with Long-lived Triplet Excited State for Triplet-Triplet-Annihilation Based Upconversion

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1 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: * 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.s K emission spectra.s43 8. Stability of the iodinated compounds with irradiation by the sun light.s48 9. Photophysics of the Acceptors.S49 S1

2 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 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 ( M) and.7 ml of acceptor solution ( M) had been added, or only.7 ml of acceptor solution ( 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

3 were performed with Gaussian 9. [2] [1] T.. Singh-Rachford,.. Castellano, Coord. Chem. Rev. 21, 254, [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, [4] C. Tahtaoui, C. Thomas,. Rohmer, P. Klotz, G. Duportail, Y. Me ly, D. onnet, M. Hibert, J. Org. Chem. 27, 72, S3

4 2. Synthesis and molecular structure characterization data O C Cl H CH 2 Cl 2 - S (1eq) CH 2 Cl S(4eq) CH 2 Cl 2-2 5) 6) 4) Si -5 Perylene 1CPEA Cl -1 1) 2) 3) a-1 a-2 S(4eq) CH 2 Cl ) 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

5 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 ): (m, 3H), (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 ) igure S2. 1 H MR of -1 (4 MHz, CDCl 3 ). S5

6 igure S3. 13 C MR of -1 (1 MHz, CDCl 3 ) (.831) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:29) TO LD e4 % m/z igure S4. MALD-HRMS of -1. S6

7 igure S5. 1 H MR of -2 (4 MHz, CDCl 3 ). igure S6. 13 C MR of -2 (1 MHz, CDCl 3 ). S7

8 (.399) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:26) TO LD e3 % m/z igure S7. MALD-HRMS of igure S8. 1 H MR of -3 (4 MHz, CDCl 3 ). S8

9 igure S9. 13 C MR of -3 (1 MHz, CDCl 3 ) (.167) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:11) TO LD e % m/z igure S1. MALD-HRMS of -3. S9

10 Si igure S11. 1 H MR of -4 (4 MHz, CDCl 3 ) Si igure S C MR of -4 (1 MHz, CDCl 3 ). S1

11 (1.98) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (33:38) TO LD e3 % m/z igure S13. MALD-HRMS of igure S14. 1 H MR of -5(4 MHz, CDCl 3 ). S11

12 igure S C MR of -5 (1 MHz, CDCl 3 ) (.698) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (18:22) TO LD % m/z igure S16. MALD-HRMS of -5 S12

13 igure S17. 1 H MR of a1 (4 MHz, CDCl 3 ) igure S C MR of a1 (1 MHz, CDCl 3 ) S13

14 igure S19. 1 H MR of a2 (4 MHz, CDCl 3 ). igure S2. 13 C MR of a2 (1 MHz, CDCl 3 ). S14

15 igure S21. 1 H MR of -6 (4 MHz, CDCl 3 ). igure S C MR of -6 (1 MHz, CDCl 3 ). S15

16 (.99) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:1) TO LD e % m/z igure S23. MALD-HRMS of igure S24. 1 H MR of a3 (4 MHz, CDCl 3 ). S16

17 igure S C MR of a3 (1 MHz, CDCl 3 ) (2.5) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (61:77) TO LD e3 % m/z igure S26. MALD-HRMS of a3. S17

18 igure S27. 1 H MR of -7 (4 MHz, CDCl 3 ). igure S C MR of -7 (1 MHz, CDCl 3 ). S18

19 (.31) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (1:19) TO LD e % m/z igure S29. MALD-HRMS of Up-conversion details. Luminescent intensity / a.u. 9 upconverted Laser Power (mw) emission ormalized PL intensity / a.u 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

20 Luminescent intensity / a.u Laser Power at 532nm 17.6 mw mw ormalized PL intensity / a.u 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 upconverted fluorescence -1 scattered laser emission of Luminescent intensity / a.u upconverted scattered fluorescence laser -2 emission of 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 CPEA 1CPEA igure S33. Emission intensity profile of upconverted fluorescent of 1CPEA in a deaerated toluene mixture of M -3 and M 1CPEA. λ ex = 635 nm, 4 mw. S2

