Supporting Information

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

Supporting Contents... 3 Table S1. Crystal data and structure refinement for Yb-1 and Yb-2.... 3 Table S2. Parameters obtained for Stern-Volmer experiment.... 4 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).... 6 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).... 7 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.... 8 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.... 9 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... 1 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 ).... 11 Figure S8. Normalized emission spectra of Gd(III) complexes in CH 3 OH/C 2 H 5 OH (v/v = 1:1) at 77K.... 12 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).... 13 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.... 14 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).... 15 Figure S12. Stern-Volmer plots of oxygen quenching of the NIR emission of Yb-1.... 16 Figure S13. Temperature-dependent emission lifetimes of Yb-1 in air-saturated CH 2 Cl 2.... 17 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 193 293 K (λ ex = 425 nm).... 18 Figure S15. Temperature-dependent emission spectra of Yb-1, Yb-3 and Yb-4 in solid state in the temperature range of 77 293 K (λ ex = 425 nm).... 19 Figure S16. Calibration curve for NIR emission detector.... 2 Figure S17. HR ESI mass spectrum of Yb-1.... 21 Figure S18. HR ESI mass spectrum of Yb-2.... 22 Figure S19. HR ESI mass spectrum of Yb-3.... 23 Figure S2. HR ESI mass spectrum of Yb-4.... 24 Figure S21. Normalized FT-IR spectrum of Yb-1.... 25 Figure S22. Normalized FT-IR spectrum of Yb-2.... 26 Figure S23. Normalized FT-IR spectrum of Yb-3.... 27 Figure S24. Normalized FT-IR spectrum of Yb-4.... 28

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 13.75 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 ) 419.68 424.69 temperature (K) 296(2) 18.(1) radiation (, Å).717.717 crystal system orthorhombic orthorhombic space group P mmn P mmn a (Å) 16.3919(11) 15.8894(6) b (Å) 23.5424(17) 23.4727(8) c (Å) 1.2182(7) 1.1435(3) Volume (Å 3 ) 3943.3(5) 3783.2(2) Z 8 8 calcd (g cm 3 ) 1.414 1.491 (mm 1 ) 1.55 1.615 F() 165 167 crystal size (mm 3 ).8.34.22.4.32.28 Theta range 1.514 to 27.486 2.92 to 24.994 reflections collected 2655 1357 independent reflections 4771 [R(int) =.371] 3546 [R(int) =.333] Completeness 99.5% 99.7% goodness-of-fit on F 2 1.92 1.61 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.614.764 and.419

Table S2. Parameters obtained for Stern-Volmer experiment. [O 2 ] (M) I /I slope τ (μs) k q,sv (M -1 s -1 ).1815 1.42122.3452 3.329 Yb-1.5178 4.7524 668 28.8 2.32 1 7.694 5.9558.863 6.1549

Normalized Intensity 1..8.6 Yb-1 Yb-2 Yb-3 Yb-4.4.2. 3 4 5 6 7 Figure S1. Normalized absorption spectra of Yb(III) complexes in CH 2 Cl 2 at room temperature.

Emission Intensity 15 12 Yb-1 Yb-2 Yb-3 Yb-4 9 6 3 9 1 11 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).

Residuals Residuals Counts Counts Residuals Residuals Counts Counts 6 2 4 1 Yb-1 1 2 Time (ns) 5-5 2 1 2 Time (ns) 5-5 Yb-2 25 2 15 15 1 1 5 1 2 5 Time (ns) -5 Yb-3 5 1 2 5 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).

Normalized Absorption Normalized Absorption Normalized Emission Normalized Emission Normalized Emission Normalized Absorption Normalized Absorption Normalized Emission 1..8 Yb-1 Excitation Emission 1..8 1..8 Yb-2 Excitation Emission 1..8.6.6.6.6.4.4.4.4.2.2.2.2. 1..8 Yb-3 4 6 8 1 Excitation Emission. 1..8. 1..8 Yb-4 4 6 8 1 12 Excitation Emission. 1..8.6.6.6.6.4.4.4.4.2.2.2.2. 3 4 5 6 7 8 9 1 11.. 4 6 8 1. 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.

