Supporting Information for: Ping Pong Energy Transfer in a Bodipy-Containing Pt(II) Schiff Base Complex: Synthesis, Photophysical Studies, and Anti- Stokes Shift Increase in Triplet Triplet Annihilation Upconversion Syed S. Razi, a Yun Hee Koo, b Woojae Kim, b Wenbo Yang, a Zhijia Wang, a Habtom Gobeze, c Francis D Souza, c Jianzhang Zhao a * and Dongho Kim b * a State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E 28 West Campus, 2 Ling Gong Rd., Dalian 11624, P. R. China. E mail: zhaojzh@dlut.edu.cn b Spectroscopy Laboratory for Functional Electronic Systems, and Department of Chemistry, Yonsei University, Seoul 12 749, Korea; E mail: dongho@yonsei.ac.kr c Department of Chemistry, University of North Texas, 1155 Union Circle, #357, Denton, TX 7623-517, USA. S1
Index Synthesis and Characterization of compounds... S3 S4 Table S1. Crystal Data Collection Parameters for the Pt Ph Complex....S5 Figure S1-S12. NMR and HRMS data.......s6 S12 Figure S13. Photoluminescence spectra of Pt BDP in different solvents. S13 Figure S14. Luminescence spectra of Pt BDP, Pt Ph and BDP.... S14 Figure S15. Singlet oxygen ( 1 O2) photosensitizing of the compounds.s15 Figure S16. Femtosecond transient absorption spectra of Pt-BDP..S16 Figure S17. Femtosecond transient absorption spectra of Pt-Ph.....S17 Figure S18. Nanosecond time resolved transient absorption spectra..s17 Figure S19. TTA upconversion...s18 Table S2. The Calculated Low-Lying Electronic Excited States of Pt-BDP..S19 S2
Synthesis and Characterization. Synthesis of 1. 3, 5-di-tert-butyl-2 hydroxybenzaldehyde (936 mg, 4. mmol) was dissolved in EtOH (3 ml), 4-bromophenylenediamine (374 mg, 2. mmol) and acetic acid (.5 ml) was added, the mixture was refluxed for 1 h until the reaction have completed (monitored by TLC). After completed the reaction, solvent was evaporated under reduced pressure, washed with water, dried in air and recrystallized from EtOH to give orange needle crystals (1.6 g, 3.47 mmol) in 84.6% yield. 1 H NMR (4 MHz, DMSO d6): δ 13.67 (s, 1H), 13.57 (s, 1H), 9.3 (s, 1H), 8.98 (s, 1H), 7.8 (s, 1H,), 7.6 (s, 1H,), 7.53 (s, 1H,), 7.5 7.47 (d, 2H, J = 5.2 Hz), 7.41 (t, 2H, J = 3.2 Hz), 1.38 (s, 18H), 1.29 (s, 18H). MALDI HRMS: calcd ([C36H47BrN2O2] + ), m/z = 618.2821, found m/z = 619.2925(m+H) +. Synthesis of 2. K2PtCl4 (415 mg, 1. mmol), 1 (619 mg, 1. mmol) and K2CO3 (414 mg, 3. mmol) were dissolved in degassed DMSO (1 ml), the flask was vacuumed and back filled with argon for several times, then the mixture was stirred at 75 C for 12 h. The red precipitation was collected and further purified by column chromatography (dichloromethane as eluent). After removal of the solvent the red solid (45.5 mg,.77 mmol) was collected in 6.6% yield. 1 H NMR (4 MHz, DMSO d6): δ 9.59 (s, 1H), 9.54 (s, 1H), 8.77 (s, 1H,), 8.45 (s, 1H,), 7.73 (d, 2H, J = 12. Hz), 7.66 (d, 1H, J = 8. Hz,), 7.61 (t, 2H, J1 = 2.4 Hz, J2 = 2.4 Hz), 1.51 (s, 18H), 1.33 (s, 18H). MALDI MS: calcd ([C36H45BrN2O2Pt] + ), m/z = 811.2312, found m/z = 811.2197. Synthesis of 4. Under an Ar atmosphere, 4 formylbenzeneboronic acid (1.5 g, 1. mmol) and pinacol (1.18 g, 1 mmol) were placed with toluene (15 ml) in a round-bottom flask. S3
