DiiodoBodipy-Perylenebisimide Dyad/Triad: Preparation and Study of the Intramolecular and. Intermolecular Electron/Energy Transfer

Transcription

1 Supporting nformation for: DiiodoBodipy-Perylenebisimide Dyad/Triad: Preparation and Study of the ntramolecular and ntermolecular Electron/Energy Transfer Zafar Mahmood, a Kejing Xu, a Betül Küçüköz, b Xiaoneng Cui, a Jianzhang Zhao, a, * Zhijia Wang, a Ahmet Karatay, b Halime Gul Yaglioglu, b Mustafa Hayvali c, * and Ayhan Elmali b a State Key Laboratory of ine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-28 West Campus, 2 Ling-Gong Road, Dalian 11624, P. R. China zhaojzh@dlut.edu.cn Web: b Department of Engineering Physics, aculty of Engineering, Ankara University, 61 Beşevler, Ankara, Turkey; c Department of Chemistry, aculty of Science, Ankara University, 61 Beşevler, Ankara, Turkey. hayvali@science.ankara.edu.tr S1

2 Contents 1. General nformation...page S3 2. Molecular Structure Characterization Data...Page S3 3. UV/Vis Spectra...Page S18 4. The luorescence Spectra...Page S23 5. Redox Properties of Compounds...Page S29 6. anosecond Time-resolved Transient Spectra...Page S32 7. Photooxidation...Page S33 8. Photophysical Processes.....Page S36 9. x,y,z Coordinates of the ptimized Geometries...Page S38 S2

3 1. 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 chemical shifts are reported in parts per million (ppm) relative to TMS, with the residual solvent peak used as an internal reference. The mass spectra were measured by T MS MALD and ES spectrometer. 2. Molecular structure characterization data igure S1. 1 H MR of compound 1 (5 MHz, CDCl 3 ), 25 C. ppm S3

4 ZM-1(CHCA) (2.87) T LD e % m/z igure S2. MALD HR MS of 1 (CH 2 Cl 2 ). 25 C Br igure S3. 1 H MR of compound 2 (5 MHz, CDCl3), 25 C. ppm S4

5 Zarfar BM (4.333) Cm (26:264-35:61) 1 GCT CA ct-21415:57:41 T MS E+ 3.3e3 % Br m/z igure S4. T MS E of Br Br igure S5. 1 H MR of compound 3 (5 MHz, CDCl3), 25 C. ppm S5

6 ZM-2(CHCA) (1.133) T LD e3 % Br Br m/z igure S6. MALD HR MS of 3 (CH 2 Cl 2 ) B B ppm igure S7. 1 H MR of compound 4 (5 MHz, CDCl3), 25 C. S6

7 ZM-4(CHCA) (5.34) T LD e3 B % B m/z igure S8. MALD HR MS of 4 (CH 2 Cl 2 ) B ppm igure S9. 1 H MR of compound 5 (4 MHz, CDCl 3 ), 25 C. S7

8 ZM-6(CHCA) (.832) T LD % B igure S1. MALD HR MS of 5 (CH 2 Cl 2 ). m/z B igure S11. The 13 C MR spectra of 5 (1 MHz, CDCl 3 ). 25 C. S8

9 B B igure S12. 1 H MR of compound 6 in CDCl3 (4 MHz), 25 C. ppm ZM-7(CHCA) (1.231) T LD e B % B m/z igure S13. MALD HR MS of 6 (CH 2 Cl 2 ). S9

10 igure S14. The 13 C MR spectra of 6 (1 MHz, CDCl 3 ). 25 C igure S15. 1 H MR of compound L-1 in CDCl3 (5 MHz), 25 C. ppm S1

11 igure S CMR of compound L-1 in CDCl3 (1 MHz), 25 C. ZM-L-1(CHCA) (.764) T LD e % m/z igure S17. MALD HR MS of L-1 (CH 2 Cl 2 ). S11

12 ppm igure S18. 1 H MR of compound L-2 in CDCl3 (5 MHz), 25 C. igure S C MR of compound L-2 in (1 MHz, CDCl3), 25 C. S12

13 ZM-L-2(CHCA) (1.9) T LD % m/z igure S2. MALD HR MS of L B igure S21. 1 H MR of compound L-3 in CDCl3 (5 MHz), 25 C. ppm S13

14 B igure S C MR of compound L-3 in CDCl3 (1 MHz), 25 C. ZM(CHCA) (.299) T LD e3 % B m/z igure S23. MALD HR MS of L-3 (CH 2 Cl 2 ). S14

15 B ppm igure S24. 1 H MR of compound B-1 (4 MHz, CDCl3), 25 C. B igure S C MR of compound B-1 (1 MHz, CDCl3), 25 C. S15

