Supporting Information

Transcription

1 Supporting Information For Bioinspired Orientation of β-substituents on Porphyrin Antenna Ligands Switches Ytterbium(III) NIR Emission with Thermosensitivity Yingying Ning, Xian-Sheng Ke, Ji-Yun Hu, Yi-Wei Liu, Fang Ma, Hao-Ling Sun, and Jun-Long Zhang*, Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 1871, P. R. China; Department of Chemistry, Beijing Normal University, Beijing 1875, P. R. China

2 Supporting Contents... 3 Table S1. Crystal data and structure refinement for Yb-1 and Yb Table S2. Parameters obtained for Stern-Volmer experiment Figure S1. Normalized absorption spectra of Yb(III) complexes in CH 2 Cl 2 at room temperature.. 5 Figure S2. NIR luminescence intensity comparison of Yb-1 to Yb-4 in degassed CH 2 Cl 2 at room temperature (λ ex = 425 nm, OD 425 nm =.1) Figure S3. NIR luminescence decay curve of Yb-1 to Yb-4 in degassed CH 2 Cl 2 at room temperature (monitored at 97 nm) Figure S4. Normalized excitation and emission spectra of Yb-1 to Yb-4 in CH 3 OH/C 2 H 5 OH (v/v = 1:1) at 77K Figure S5. Integrated emission intensity vs absorbance plots for relative quantum yield determination of Yb-1 to Yb-4 vs YbTPP(L OEt ) (λ ex = 425 nm, Φ r =.24) in degassed CH 2 Cl 2 at room temperature Figure S6. Absorption spectra of the f-f transitions of Yb(III) in Yb-1 and Yb-2 (1 mm) in CD 2 Cl Figure S7. Transient absorption spectra of Yb-1 to Yb-4 in degassed CH 2 Cl 2 (OD 42 nm =.5) following the 42 nm OPO laser excitation pulse (1 Hz, 2 mj pulse -1 ) Figure S8. Normalized emission spectra of Gd(III) complexes in CH 3 OH/C 2 H 5 OH (v/v = 1:1) at 77K Figure S9. Emission spectra of Yb-1 to Yb-4 in air-saturated or degassed CH 2 Cl 2 at room temperature (λ ex = 425 nm, OD 425 nm =.1) Figure S1. Integrated emission intensity vs absorbance plots for relative quantum yield determination of Yb-1 to Yb-4 vs YbTPP(L OEt ) (λ ex = 425 nm, Φ r =.24) in air-saturated CH 2 Cl 2 at room temperature Figure S11. NIR luminescence decay curve of Yb-1 to Yb-4 in air-saturated CH 2 Cl 2 at room temperature (monitored at 97 nm) Figure S12. Stern-Volmer plots of oxygen quenching of the NIR emission of Yb Figure S13. Temperature-dependent emission lifetimes of Yb-1 in air-saturated CH 2 Cl Figure S14. Temperature-dependent emission spectra of Yb-1, Yb-3 and Yb-4 in degassed CH 2 Cl 2 in the temperature range of K (λ ex = 425 nm) Figure S15. Temperature-dependent emission spectra of Yb-1, Yb-3 and Yb-4 in solid state in the temperature range of K (λ ex = 425 nm) Figure S16. Calibration curve for NIR emission detector Figure S17. HR ESI mass spectrum of Yb Figure S18. HR ESI mass spectrum of Yb Figure S19. HR ESI mass spectrum of Yb Figure S2. HR ESI mass spectrum of Yb Figure S21. Normalized FT-IR spectrum of Yb Figure S22. Normalized FT-IR spectrum of Yb Figure S23. Normalized FT-IR spectrum of Yb Figure S24. Normalized FT-IR spectrum of Yb

3 Supporting Tables and Figures Table S1. Crystal data and structure refinement for Yb-1 and Yb-2. Complex Yb-1 Yb-2 molecular formula C H 8.25 Co.25 F 5 NO 3.5 P.75 Yb.25 C 14.5 H 8.25 Co.25 F 5 NO 3.25 P.75 Yb.25 formula wt. (g mol -1 ) temperature (K) 296(2) 18.(1) radiation (, Å) crystal system orthorhombic orthorhombic space group P mmn P mmn a (Å) (11) (6) b (Å) (17) (8) c (Å) (7) (3) Volume (Å 3 ) (5) (2) Z 8 8 calcd (g cm 3 ) (mm 1 ) F() crystal size (mm 3 ) Theta range to to reflections collected independent reflections 4771 [R(int) =.371] 3546 [R(int) =.333] Completeness 99.5% 99.7% goodness-of-fit on F final R indices [R > 2 (I)] R indices (all data) largest diff. peak and R1 a =.383 wr 2 b =.1123 R1 a =.464 wr 2 b =.1177 R1 a =.34 wr 2 b =.976 R1 a =.397 wr 2 b =.18 hole (e Å -3 ).852 and and.419

4 Table S2. Parameters obtained for Stern-Volmer experiment. [O 2 ] (M) I /I slope τ (μs) k q,sv (M -1 s -1 ) Yb

5 Normalized Intensity Yb-1 Yb-2 Yb-3 Yb Figure S1. Normalized absorption spectra of Yb(III) complexes in CH 2 Cl 2 at room temperature.

6 Emission Intensity Yb-1 Yb-2 Yb-3 Yb Figure S2. NIR luminescence intensity comparison of Yb-1 to Yb-4 in degassed CH 2 Cl 2 at room temperature (λ ex = 425 nm, OD 425 nm =.1).