The mixture was refluxed for 12 h at 12 C. Evaporation of the solvent under reduced pressure lead to formation of a white yellow solid 3 (2.3 g, yield: 99%). This crude product was used for the next step of the synthesis without further purification. Under an Ar atmosphere, the above crude product 3 (2. g, 8.7 mmol) and 2,4 dimethylpyrrole (2 ml, 2 mmol) were dissolved in dry CH2Cl2 (15 ml). A few drops of trifluoroacetic acid were added to the solution, and the mixture was stirred 12 h at room temperature. After completion of the reaction (monitored via TLC), a solution of DDQ (2. g, 8.7 mmol) in freshly distilled THF was added to the reaction mixture. The reaction mixture was stirred for 2 h. Absolute triethylamine (1 ml) was added to the reaction mixture. After this mixture was stirred for 15 min, BF3 Et2O (1 ml) was added dropwise under ice cold conditions. After the reaction mixture was stirred for 2 h more, the mixture was washed with water several times and then extracted with DCM. The organic phase was dried over anhydrous Na2SO4, and then the solvent was evaporated under reduced pressure. The residue was purified with column chromatography (silica gel, CH2Cl2) to give a red solid (1.2 g, yield 31%). 1 H NMR (CDCl3, 5 MHz): δ 7.91 (d, 2H, J = 5. Hz), 7.3 (d, 2H, J = 5. Hz), 5.97 (s, 2H), 2.55 (s, 6H), 1.39 (s, 12H), 1.37 (s, 6H). TOF MALDI HRMS: calcd ([C25H3N2O2B2F2] + ), m/z = 45.2462, found m/z = 45.2446. S4
Table S1. Crystal Data Collection Parameters for the Pt Ph Complex Complexes Pt Ph Sum Formula C42H5N2O2Pt M (g mol 1 ) 89.93 Temp K 296 (2) Crystal System Orthorhombic Space group Pbcn a (Å) 17.316 b (Å) 3.68 c (Å) 14.133 α (deg) 9 β (deg) 9 γ (deg) 9 Volume Å 3 758 Z 8 Dcalc g.cm 3 1.433 Crystal size (mm).23.12.9 F () 328 (Mo K ) mm 1 3.774 θ (deg) 2.29 19.15 Reflections collected 6623 Independent reflections 3541 Parameters 437 Largest diff. peak and hole (e Å 3 ).23,.9 Goodness of fit.984 R a R2 a.582 b.1386 b a 2 2 2 2 2 o c o, wr2 w Fo Fc w Fo R F F F Based on all data. 12 ; Fo 4 Fo. b S5
Br N N OH HO Figure S1. 1 H NMR spectrum of compound 1 (4 MHz, DMSO-d6), 25 C. RAZI-1 1642813 11 (.364) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (11:19) 621.2872 1 619.2925 3.88e3 % 622.2937 618.2935 623.316 65.2764 613.3674 65 61 615 62 625 63 635 64 645 Figure S2. TOF-HR mass spectrum of compound 1. 624.3253 639.3613 641.3854 643.3546 m/z S6
Br N N Pt O O Figure S3. 1 H NMR spectrum of compound 2 with partial enlarged details (4 MHz, DMSO-d6), 25 C. RAZI-3 16126 17 (.566) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (15:19) 811.2197 1 1.33e3 81.2252 812.2195 813.2128 % 89.2195 595.911 594.988 596.919 814.2228 593.993 675.38 732.3252 815.286 187.1223 592.922 828.2491 673.386 112.6415 19.1521 m/z 5 6 7 8 9 1 11 12 Figure S4. MALDI TOF HR mass spectrum of compound 2. S7
7.91 7.9 7.3 7.29 7.26 5.97 2.55 1.39 1.37. O O B N N B F F 2. 2. 2. 6.2 12.3 8 7 6 5 4 3 2 1 Figure S5. 1 H NMR spectrum of compound 4 (4 MHz, CDCl3), 25 C. ZM-4(CHCA) 14716 151 (5.34) TOF LD+ 1 45.2446 1.81e3 449.2456 % 431.2941 451.2457 43.2985 43.3826 452.245 35 375 4 425 45 475 5 525 55 575 6 625 65 675 Figure S6. MALDI TOF HR mass spectrum of compound 4. m/z S8
9. 8.92 8.22 8.1 8.8 7.88 7.86 7.69 7.63 7.61 7.46 7.45 7.4 7.36.93.95 1.1 1.6 2.3 2.3 1.6 2.5 1.5 1.4 9. 8.5 8. 7.5 9. 8.92 8.22 8.8 7.88 7.86 7.69 7.46 7.45 7.4 7.36 7.26 6.2 N F B F N 2.58 1.59 1.5 1.37. N N Pt O O.95 2.3 1.4 2.6 6.13 18. 9 8 7 6 5 4 3 2 1 Figure S7. 1 H NMR spectrum of compound Pt BDP with partial enlarged details (4 MHz, CDCl3), 25 C. S9
RAZI-1(CHCA) 165182 37 (1.232) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (37:61) 155.4642 1 3.71e3 154.476 % 839.89 838.79 84.829 157.455 158.4574 697.767 837.697 841.822 153.4628 779.8143 842.692 129.387 869.977 982.2687 17.437 1142.5223 1199.567 123.52881285.657 7 8 9 1 11 12 13 m/z Figure S8. MALDI TOF HR mass spectrum of compound Pt BDP. N N Pt O O Figure S9. 1 H NMR spectrum of compound Pt Ph with partial enlarged details (4 MHz, CDCl3), 25 C. S1
Figure S1. 13 C NMR spectrum of compound Pt BDP with partial enlarged details (1 MHz, CDCl3), 25 C. The asterisks indicated solvent peak of ether. SSR 1612216 62 (2.68) Cn (Cen,4, 5., Ht); Sm (SG, 2x3.); Sb (15,1. ); Cm (62:7) 756.2681 1 757.273 755.2667 794.341 795.3547 1.44e3 81.357 % 811.3571 812.3538 813.3595 68.2251 814.3571 578.1295 594.1667 865.4281 944.4826 m/z 5 55 6 65 7 75 8 85 9 95 1 Figure S11. MALDI TOF HR mass spectrum of compound Pt Ph. S11