16 ZM-B1(CHCA) (4.71) T LD e % B m/z igure S26. MALD HR MS of B-1 (CH 2 Cl 2 ) B B igure S27. 1 H MR of compound B-2 (4 MHz, CDCl3), 25 C ppm S16

17 B B igure S C MR of compound B-2 (1 MHz, CDCl3 ), 25 C. ZM-B2(CHCA) (1.581) T LD e B % B m/z igure S29. MALD HR MS of B-2 (CH 2 Cl 2 ). S17

18 3. UV vis absorption spectra a.25 x 1-5 M.5 x 1-5 M 1. x 1-5 M b.25 x 1-5 M.5 x 1-5 M 1. x 1-5 M c.5 x 1-5 M 1. x 1-5 M 2. x 1-5 M d.5 x 1-5 M 1. x 1-5 M 2. x 1-5 M e.5 x 1-5 M 1. x 1-5 M 2. x 1-5 M f.25 x 1-5 M.5 x 1-5 M 1. x 1-5 M igure S3. UV vis absorption spectra of (a) B-1, (b) B-2, (c) L-1, (d) L-2, (e) 5 and (f) 6 at different concentration. in toluene, 2 C. S18

19 Solvent-dependency UV Vis absorption of compounds a CH 3 C DCM PhCH 3 CH 3 H b CH 3 C DCM PhCH 3 CH 3 H c CH 3 C DCM PhCH 3 CH 3 H d CH 3 C DCM PhCH 3 CH 3 H e CH 3 C DCM PhCH 3 CH 3 H f CH 3 C DCM PhCH 3 CH 3 H g CH 3 C DCM PhCH 3 CH 3 H h CH 3 C DCM PhCH 3 CH 3 H igure S31. UV Vis absorption spectra of the compounds in different solvents of (a) B-1; (b) B-2; (c) L-1; (d) L-2; (e) L-3; (f) 5; (g) 6 and (h) BDPY. c = M; 2 C. S19

20 a B-1 L-1 L b B-1 L-1 L c B-1 L-1 L igure S32. UV vis absorption spectra of B-1, L-1 and L-3 in (a) CH 3 C; (b) DCM; (c) CH 3 H. c = M, 2 C a B-2 L-2 L b B-2 L-2 L c B-2 L-2 L igure S33. UV vis absorption spectra of B-2, L-2 and L-3 in (a) CH 3 C; (b) DCM; (c) CH 3 H. c = M, 2 C. S2

21 a 5 L-1 L b 5 L-1 L c 5 L-1 L d 5 L-1 L igure S34. UV vis absorption spectra of 5, L-1 and L-4 (Bodipy) in (a) CH 3 C; (b) DCM; (c) toluene and (d) CH 3 H. c = M, 2 C. S21

22 a 6 L-2 L b 6 L-2 L c 6 L-2 L d 6 L-2 L igure S35. UV vis absorption spectra of 6, L-2 and L-4 (Bodipy) in (a) CH 3 C; (b) DCM; (c) toluene and (d) CH 3 H. c = M, 2 C. S22

23 4.luorescence spectra 6 45 a 4 3 b ntensity 3 15 L-3 ntensity 2 1 L-3 B B igure 36. luorescence emission spectra of B-1 and L-3 in (a) DCM and (b) CH 3 C. λ ex = 58 nm. The absorption in the excitation wavelength is same. 2 C. ntensity L-3 a 15 B ntensity L-3 b 1 B igure S37. luorescence emission spectra of B-2 and L-3 in (a) DCM and (b) CH 3 C. λ ex =48 nm. The absorption in the excitation wavelength is same. 2 C. S23

24 8 6 a 8 6 b ntensity 4 2 L-1 ntensity 4 2 L-1 B B wavelength / nm igure S38. To confirm the photo-induced electron transfer in B-1. luorescence emission spectra of B-1 and L-1 in (a) DCM and (b) CH 3 C. λ ex = 515 nm. The absorption in the excitation wavelength is same. 2 C. 15 a 2 b ntensity 1 5 L-2 B ntensity L-2 B igure S39. To confirm the photo-induced electron transfer in B-2. luorescence emission spectra of B-2 and L-2 in (a) DCM and (b) CH 3 C. λ ex =46 nm. The absorption in the excitation wavelength is the same. 2 C. S24

25 Solvent-dependency Emission of compounds a PhCH 3 DCM CH 3 C 6 b PhCH 3 DCM 45 CH 3 C ntensity 1..5 ntensity c PhCH 3 DCM CH 3 C ntensity igure S4. luorescence emission spectra of (a) B-2 (λ ex =48 nm) ; (b) L-3 (λ ex = 48 nm) and (c) L-2 (λ ex = 46 nm). The absorption in the excitation wavelength is same. 2 C. S25