7 Residuals Residuals Counts Counts Residuals Residuals Counts Counts Yb Time (ns) Time (ns) 5-5 Yb Time (ns) -5 Yb Time (ns) -5 Yb-4 Figure S3. NIR luminescence decay curve of Yb-1 to Yb-4 in degassed CH 2 Cl 2 at room temperature (monitored at 97 nm).

8 Normalized Absorption Normalized Absorption Normalized Emission Normalized Emission Normalized Emission Normalized Absorption Normalized Absorption Normalized Emission 1..8 Yb-1 Excitation Emission Yb-2 Excitation Emission Yb Excitation Emission Yb Excitation Emission Figure S4. Normalized excitation and emission spectra of Yb-1 to Yb-4 in CH 3 OH/C 2 H 5 OH (v/v = 1:1) at 77K.

9 Integrated Intensity 2 15 Yb-1 Yb-2 Yb-3 Yb-4 YbTPP(LOEt) Absorbance at 425 nm Figure S5. Integrated emission intensity vs absorbance plots for relative quantum yield determination of Yb-1 to Yb-4 vs YbTPP(L OEt ) (λ ex = 425 nm, Φ r =.24) in degassed CH 2 Cl 2 at room temperature.

10 Absorbance.6.5 Yb-1 Yb Figure S6. Absorption spectra of the f-f transitions of Yb(III) in Yb-1 and Yb-2 (1 mm) in CD 2 Cl 2.

11 OD.1 Yb-1 Yb-2 Yb-3 Yb s 5 s 1 s 15 s 2 s 25 s 3 s s 2 s 4 s 6 s 8 s 1 s s 5 s 1 s 15 s 2 s 25 s 3 s s 5 s 1 s 15 s 2 s 25 s 3 s Figure S7. Transient absorption spectra of Yb-1 to Yb-4 in degassed CH 2 Cl 2 (OD 42 nm =.5) following the 42 nm OPO laser excitation pulse (1 Hz, 2 mj pulse -1 ).

12 Normalized Emission Gd-1 Gd-2 Gd-3 Gd Figure S8. Normalized emission spectra of Gd(III) complexes in CH 3 OH/C 2 H 5 OH (v/v = 1:1) at 77K.

13 Emission Intensity Emission Intensity Emission Intensity Emission Intensity 6 Yb-1 air degassed 6 Yb-2 air degassed Yb-3 air degassed 6 Yb-4 air degassed Figure S9. Emission spectra of Yb-1 to Yb-4 in air-saturated or degassed CH 2 Cl 2 at room temperature (λ ex = 425 nm, OD 425 nm =.1).

14 Integrated Intensity 2 15 Yb-1 Yb-2 Yb-3 Yb-4 YbTPP(LOEt) Absorbance at 425 nm Figure S1. Integrated emission intensity vs absorbance plots for relative quantum yield determination of Yb-1 to Yb-4 vs YbTPP(L OEt ) (λ ex = 425 nm, Φ r =.24) in air-saturated CH 2 Cl 2 at room temperature.

15 Residuals Counts Counts Residuals Residuals Counts Counts Yb-1 4 Yb Time (ns) Time (ns) Yb Yb Time (ns) Time (ns) Figure S11. NIR luminescence decay curve of Yb-1 to Yb-4 in air-saturated CH 2 Cl 2 at room temperature (monitored at 97 nm).

16 I /I 6 5 Equation y = a + b Adj. R-Squ Value Standard Er Yb-1 Intercept Yb-1 Slope Concentration of oxygen (M) Figure S12. Stern-Volmer plots of oxygen quenching of the NIR emission of Yb-1.

17 Lifetime ( s) Yb Temperature (K) Figure S13. Temperature-dependent emission lifetimes of Yb-1 in air-saturated CH 2 Cl 2.

18 Emission Intensity Emission Intensity Emission Intensity Yb-1 293K 273K 253K 233K 213K 193K Yb-3 293K 273K 253K 233K 213K 193K Yb-4 293K 273K 253K 233K 213K 193K Figure S14. Temperature-dependent emission spectra of Yb-1, Yb-3 and Yb-4 in degassed CH 2 Cl 2 in the temperature range of K (λ ex = 425 nm).

19 Emission Intensity Emission Intensity Emission Intensity Yb-1 77K 113K 143K 173K 23K 233K 263K 293K Yb-3 77K 113K 143K 173K 23K 233K 263K 293K Yb-4 293K 263K 233K 23K 173K 143K 113K 77K Figure S15. Temperature-dependent emission spectra of Yb-1, Yb-3 and Yb-4 in solid state in the temperature range of K (λ ex = 425 nm).

20 Figure S16. Calibration curve for NIR emission detector.

21 Simulation result Experiment result Figure S17. HR ESI mass spectrum of Yb-1.

22 Simulation result Experiment result Figure S18. HR ESI mass spectrum of Yb-2.

23 Figure S19. HR ESI mass spectrum of Yb-3.

24 Figure S2. HR ESI mass spectrum of Yb-4.

25 Normalized Absorption Wavenumber (cm -1 ) Figure S21. Normalized FT-IR spectrum of Yb-1.

26 Normalized Absorption Wavenumbers (cm -1 ) Figure S22. Normalized FT-IR spectrum of Yb-2.

27 Normalized Absorption Wavenumber(cm -1 ) Figure S23. Normalized FT-IR spectrum of Yb-3.

28 Figure S24. Normalized FT-IR spectrum of Yb-4.