21 ntensity / a.u mw a ntensity / a.u. b 16.8 mw mw 11.6 mw mw 7.6 mw mw 3.6 mw 2 2. mw 1.2 mw ntensity / a.u. 4 b 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 h.5 h 1. h 1.5 h 2. h 3. h igure S35. The variety of the upconverted fluorescence intensity of -2 under illumination. Excited with 532 nm laser (5 mw). c[sensitizer] = M. c[perylene] = 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 Transient absorption details.1 Δ O.D Delayed time (ns) igure S36. Transient absorption difference spectra of - in deaerated MeC at room temperature after pulsed laser excitation (λ ex = 532 nm) M. 2 C. S21

22 .2.6 Δ O.D Delayed time (μs) Δ O.D. Residules Time / μs Time / μs igure S37. Transient absorption difference spectra of -1 in deaerated MeC at room temperature after pulsed laser excitation (λ ex = 532 nm) M. 2 C..2 Δ O.D μs μs μs μs μs 8.41 μs 5.5 μs 3.37 μs igure S38. anosecond time-resolved transient absorption difference spectra of -1 with of perylene was added, in deaerated CH 3 C after pulsed laser excitation (λ ex = 532 nm), 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 Delayed time (μs) Delta OD/ Residuals Time/ 祍 igure S39. Transient absorption difference spectra of -3 in deaerated CH 3 C at room temperature after pulsed laser excitation (λ ex = 532 nm) M. 2 C. S22

23 .3.12 Δ O.D Delayed time (μs) Δ O.D. Residules Time / μs Time / μs igure S4. Transient absorption difference spectra of -4 in deaerated MeC at room temperature after pulsed excitation (λ ex = 532 nm) M. 2 C..2 Δ O.D μs μs μs 19.7 μs 9.85 μs 6.57 μs 4.92 μs Si igure S41. anosecond time-resolved transient absorption difference spectra of -4 with of perylene was added, in deaerated CH 3 C after pulsed laser excitation (λ ex = 532 nm), M. 2 C..5.2 Δ O.D.. 28μs 144μs μs 8μs 32μs μs 16μs μs Delayed time (μs) Δ O.D. Residules Time / μ s Time / μ s igure S42. Transient absorption difference spectra of -5 in deaerated toluene at room temperature after pulsed excitation (λ ex = 532 nm) M. 2 C. S23

24 .5 Δ O.D μs 58.1 μs 42.3 μs 31.7 μs 23.8 μs 15.8 μs 1.6 μs 5.3 μs igure S43. anosecond time-resolved transient absorption difference spectra of -5 with of 1CPEA was added, in deaerated CH 3 C after pulsed laser excitation (λ ex = 532 nm), M. 2 C. Δ O.D 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 Δ O.D. Residules Time / μs Time / μs igure S44. Transient absorption difference spectra of -6 in deaerated toluene at room temperature after pulsed excitation (λ ex = 532 nm) M. 2 C Δ O.D.. 21 μs 12 μs μs 7 μs 5 μs 4 μs μs 2 μs 1 μs Δ O.D. Residuals Time / μs Time / μs igure S45. Transient absorption difference spectra of -7 in deaerated toluene at room temperature after pulsed excitation (λ ex = 532 nm) M. 2 C. S24

25 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 ev 816 nm. -1 S T ev 82 nm. -2 S T ev 827 nm. -3 S T ev 175 nm. -4 S T ev 829 nm. -5 S T ev 878 nm. -6 S T ev 893 nm. -7 S T 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 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

26 LUMO LUMO LUMO LUMO HOMO HOMO HOMO HOMO 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

27 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 igure S48. Transient absorption difference spectra of -. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S27

28 89A 88A 86A 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 ev > nm 8 -> T 1 T ev > nm 86A -> 89A.2295 T 1 T ev A -> 88A nm 8 -> 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