Figure S12. 13 C NMR spectrum of compound Pt Ph (1 MHz, CDCl3), 25 C. S12
3 a 3 b Intensity / a.u. 2 1 N 2 Air 5 6 7 8 Wavelength / nm Intensity / a.u. 2 1 Air N 2 5 6 7 8 Wavelength / nm 3 c Intensity / a.u. 2 1 Air N 2 5 6 7 8 Wavelength / nm Figure S13. Photoluminescence spectra of Pt BDP in different solvents (a) CH2Cl2, (b) CH3CN and (c) CH3OH under air and N2 atmosphere. ex = 475 nm. c = 1. 1 5 M. 2 C. Note we found Pt-BDP is unstable toward photo-irradiation, the resulted decomposition may induce a stronger emission at 515 nm. However, for the above results in Figure S13, we confirmed that the samples are pure, and the phosphorescence emission band becomes weaker in polar solvents. With the same sample (solution), we reproduced the results in toluene (Figure 2b in the main text of the manuscript). S13
Intensity / a.u. 16 12 8 4 BDP Pt-BDP Pt-Ph 5 55 6 65 7 Wavelength / nm Figure S14. Luminescence spectra of Pt BDP, Pt Ph and BDP. Determined with optically matched solution ( ex = 475 nm). c = ca. 1. 1 5 M in toluene. 2 C. S14
Absorbance.8.4 a Absorbance 1.2 1..8.6.4 b. 4 8 12 Time / s.2 4 8 12 Time / s Figure S15. Singlet oxygen ( 1 O2) photosensitizing of (a) Pt BDP ( ex = 5 nm). c = 1. 1 5 M and (b) Pt Ph, Xenon lamp was used as light source. ( ex = 5 nm, optically matched solutions were used), c = 1. 1 5 M. In toluene. 2 C. S15
O.D.. a 1 ps -.2 5 ns O.D.. b -.2 B (143 ps) C (long) c O.D..2. -.2 45 B (143 ps) C (long) 525 6 675 Wavelength / nm 75 Figure S16. Femtosecond transient absorption spectra measured (a) from 1 ps to 5 ns and (b) Evolution-Associated and (c) Decay-Associated Difference Spectra of Pt BDP in toluene obtained from global target analysis at 56 nm excitation. S16
O.D..2.1 1 ps 1 ps 1 ps 1 ns 5 ns. 45 5 55 6 65 7 75 Wavelength (nm) Figure S17. Femtosecond transient absorption spectra measured from 1 to 5 ns of Pt-Ph in toluene. 56 nm excitation).. O. D..2 = 3.35 ns O. D..1 =.52 s a.2 b.4 1 2 3 4 Time / ns 2 4 6 8 1 Time / s Figure S18. The nanosecond time resolved transient difference absorption spectra. (a) Pt BDP and (b) Pt Ph in aerated toluene. ex = 532 nm laser, 2 C. S17
8 Pt-BDP + Py a 12 * Pt-Ph b Intensity / a.u. 6 4 2 * Pt-BDP Intensity / a.u. 8 4 Pt-Ph + Py Intensity / a.u. 4 2 4 5 6 7 Wavelength / nm Pt-BDP + Py c Pt-BDP 4 5 6 7 Wavelength / nm * Intensity / a.u. 4 5 6 7 8 Wavelength / nm 2 1 Pt-Ph Pt-Ph + Py * d 4 5 6 7 8 Wavelength / nm Figure S19. Comparable TTA upconversion with (a) Pt BDP and (b) Pt Ph at 51 nm laser in toluene. For (c) Pt BDP and (d) Pt Ph at 589 nm laser as the triplet sensitizers (c = 1. 1 5 M) and perylene as the acceptor (4. 1 5 M) in optically matched toluene solution. The asterisks indicate the scattered laser. Excited with CW laser ( ex = 51 and 589 nm), 4 mw, 2 C. S18
Table S2. Properties of the Low-Lying Electronic Excited States of Pt BDP Calculated by TDDFT B3LYP GENECP, based on the DFT B3LYP GENECP-Optimized Ground-State Geometries. Electronic transition Energy / ev/nm a f b Compositio n c CI d Character Singlet S S1 2.29 542.1592 H L 1.6938 ILCT S S6 2.86 433.5827 H 1 L.6937 ILCT S S9 3.2 387.3539 H 2 L 2.6618 ILCT S S1 3.23 384.7775 H 2 L 2.6618 ILCT Triplet e S T1 1.52 815. H 1 L.785 MLCT S T2 1.84 673. H 2 L 2.6653 MLCT ILCT S T3 2.1 617. H 2 L 1.5425 MCT ILCT a Only the selected low-lying excited states are presented. b Oscillator strengths. c Only the main configurations are presented. d e The CI coefficients are in absolute values. No spin-orbital coupling effect is considered; thus, the oscillator strength, i.e. the f values, are zero. S19