Haiyang Sun, Huimin Guo,* Wenting Wu, Xin Liu, Jianzhang Zhao*

Transcription

1 Electronic Supplementary Information for: Coumarin phosphorescence observed with ^ Pt(II) bisacetylide complex and its applications for luminescent oxygen sensing and triplet-triplet-annihilation based upconversion Haiyang Sun, Huimin Guo,* Wenting Wu, Xin Liu, Jianzhang Zhao* State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, , P. R. China. zhaojzh@dlut.edu.cn (J.Z.); guohm@dlut.edu.cn (H.G.) Index General information...s2 Scheme 1 S1. Synthesis of Pt S2 Figure S1. 1 H MR of S3 Figure S2. 1 H MR of S3 Figure S3. 13 C MR of S4 Figure S4. TF MS of L-c of S4 Figure S5. 1 H MR of Pt-1... S5 Figure S6. 13 C MR of Pt-1... S5 Figure S7. HR-MALDI-MS of Pt S6 Figure S8. UV-Vis absorption spectra of Pt-1 and Pt-2 in toluene.....s6 Figure S9. Lifetime of Pt S7 Figure S10. Emission of Pt-1 at 77 K..... S7 Figure S11. Emission of Pt-1 in solid state..... S8 Figure S12. ptimzied T 1 state geometry of Pt S9 Table S1. B analysis of SMs of T 1 state of Pt-1... S9 Table S2. Mulliken and B population analysis on T 1 and S 0 of Pt-1.. S10 S1

2 Experimental section General information MR spectra were taken on a 400 MHz Varian Unity Inova spectrophotometer. Mass spectra were recorded with a Q-TF Micro MS spectrometer. UV-Vis spectra were taken on a HP8453 UV-visible spectrophotometer. Fluorescence spectra were recorded on a JASC FP-6500 or a Sanco 970 CRT spectrofluorometer. Luminescence quantum yields were measured with [Ru(bpy) 2 (Phen)][PF 6 ] 2 as the reference (Φ = 6.0 % in actonitrile). Diode pumped solid state laser (DPSSL) with 473 nm or 532 nm were used as excitation soruce for the upconversion experiments. The diameter of the laser spot is ca. 3 mm. The output power of the DPSS laser can be adjusted continuously. The laser power was measured with phototube. For 532 nm laser, the variation of the power is less than ±5% over eight hours. The noise of the 532 nm DPSS laser is 20%-25% in the range of 1 khz- 1 MHz. The noise of the 473 nm DPSS laser is 20%-25% in the range of 1 khz- 1MHz. For the upconversion experiments, the mixed solution of the complex (triplet sensitizer) and perylene (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 was observed with fluorospectrometer. In 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 upconversion quantum yields were calculated with a reported method. 1 In the two-site model for the oxygen sensing (please refer to the Fig. 13 in the main text), the 2 -sensitive dyes are treated as two different portions. Fraction of the two portions are defined as f 1 and f 2, respectively (f 1 +f 2 = 1), the two portions show different quenching constants (K SV1 and K SV2, Eq. 1). I I 0 = f 1+ K 1 SV 1 p 1 f + 1+ K 2 2 SV 2 p 2 (Eq. 1) CH H 1) CH 2 (CC 2 H 5 ) 2) HCl/AcH Br 2 Br AcH 5 4 PdCl 2 (PPh 3 ) 2,CuI H DMF TEA TMS Pt Pt-1 Pt(dbbpy)Cl 2 CH 2 Cl 2, DMF 2 THF TBAF MeH 3 TMS Scheme S1. Synthesis of Pt-1. S2

3 Figure S1. 1 H MR of 5 (CDCl 3, 400 MHz) Figure S2. 1 H MR of 2 (CDCl 3, 400 MHz). S3

4 Figure S3. 13 C MR of 2 (CDCl 3, 100 MHz). s zjz (5.801) Cm (348:363-72:125) 100 GCT CA Dec :35:56 TF MS EI+ 1.75e5 % m/z Figure S4. TF MS of 2. S4

5 Pt Pt Figure S5. 1 H MR of Pt-1 (CDCl 3, 400 MHz) Figure S6. 13 C MR of Pt-1 (CDCl 3, 100 MHz). S5

6 SHY(CHCA) (0.566) Cn (Cen,4, 50.00, Ht); Sm (SG, 2x3.00); Sb (15,10.00 ); Cm (6:23) TF LD e % Pt Pt m/z Figure S7. HR-MALDI-MS of Pt Absorbance Pt-1 Pt Wavelength / nm Figure S8. Comparison of the UV-Vis absorption spectra of Pt-1 and Pt-2 in toluene solution at room temperature. c = mol/l. 20 C. S6

7 0.020 Pt-1 Intensity τ = 2.52 µs Lifetime / ns Figure S9. The lifetime of Pt-1 by following decay at the bleaching wavelength. 20 C Figure S10. Fluorescence intensity / a.u K RT Wavelength / nm Emission spectra of Pt-1 in the solution of EtH:MeH (v/v= 4:1) in 77 K and room temperature (RT), λex = 414 nm. S7

8 100 Fluorescence intensity / a.u Wavelength / nm Figure S11. Emission spectra of Pt-1 in solid state, λex = 420 nm, 20 C. We performed B analysis on the optimized T 1 state, as shown in Table S1. We found that the SM states of T 1 are contributed by C73, C83 and the localized the interaction among C71, C72, C75, C76, 77 C78, C79, C80, C81, C83 and 86. This is consistent with the contour plot of the spin density. Due to the charge transfer involved from the electronic process during the excitation-annealing circle from S 0 to S 1 and then to T 1, and the localization nature of the π and π* states of the molecule, dbbpy part of the molecule also bear spin. To support this, we also performed population analysis. As the B doesn t provide information on spin population, we also studied the population of T 1 with respect to S 0 within Mulliken scheme. The results are shown in Table S2. It s apparent from Table S2 that the results of B and Mulliken analysis show the same trend. And, we show that the overall result of the excitation-annealing on the population is the formation of the localized spin state crossing dbbpy and the coumarin acetylide ligand. The IL character of the T 1 state is obvious. (In Table S2, the red highlighted items indicate a significant charge transfer). S8

9 Figure S12. ptimzied T 1 state geometry of Pt-1. Table S1. B analysis of SMs of T 1 state of Pt-1. B o. Bond Type ccupation (e) Energy (a.u.) Principal Delocalizations a (geminal,vicinal,remote) 183 LP*(1) C [0.668(p)C (p)C72](v), 336[(p)76](v), 329[(p)C73](g), 320[(p)C47] (v), 340[(p)77] (r) 198 LP*(1) C [0.549(p) (sp 3 )C78](v) 561[0.763(p)C (p)C81](v), 428[(p)C83](g), 422[(p)C81](v), 419[(p)C80](v), 432[(p)86](v) S9

10 Table S2. Mulliken and B population analysis on T 1 and S 0 of Pt-1. o. El. T 1 S 0 Diff. Mulliken B Spin Mulliken B Mulliken B 1 C C C C C C C C C C H H H H Pt C H H C C C H H H C H H H C H H H C H H H C H H H C S10

11 44 H H H C C C C H C C C C H C H H C C H H H H H H C C C C H C C C C H C H H C C H S11

12 90 H H H H H C C C S12