29 -1 6 Absorption 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 igure S51. Selected frontier molecular orbitals of -1 S29

30 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 ev > nm 83 -> A -> 93A.2222 T 1 T ev 423 nm A -> 92A > 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 Absorption igure S52. Transient absorption difference spectra of -2. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S3

31 97A 96A 92A 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 ev > nm 92A -> 97A > T 1 T ev A -> 96A nm 88 -> 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

32 Absorption igure S54. Transient absorption difference spectra of -3. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian A 127A 126A igure S55. Selected frontier molecular orbitals of -3 S32

33 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 A ->128A nm 125 -> > T 1 T eV 574 nm > A ->128A T 1 T ev 387 nm A ->128A > 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 Absorption igure S56. Transient absorption difference spectra of -4. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S33

34 12A 119A 117A 115A 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 ev nm 115A ->12A T 1 T ev A ->119A 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

35 3-5 Absorption igure S58. Transient absorption difference spectra of -5. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian A 144A 143A 142A igure S59. Selected frontier molecular orbitals of -5 S35

36 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 ev / 685 nm T 1 T ev / 564 nm A 144A A 143A.5984 T 1 T ev / 429 nm A 147A 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 igure S6. Transient absorption difference spectra of -6. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S36

37 189A 187A 186A 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 ev nm T 1 T ev A 189A nm T 1 T eV A 189A nm 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

38 -7 Absorption igure S62. Transient absorption difference spectra of -7. Calculated by DT at the 3LYP/6-31G((d)/LanL2DZ level using Gaussian A 183A igure S63. Selected frontier molecular orbitals of -7 S38

39 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 ev nm T 1 T ev 531 nm A 183A T 1 T ev 447 nm 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 igure S64. Transient absorption difference spectra of -8. Calculated by DT at the 3LYP/6-31G((d)/ LanL2DZ level using Gaussian 9. S39

40 93A 92A 89A 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 > > T 1 T ev > nm 89A -> 93A T 1 T ev.31 89A -> 92A nm 84 -> 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

41 3 2 A igure S66. Transient absorption difference spectra of Perylene. Calculated by DT at the 3LYP/3-21G level using Gaussian 9. 7A 68A 67A igure S67. Selected frontier molecular orbitals of Perylene. S41

42 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 ev A -> 68A nm 65 -> T 1 T ev 45 nm A -> 7A > 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 A igure S68. Transient absorption difference spectra of 1CPEA. Calculated by DT at the 3LYP/6-31G level using Gaussian 9. S42

43 11A 1A 99A 96A 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 ev 453 nm A -> 99A A ->1A.4445 T 1 T ev nm A ->11A > 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

44 7. 77 K emission spectra ormalized ntensity / a.u K 77K 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 K 77K 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

45 ormalized ntensity / a.u K 77K 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 K 77K 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

46 ormalized ntensity / a.u K 77K 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 K 77K 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

47 ormalized ntensity / a.u K 77K 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 K 77K 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

48 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 h -4 After 2 h.6 After 4 h.9-5 h After 2 h.6 After 4 h A h After 2 h After 4 h -6 A A Wavvelength / nm wavelength / nm h -7 After 2 h.6 After 4 h A 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 M. S48

49 ntensity / a.u h After 2 h After 4 h ntensity / a.u h After 2h After 4h ntensity / a.u. 6-3 h After 2h After 4h ntensity / a.u. 3-4 h After 2h After 4 h ntensity / a.u h After 2h After 4h ntensity / a.u. 4-6 h 3 After 2h After 4h ntensity / a.u. 6-7 h After 2 h After 4 h 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 M. S49

50 9. Photophysics of the Acceptors ntensity / a.u..9 a Absorption Emission.6.3 ntensity / a.u b Absorption Emission igure S8. (a) Absorption and fluorescence spectra of Perylene, λex = 39 nm; (b) absorption and emission spectra of 1CPEA, λex = 46 nm, M 2 C Cl Perylene 1CPEA S5