Integrated Intensity 2 15 Yb-1 Yb-2 Yb-3 Yb-4 YbTPP(LOEt) 1 5..2.4.6.8.1 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.

Absorbance.6.5 Yb-1 Yb-2.4.3.2.1. 9 92 94 96 98 1 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.

OD.1 Yb-1 Yb-2 Yb-3 Yb-4. -.1 -.2 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 -.3 3 4 5 6 7 3 4 5 6 7 3 4 5 6 7 3 4 5 6 7 8 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 ).

Normalized Emission 1..8.6 Gd-1 Gd-2 Gd-3 Gd-4.4.2. 7 8 9 1 11 12 Figure S8. Normalized emission spectra of Gd(III) complexes in CH 3 OH/C 2 H 5 OH (v/v = 1:1) at 77K.

Emission Intensity Emission Intensity Emission Intensity Emission Intensity 6 Yb-1 air degassed 6 Yb-2 air degassed 4 4 2 2 85 9 95 1 15 11 115 9 1 11 6 Yb-3 air degassed 6 Yb-4 air degassed 4 4 2 2 85 9 95 1 15 11 115 85 9 95 1 15 11 115 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).

Integrated Intensity 2 15 Yb-1 Yb-2 Yb-3 Yb-4 YbTPP(LOEt) 1 5..2.4.6.8.1 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.

Residuals Counts Counts Residuals Residuals Counts Counts 3 2 1 8 6 1 Yb-1 4 Yb-2 5 1 Time (ns) 5-5 2 5 1 Time (ns) 5-5 5 1 4 3 8 2 1 Yb-3 6 4 Yb-4 1 2 Time (ns) 5 2 1 2 Time (ns) 5-5 -5 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).

I /I 6 5 Equation y = a + b Adj. R-Squ.98264 Value Standard Er Yb-1 Intercept.47282.254 Yb-1 Slope 668.444 44.32895 4 3 2 1.2.4.6.8 Concentration of oxygen (M) Figure S12. Stern-Volmer plots of oxygen quenching of the NIR emission of Yb-1.

Lifetime ( s) 32 28 Yb-1 24 2 16 12 18 2 22 24 26 28 3 Temperature (K) Figure S13. Temperature-dependent emission lifetimes of Yb-1 in air-saturated CH 2 Cl 2.

Emission Intensity Emission Intensity Emission Intensity 2 16 12 Yb-1 293K 273K 253K 233K 213K 193K 8 4 9 95 1 15 11 115 14 12 1 8 Yb-3 293K 273K 253K 233K 213K 193K 5 4 3 Yb-4 293K 273K 253K 233K 213K 193K 6 2 4 2 1 9 95 1 15 11 115 9 95 1 15 11 115 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 193 293 K (λ ex = 425 nm).

Emission Intensity Emission Intensity Emission Intensity 5 4 3 2 Yb-1 77K 113K 143K 173K 23K 233K 263K 293K 1 9 95 1 15 11 115 8 6 4 Yb-3 77K 113K 143K 173K 23K 233K 263K 293K 12 9 6 Yb-4 293K 263K 233K 23K 173K 143K 113K 77K 2 3 9 95 1 15 11 115 9 95 1 15 11 115 Figure S15. Temperature-dependent emission spectra of Yb-1, Yb-3 and Yb-4 in solid state in the temperature range of 77 293 K (λ ex = 425 nm).

Figure S16. Calibration curve for NIR emission detector.

Simulation result Experiment result 1633.92749 163 1635 164 15 155 16 165 Figure S17. HR ESI mass spectrum of Yb-1.

Simulation result Experiment result 1633.92281 163 1635 156 159 162 165 Figure S18. HR ESI mass spectrum of Yb-2.

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

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

Normalized Absorption 1..8.6.4.2. 5 1 15 2 25 3 35 4 Wavenumber (cm -1 ) Figure S21. Normalized FT-IR spectrum of Yb-1.

Normalized Absorption 1..8.6.4.2. 5 1 15 2 25 3 35 4 Wavenumbers (cm -1 ) Figure S22. Normalized FT-IR spectrum of Yb-2.

Normalized Absorption 1..8.6.4.2. 5 1 15 2 25 3 35 4 Wavenumber(cm -1 ) Figure S23. Normalized FT-IR spectrum of Yb-3.

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