26 15 12 a b ntensity 9 6 PhCH 3 DCM CH 3 C ntensity.9.6 PhCH 3 DCM CH 3 C c ntensity PhCH 3 DCM CH 3 C igure S41. luorescence emission spectra of (a) 5; (b) 6 and (c) L-4 (Bodipy), λ ex = 467 nm. c = M; 2 C. S26

27 a 45 b 45 c ntensity 2 1 L ntensity 3 15 L ntensity 3 15 L-4 5 B L igure S42. luorescence emission spectra of 5 and L-4 in (a) Toluene; (b) DCM; (c) CH 3 C. λ ex = 467 nm. 2 C. The absorption in the excitation wavelength is same. 2 C. 4 3 a 6 45 b 6 45 c ntensity 2 1 L-4 ntensity L-4 ntensity L-4 B L igure S43. luorescence emission spectra of 6 and L-4 in (a) Toluene; (b)dcm ; (c) CH 3 C. λ ex =467 nm. M. 2 C. The absorption in the excitation wavelength is same. 2 C. S27

28 ntensity L-1 a ntensity L-1 b igure S44. To confirm the PET effect in dyad 5: fluorescence emission spectra of 5 and L-1 in (a) toluene and (b) CH 3 C. λ ex = 58 nm. ptically matched solutions were used (the absorption of the solutions are the same at the excitation wavelength. The concentration is ca. 1 5 M 1 ). 2 C. 5 4 a 3 b ntensity 3 2 L-2 ntensity 2 1 L igure S45. To confirm the PET effect in triad 6: luorescence emission spectra of 6 and L-2 in (a) toluene and (b) CH 3 C. λ ex = 58 nm. ptically matched solutions were used (the absorption of the solutions are the same at the excitation wavelength. The concentration is ca. 1 5 M 1 ). 2 C. S28

29 5.Redox properties of compounds. a c + / c b c + / c c c + / c Current Current Potential / V Potential / V 6 Current L-4 B B L Potential / V 5 igure S46. Cyclic voltammogram of (a) 5; (b) 6 and (c) L-4. B B 6 S29

30 a c + / c b c + / c Current Current 5 BDP Potential / V 6 BDP Potential / V igure S47. Cyclic voltammogram of (a) L-4 (bodipy) and 5 and (b) L-4 and 6. The curve of BDP is presented in both figure for comparison. errocene (c) was used as internal reference (E 1/2 = +.64 V (c + /c) vs. standard hydrogen electrode. n deaerated CH 2 Cl 2 solutions containing.5 mm photosensitizers and ferrocene, and.1 M Bu 4 P 6 as supporting electrolyte, Ag/Ag 3 reference electrode. Scan rates: 5 mv/s. 2 C. Calculation of the Gibbs free energy changes of the photo-induced electron transfer The free energy changes of the intramolecular electron transfer process, can be calculated with the Weller equation (Eq. 1 and Eq. 2). Δ G CS = e[ EX ERED] E + ΔGS (Eq. 1) ΔG = 2 e πε ε R 2 e πε R D R 4 S CC A 1 ε RE 1 ε S S (Eq.2) S3

31 Where ΔG S is the static Coulombic energy, which is described by eq. 3. e = electronic charge, E X = half-wave potential for one-electron oxidation of the electron-donor unit, E RED = halfwave potential for one-electron reduction of the electron-acceptor uni; E = energy level approximated with the fluorescence emission (for the singlet excited state), ε S = static dielectric constant of the solvent, R CC = center-to-center separation distance between the electron donor (Bodipy) and electron acceptor (PB), determined by DT optimization of the geometry, R D is the radius of the electron donor, R A is the radius of the electron acceptor, ε RE is the static dielectric constant of the solvent used for the electrochemical studies, ε is permittivity of free space. The solvents used in the calculation of free energy of the electron transfer is toluene (ε S = 2.38), CH 2 Cl 2 (ε S = 8.93) and acetonitrile (ε S = 37.5). The Redox properties of Reference compound L-4 (BDP) are give below. Table S2. Electrochemical redox potentials (V vs. c/c + ) and driving forces of charge recombination (ΔG CR ) and charge separation (ΔG CS ) for reference compounds L-4 via 1 BDP* and 1 PB* in toluene, dichloromethane and acetonitrile Compound xidation(v) Reduction(V) L Energies of the charge-separated states (E CS ) and charge recombination energy state (ΔG (CR) ) can be calculated with the Eq. 3 and Eq. 4. E = ee [ E ] +Δ G (Eq. 3) CS X RED S Δ G = ( Δ G + E ) (Eq. 4) CR CS The data were collected in Table 3. S31

