Supporting Information for

Transcription

1 Supporting Information for Photophysics of Pyrenyl-Functionalized Poly(isobutylene-alt-maleic anhydride) and Poly(isobutylene-alt-maleic N-alkylimide). Influence of Solvent, Degree of Substitution, and Temperature Mei-Jin Li, a,b Michael J. Bertocchi, b and Richard G. Weiss b,c * a Key Laboratory of Analysis and Detection Technology for Food Safety (Ministry of Education and Fujian Province), Department of Chemistry, Fuzhou University, Fuzhou 35116, P. R. China and b Department of Chemistry and c Institute for Soft Matter Synthesis and Metrology, Georgetown University, Washington, D.C , USA 95 % % 2 % 1.1 % Figure S1. 1 H NMR spectra of 1.1%, 2%, 5% and 95%Py-PIMA in DMSO-d 6. 1

2 decyl-1%py-pima Figure S2. 1 H NMR spectra of 1%Py-PIMA (DMSO-d 6 ), hexyl-1%py-pima (CDCl 3 ) and decyl-1%py-pima (CDCl 3 ) f1(ppm) hexyl-1%py-pima f1(ppm) %Py-PIMA f1(ppm) Absorbance PyCH 2 NH 2 1% Py-PIMA decyl-1% Py-PIMA hexyl-1% Py-PIMA Figure S3. The UV-vis spectra of Py-PIMA polymers ([Py]= mol.l -1 ) and PyCH 2 NH 2 ( mol.l -1 ) in THF. 2

3 1%Py-PIMA 2%Py-PIMA λ em =48 nm λ em =377 nm λ em = 48nm λ em = 37nm Wavlenghth / nm (c) 5%Py-PIMA λ em = 48nm λ em = 37nm (d) 95%Py-PIMA λ em = 48nm λ em = 37nm Figure S4. Excitation spectra of Py-PIMA polymers with different pyrenyl contents in degassed THF ([Py] = 1-5 mol.l -1 ) Wavlength / nm 3

4 Normalized intensity THF:Et 2 O 1: 1:1 5:1 2:1 1:1 1:2 1:5 1:7.5 THF:Et 2 O 1: 1:1 5:1 2:1 1:1 1: (c) THF:Et 2 O 1: 1:1 4:1 2:1 1:1 1: Normalized intensity (d) λ em = 48 nm λ em = 377 nm Figure S5. Emission spectra of 1%Py PIMA, hexyl 1%Py PIMA and decyl 1%Py PIMA (c) ([Py] = 1-5 mol.l -1 ) in N 2 -saturated THF diethyl ether solutions (λ ex 344 nm) and excitation spectra of 1%Py PIMA in 1:5 (v:v) THF:diethyl ether (d). 4

5 Figure S6. Emission spectra of 1%Py PIMA in methanol, ethanol, and THF (c) as a function of pyrenyl concentration. Table S1. I E /I M ratios in different solvents. Solvent (1%Py-PIMA) (hexyl-1%py-pima) (decyl-1%py-pima) THF CH 2 Cl ,4-Dioxane.11 a 9 8 Ethylene glycol DMF a Very small particles visible at [Py] = 1-5 mol.l -1, but not at [Py] = 1-6 mol.l -1. 5

6 1%Py-PIMA in DMF λ em =48nm λ em =377nm decyl-1%py-pima in DMF λ em =48 nm λ em =37 nm hexyl-1%py-pima in DMF λ em =48nm λ em =377nm Wavlength / nm Figure S7. Excitation spectra of polymers in degassed DMF ([Py] = 1-5 mol.l -1 ) Table S2. Dielectric constants, Py-scale values and I 1 /I 3 ratios for 1%Py-PIMA, hexyl-1%py- PIMA and decyl-1%py-pima in different solvents, arranged according to increasing Py-scale values. ([Py] = 1-5 mol.l -1 ). I /I Solvent Dielectric Py-scale I 1 /I 3 I 1 /I 3 constant values (1%Py-PIMA) (hexyl-1%py-pima) (decyl-1%py-pima) THF CH 2 Cl ,4-Dioxane Ethylene glycol DMF Heating -3.8 o C.5 o C 11 o C 2.3 o C 3 o C 39.7 o C 5.1 o C 57.9 o C I E / I M.3 Heating Cooling Temperature / o C Figure S8. Temperature-induced changes in the emission spectra and I E /I M ratios upon heating and cooling hexyl-1%py-pima ([Py] = 1-5 mol.l -1 ) in degassed THF (λ ex 344 nm). 6

7 Heating -4. o C.7 o C 1.9 o C 19.7 o C 29.9 o C 39.6 o C 5.1 o C 57.9 o C I E / I M Heating Cooling Temperature / o C Figure S9. Temperature-induced changes in the emission spectra and I E /I M ratios upon heating and cooling decyl-1%py-pima ([Py] = 1-5 mol.l -1 ) in degassed THF (λ ex 344 nm). Table S3. Parameters (B, pre-exponential factor; f, the percentage of the relative fluorescence intensity of one component; τ, decay times in ns; χ 2, goodness of fit value) from exponential deconvolution of decay curves for hexyl-1%py-pima at 377 nm and 48 nm in different solvents (344 nm excitation). Solvent λ em = 377 nm χ 2 B M1 (f M1 ) B M2 (f M2 ) B M3 (f M3 ) τ Μ1 τ Μ2 τ Μ3 THF 7 (2.4%).19 (26.1%) 4 (71.5%) CH 2 Cl 2.11(4.9%).19(29.2%) 5(65.9%) ,4-Dioxane 8 (5.%).17 (19.6%).32 (75.4%) DMF.12 (2.6%).18 (17.9%).34 (79.5%) λ em = 48 nm χ 2 B E1 (f E1 ) B E2 (f E2 ) B E3 (f E3 ) τ E1 τ E2 τ E3 THF -.5(11.1%) 6(64.6%).12(24.3%) CH 2 Cl 2-5(9.8%).71(72.2%) 9(17.9%) ,4-Dioxane -.7(14.1%).72(53.2%) 2(32.7%) DMF -6 (13.5%).72(56.2%) 1(3%)

