1 T 24 2.89eV.3368 186A 189A.68822 429 nm 185 188.43114 176 187.317 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. S37
-7 Absorption 2 1 4 5 6 7 8 igure S62. Transient absorption difference spectra of -7. Calculated by DT at the 3LYP/6-31G((d)/LanL2DZ level using Gaussian 9. 181A 183A 182 181 18 176 175 168 167 igure S63. Selected frontier molecular orbitals of -7 S38
Table S9. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -7, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 6 1.84 ev.2713 176 181.8777 675 nm 175 181.2845 T 1 T 12 2.33 ev 531 nm.237 181A 183A.63 18 182.6847 T 1 T 18 2.77 ev 447 nm.1251 168 181.7729 167 181.3354 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. 6-8 Absorption 4 2 4 6 8 igure S64. Transient absorption difference spectra of -8. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S39
93A 92A 89A 85 84 8 igure S65. Selected frontier molecular orbitals of -8 Table S1. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of ODPY based organic sensitizer -8, Calculated by TDDT//3LYP/6-31G(d)/LanL2DZ, based on the DT//3LYP/6-31G(d)/LanL2DZ Optimized Excited State Geometries Triplet Electronic transition T 1 T 3 TDDT//3LYP/6-31G(d) Energy f b Composition C c (ev) a 1.51 ev 822 nm.174 87 -> 88.9594 84 -> 88.19242 T 1 T 5 2.21 ev.572 84 -> 88.92176 56 nm 89A -> 93A.23532 T 1 T 8 2.65 ev.31 89A -> 92A.97319 467 nm 84 -> 88.18435 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. S4
3 2 A 1 4 6 8 igure S66. Transient absorption difference spectra of Perylene. Calculated by DT at the 3LYP/3-21G level using Gaussian 9. 7A 68A 67A 66 65 64 igure S67. Selected frontier molecular orbitals of Perylene. S41
Table S11. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of the acceptor Perylene, Calculated by TDDT//3LYP/3-21G, based on the DT//3LYP/3-21G Optimized Excited State Geometries Triplet Electronic TDDT//3LYP/6-31G(d) transition Energy (ev) a f b Composition C c T 1 T 7 2.65 ev.1194 67A -> 68A.66948 467 nm 65 -> 66.6919 T 1 T 9 3.6 ev 45 nm.4533 67A -> 7A.72568 64 -> 66.6754 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. 15 1 A 5 4 6 8 igure S68. Transient absorption difference spectra of 1CPEA. Calculated by DT at the 3LYP/6-31G level using Gaussian 9. S42
11A 1A 99A 96A 95 94 igure S69. Selected frontier molecular orbitals of 1CPEA Table S12. Electronic Excitation Energies (ev) and corresponding Oscillator Strengths (f), main configurations and C coefficients of the Low-lying Electronically Excited States of the acceptor 1CPEA, Calculated by TDDT//3LYP/3-21G, based on the DT//3LYP/3-21G Optimized Excited State Geometries Triplet Electronic transition TDDT//3LYP/6-31G(d) Energy f b Composition C c (ev) a T 1 T 1 2.73 ev 453 nm.341 96A -> 99A.55844 96A ->1A.4445 T 1 T 9 2.9553 ev 419.53 nm.824 96A ->11A.77993 94 -> 95.25261 a Only the selected low-lying excited states are presented. b Oscillator strength. o spin-orbital coupling effect was considered in the calculation thus the oscillators are zero. c The C coefficients are in absolute values. S43
7. 77 K emission spectra ormalized ntensity / a.u..9.6.3. 298K 77K 5 6 7 8 - igure S7. Emission spectra of - in ethanol-methanol (4:1, V/V) glass at 77 K and solution at 298 K. Excitation wavelength at 49 nm. ormalized ntensity / a.u..9.6.3 298K 77K. 5 6 7 8 igure S71. Emission spectra of -1 in ethanol-methanol (4:1, V/V) glass at 77 K and solution at 298 K. Excitation wavelength at 49 nm. S44
ormalized ntensity / a.u..9.6.3. 298K 77K 6 7 8 igure S72. Emission spectra of -2 in ethanol-methanol (4:1, V/V) glass at 77K and solution at 298K. Excitation wavelength at 51 nm. ormalized ntensity / a.u..9.6.3. 298K 77K 65 7 75 8 85 igure S73. Emission spectra of -3 in ethanol-methanol (4:1, V/V) glass at 77K and solution at 298K. Excitation wavelength at 62 nm. S45
ormalized ntensity / a.u..9.6.3. 298K 77K 6 7 8 Si igure S74. Emission spectra of -4 in ethanol-methanol (4:1, V/V) glass at 77 K and solution at 298 K. Excitation wavelength at 52 nm. ormalized ntensity / a.u..9.6.3. 298K 77K 6 7 8 igure S75. Emission spectra of -5 in ethanol-methanol (4:1, V/V) glass at 77 K and solution at 298 K. Excitation wavelength at 56 nm. S46
ormalized ntensity / a.u..9.6.3. 298K 77K 6 7 8 igure S76. Emission spectra of -6 in ethanol-methanol (4:1, V/V) glass at 77 K and solution at 298 K. Excitation wavelength at 56 nm. ormalized intensity / a.u..9.6.3. 298K 77K 6 7 8 igure S77. Emission spectra of -7 in ethanol-methanol (4:1, V/V) glass at 77K and solution at 298K. Excitation wavelength at 58 nm. S47
8. Stability of the iodinated compounds with irradiation by the sun light.9.6 h After 2 h After 4 h -1.9 h -2 After 2 h.6 After 4 h.9 h -3 After 2 h.6 After 4 h A A A.3.3.3. 3 4 5 6 7. 3 4 5 6 7. 4 6 8.9 h -4 After 2 h.6 After 4 h.9-5 h After 2 h.6 After 4 h A 1.6 1.2.8 h After 2 h After 4 h -6 A A.3.3.4. 3 4 5 6 7 Wavvelength / nm. 3 4 5 6 wavelength / nm 7. 3 4 5 6 7.9 h -7 After 2 h.6 After 4 h A.3. 3 4 5 6 7 igure S78. UV-vis absorption spectra of the sensitizers -1,-2, -4 (in MeC) and -3, -5, -6, -7 (in toluene) before and after the irradiation by sunlight. 1. 1-5 M. S48
ntensity / a.u. 6 4 2-1 h After 2 h After 4 h 5 6 7 ntensity / a.u. 3 2 1-2 h After 2h After 4h 55 6 65 7 ntensity / a.u. 6-3 h After 2h After 4h 4 2 675 75 825 9 ntensity / a.u. 3-4 h After 2h After 4 h 2 1 55 6 65 7 ntensity / a.u. 6 4 2-5 h After 2h After 4h 6 7 8 ntensity / a.u. 4-6 h 3 After 2h After 4h 2 1 6 7 8 ntensity / a.u. 6-7 h After 2 h After 4 h 4 2 6 7 8 igure S79. luorescence spectra of the sensitizers -1,-2, -4 (in MeC) and -3, -5, -6, -7 (in toluene) before and after the irradiation by sunlight. 1. 1-5 M. S49
9. Photophysics of the Acceptors ntensity / a.u..9 a Absorption Emission.6.3 ntensity / a.u..9.6.3 b Absorption Emission. 3 4 5 6. 4 6 igure S8. (a) Absorption and fluorescence spectra of Perylene, λex = 39 nm; (b) absorption and emission spectra of 1CPEA, λex = 46 nm, 1. 1-5 M 2 C Cl Perylene 1CPEA S5