32 6. anosecond Transient Spectra Δ..D μs μs μs 4. μs L-3/L-1 = 1:.1 a Time / μs Δ..D μs 68 μs μs 4 μs L-3/L-1 = 1:.5 b Time / μs Δ..D μs μs μs 4. μs L-3/L-1 = 1: Time / μs c Δ..D μs μs μs 4. μs L-3/L-1 = 1:.1 d Time / μs igure S48. ntermolecular triplet energy transfer: anosecond transient absorption spectra of the mixture of L-1 and L-3, with L-3 as the triplet energy donor and L-1 as the triplet energy acceptor. The concentration of L-3 is fixed at M and the increasing concentration of L-1 at (a) M, (b) M, (c) M, (d) M. Excited with pulsed nanosecond laser at 532 nm in deaerated toluene at 2 C. S32

33 7. Photooxidation Comparison of singlet oxygen generation ability of Photosensitizers and reference compounds. Here -BDP stands for single iodo-bodipy BDP a BDP b Time / s Time / s igure S photosensitizing effect of 5, 6 and -BDP, demonstrated by the photooxidation of 1,3-diphenylisobenzofuran (DPB). Plotting of the absorption changes of DPB at 414 nm vs. photoirradiation time for (a) 5 and -BDP, (b) 6 and -BDP. Excited with 51 nm monochromatic light, the absorption at excitation wavelength is same. n toluene, 2 C. ote the 1 2 photosensitizing ability of compounds 5 and 6 may be due to the PB moiety, which show 12 photosensitizing ability (Table 1 in the main text). n other solvents, the singlet oxygen ( 1 2 ) photosensitizing ability of compounds 5 and 6 are very weak. S33

34 1. a 1. b L-3 B L-3 B Time / s Time / s igure S photosensitizing effect of B-1, B-2 and L-3, demonstrated by the photooxidation of 1,3-diphenylisobenzofuran (DPB), by plotting of the absorption changes of DPB at 414 nm vs. photoirradiation time for (a) B-1 and L-3, (b) B-2 and L-3. Excited with 531 nm monochromatic light, the absorption at excitation wavelength is same. n toluene, 2 C. S34

35 1. a 1. b B-1 L B-2 L Time / s Time / s igure S photosensitizing effect of B-1, B-2 and L-3 in photooxidation of 1,3- diphenylisobenzofuran (DPB), by plotting of the absorption changes of DPB at 414 nm vs. photoirradiation time for (a) B-1 and L-3, (b) B-2 and L-3. Excited with 531 nm monochromatic light, the absorption at excitation wavelength is same. n acetonitrile, 2 C. 1,3-Diphenylisobenzofuran (DPB) S35

36 8. Photophysical processes 1 [BDP-PB*] RET 2.16 ev 2.15 ev CTS 3 [BDP*-PB] SC 1 [BDP*-PB] 2.24 ev 534 nm 3 [BDP-PPB*] TTET 1.69 ev 538 nm 1.2 ev S S igure S52. Simplified Jablonski diagram illustrating the photophysical processes involved in B-1 (in toluene) ev 1 [BDP-PB*] RET SC 1 [BDP*-PB] 2.25 ev 528 nm 3 CTS [BDP*-PB] 1.73 ev 1.69 ev TTET 3 [BDP-PPB*] 1.2 ev 53 nm S S igure S53. Simplified Jablonski diagram illustrating the photophysical processes involved in B-1 (in acetonitrile). S36

37 1 [BDP-PB*] 2.7 ev 546 nm 3 [BDP-PPB*] RET SC 3 [BDP*-PB] CTS 1.7 ev TTET 1.69 ev 1.2 ev 1 [BDP*-PB] 2.25 ev 53 nm S S igure S54. Simplified Jablonski diagram illustrating the photophysical processes involved in B-2 (in toluene). 2.7 ev 1 [BDP-PB*] 1.82 ev CTS RET 3 [BDP*-PB] SC 1 [BDP*-PB] 2.24 ev 554nm 3 [BDP-PPB*] TTET 1.69 ev 538 nm 1.2 ev S S igure S55. Simplified Jablonski diagram illustrating the photophysical processes involved in B-2 (in acetonitrile). S37

38 9. x,y,z coordinates of the optimized geometries DT calculation by rcam-b3lyp/genecp. B-1 1 C C C C C C C C C C H H H C C C C C C C C H H C C C C C H H C H C H H S38

39 C H H C H H C H H H C H H C H C H H C H H C H H C H H H C H H C H H H C H H C H H H C C H C C C C C C C S39

40 B C H H H C H H H C H H H C H H H C C C C C H H H C H C C H B-2 1 C C C C C C C C C S4

41 C H H H C C C C C C C C H H C C C C C H H C H C H H C H H C H H C H H H C H H C H C H S41

42 H C H H C H H C H H H C H H C H H H C H H C H H H C C H C C C C C C C B C H H H C H H H C S42

43 H H H C H H H C C C C C H H H C H C C C C C C C C C B C H H H C H H H C H H H C H H H S43

44 C C C C C H H H C H C C S44