8 Table S4. Parameters (B, pre-exponential factor; f, the percentage of the relative fluorescence intensity of one component; τ, decay time; χ 2, goodness of fit value) from exponential deconvolution of decay curves for decyl-1%py-pima at 377 nm and 48 nm in different solvents (344 nm excitation) Solvent λ em = 377 nm χ 2 B M1 (f M1 ) B M2 (f M2 ) B M3 (f M3 ) τ Μ1 (ns) τ Μ2 (ns) τ Μ3 (ns) THF.15 (2.5%).16 (15.7%).32 (81.8%) CH 2 Cl 2 8 (3.4%).15 (25.9%) 5 (7.7%) ,4-Dioxane 6 (1.1%).14 (16.7%).35 (82.3%) DMF.13 (2.8%).16 (14.7%).35 (82.5%) λ em = 48 nm χ 2 B E1 (f E1 ) B E2 (f E2 ) B E3 (f E3 ) τ Ε1 (ns) τ Ε2 (ns) τ Ε3 (ns) THF -8 (1.1%).59 (57.7%).16 (32.2%) CH 2 Cl (8.2%).56 (7.3%) 8 (21.5%) ,4-Dioxane -1 (8.%).57 (55.7%).18 (36.3%) DMF -.51 (1.3%) 1 (53.9%) 1 (35.8%) Intensity / a.u ns 2 ns 5 ns 1 ns 2 ns Figure S1. Time-resolved emission spectra (TRES) for 1%Py-PIMA ([Py] = 1-5 mol.l -1 ) in degassed DMF (λ ex 344 nm). Table S5. Individual HSPs and Hildebrand parameters (MPa 1/2 ) for polymers from the groupcontribution method. δ d δ p δ h δ δ Hildebrand 1%Py-PIMA hexyl-1%py-pima decyl-1%py-pima

9 Table S6. Calculated χ 12 values for the three 1%Py-PIMA polymers in different solvents using HSPs. Solvent MeOH EtOH THF DMF 1,4-Dioxane Ethylene CH 3 CN CH 2 Cl 2 glycol 1%Py-PIMA hexyl-1%py-pima decyl-1%py-pima Table S7. Distribution analyses of monomer decays (τ M3 in ns) for the three 1%Py-PIMA polymers ([Py] = 1-5 mol.l -1 ) in DMF. Numbers in parentheses are one standard deviation in distribution widths. 1%Py hexyl-1%py-pima decyl-1%py-pima 218(1.7) 189(16.1) 194(13.5) Relative Intensity Relative Intensity Time / ns Time / ns 6 (c) 5 Relative Intensity Time / ns Figure S11. Distribution analyses of monomer decays for 1%Py-PIMA, hexyl-1%py- PIMA (c) and decyl-1%py-pima (e) ([Py] = ⅹ1-5 mol.l -1 ) in degassed DMF. 9

10 .3.3 THF THF I E /I M.1 Ethylene Glycol DMF CH 2 Cl 2 Dioxane I E /I M.1 Dioxane CH 2 Cl 2 Ethylene Glycol DMF δ d / MPa 1/ δ p / MPa 1/2.3 (c).3 (d) THF THF I E /I M CH 2 Cl 2 DMF I E /I M CH 2 Cl 2.1 Dioxane Ethylene Glycol.1 Dioxane DMF Ethylene Glycol δ h / MPa 1/ δ / MPa 1/2 Figure S12. Intensity ratios (I E /I M ) for 1%Py PIMA ( ), hexyl 1%Py PIMA ( ) and decyl 1%Py PIMA ( ) ([Py] = 1-5 mol.l -1 ) in degassed solvents as a function of δ d, δ p, (c) δ h and (d) overall δ Hansen solubility parameters. 1

11 f E2 /f E THF CH 2 Cl 2 Dioxane DMF Ethylene Glycol δ / MPa 1/2 B E1 /B E2 CH2Cl2 THF Dioxane DMF Ethylene Gycol δ h / MPa 1/2 Figure S13. The ratio between excimer and monomer percentages (f E2 /f E3 ) from decays at 48 nm as a function of the overall Hansen solubility parameter δ and the ratio between the formation of dynamic and total excimer percentages (B E1 /B E2 ) from decays at 48 nm as a function of the Hansen solubility parameter δ h in degassed solvents for 1%Py PIMA ( ), hexyl 1%Py PIMA ( ) and decyl 1%Py PIMA ( ) ([Py] = ⅹ1-5 mol.l -1 ). 11

12 3 3 Time / ns 2 1 Time / ns δ / MPa 1/2 δ / MPa 1/2 3 (c) 2 Time / ns δ / MPa 1/2 Figure S14. The monomer (τ M3, ), excimer (τ E2, ) and dynamic formation (τ E1, ) decay constants for 1%Py-PIMA, hexyl-1%py-pima and (c) decyl-1%py-pima ([Py] = ⅹ1-5 mol.l -1 ) in degassed solvents as a function of the overall Hansen solubility parameter. 1 Dong, D. C.; Winnik, M. A. The Py Scale of Solvent Polarities. Can. J. Chem. 1984, 62,