Supporting Information Exploring Förster Electronic Energy Transfer in a Decoupled Anthracenyl-based Borondipyrromethene (Bodipy) Dyad Dan Bai, Andrew C. Benniston, Jerry Hagon, Helge Lemmetyinen, ikolai Tkachenko, William Clegg and Ross W. Harrington S1. X-ray determined molecular structure for compound 4 showing the atomic labelling.
S2. Crystal packing diagram for ATBD in which pairwise stacking of anthracene units and a close approach of triazole CH to an F atom can be seen. H atoms are omitted for clarity; the view is down the a axis.
10000 ε max M -1 cm -1 8000 6000 4000 2000 0 300 350 400 450 Wavelength / mn S3. Ambient temperature absorption spectrum for PHAT in dry toluene.
ormalized Absorbance 1.0 0.8 0.6 0.4 0.2 1.0 0.8 0.6 0.4 0.2 0.0 0.0 300 350 400 450 500 550 600 Wavelength / nm ormalized Intensity S4. Ambient temperature absorption and fluorescence spectra for PHAT in dry toluene.
ormalised 1.0 0.8 0.6 0.4 0.2 0.0 26000 28000 30000 32000 Wavenumber / cm -1 S5. Comparison of the corrected fluorescence excitation spectrum (red) with the absorption spectrum (black) for PHAT in dry toluene.
4 log (I) 3 2 1 0 0 5 10 15 20 25 30 Time / ns S6. Time-correlated single photon counting fluorescence decay collected for PHAT in dry toluene and the least-squares fit to the single exponential (red line). Also shown is the instrument response function.
80000 F B F ε max M -1 cm -1 60000 40000 20000 0 300 400 500 600 Wavelength / nm S7. Ambient temperature absorption spectrum for BD1 in dry toluene.
ormalised Absorbance 1.0 0.8 0.6 0.4 0.2 F B F 1.0 0.8 0.6 0.4 0.2 0.0 0.0 300 350 400 450 500 550 600 650 Wavelength / nm ormalised Intensity S8. Ambient temperature absorption and fluorescence spectra for BD1 in dry toluene.
80000 Toluene F B F ε max M -1 cm -1 60000 40000 UC TA F B F 20000 0 300 400 500 600 700 Wavelength / nm S9. Comparison of the ambient temperature absorption spectra for BD1 and ATBD in dry toluene. Arrows depict excitation wavelength used for transient absorption (TA) and up-conversion (UC) experiments.
1.0 ormalised Intensity 0.8 0.6 0.4 0.2 F B F 0.0 20000 24000 28000 32000 Wavenumber / cm -1 S10. Comparison of the corrected fluorescence excitation spectrum (red) with the absorption spectrum (black) for BDAT in dry toluene.
1.0 ormalised Intensity 0.8 0.6 0.4 0.2 0.0 18000 20000 22000 24000 26000 28000 30000 Wavenumber / cm -1 S11. Comparison of the normalised corrected fluorescence excitation spectra for BDAT in dry toluene at 293.8K (black) and 279.7 K (red).
40 Current /µa 20 0-20 Fc + /Fc -40-2.0-1.5-1.0-0.5 0.0 0.5 1.0 1.5 2.0 Potential / V S12. Cyclic voltammogram for PHAT in dry DCM (0.2 M TBATFB background electrolyte) at a glassy carbon working electrode and vs Ag wire reference electrode. Scan rate = 50 mv s -1
Current / µa 30 20 10 0 F B F Fc + /Fc -10-1.0-0.5 0.0 0.5 1.0 1.5 Potential / V S13. Cyclic voltammogram for BD1 in dry DCM (0.2 M TBATFB background electrolyte) at a glassy carbon working electrode and vs Ag/AgCl reference electrode. Scan rate = 50 mv s -1
40 Current / µa 20 0 B F F Fc + /Fc -20-1.5-1.0-0.5 0.0 0.5 1.0 1.5 Potential / V S14. Cyclic voltammogram for ATBD in dry DCM (0.2 M TBATFB background electrolyte) at a glassy carbon working electrode and vs Ag/AgCl reference electrode. Scan rate = 50 mv s -1
S15. Overlap between emission spectrum for PHAT (red) with S 0 -S 1 (blue) and S 0 -S 2 (green) electronic absorption transitions for BD1 (black)
S16. Comparison of the X-ray crystallographic determined structure for ATBD (top) and the computer generated model (middle). The bottom figure shows an overlay of the two structures ( and C atoms of bodipy core)
S17. HOMO and LUMO molecular orbitals calculated for PHAT using Gaussian-03 at the Hartree-Fock level and using a 6-311G basis set.
S18. HOMO and LUMO molecular orbitals calculated for PHAT using Gaussian-03 and DFT- B3LYP (6-311G basis set).
S19. HOMO and LUMO molecular orbitals calculated for ATBD using Gaussian-03 and Hartree- Fock (6-31G basis set).
0.02 MeTHF 528 nm A 0.00-0.02-0.04 ATBD F B F -0.06-0.08 0 200 400 600 800 1000 Time / ps S20. Kinetics recorded at 530 nm ( ) and the least-squares fit (red line) to the data points from the transient absorption profiles recorded after excitation of ATBD in Me-THF at 400 nm with a 70 fs laser pulse.
10000 MeTHF (545 nm) 8000 Counts 6000 4000 ATBD F B F 2000 0 20 40 60 80 100 Time / ps Counts 500 400 300 MeTHF (460 nm) ATBD F B F 200 100 0 20 40 60 80 100 120 Time / ps S21. Femtosecond up-conversion profiles recorded at two different wavelengths following excitation of ATBD in MeTHF at 380 nm with a 70 fs laser pulse. Least-squares fit to data points ( ) is shown by red line.
0.01 0.00 DCE 530 nm -0.01 A -0.02-0.03 ATBD F B F -0.04-0.05 0 200 400 600 800 1000 Time / ps S22. Kinetics recorded at 530 nm ( ) and the least-squares fit (red line) to the data points from the transient absorption profiles recorded after excitation of ATBD in DCE at 400 nm with a 70 fs laser pulse.
5000 DCE (545 nm) 4000 Counts 3000 2000 ATBD F B F 1000 0 20 40 60 80 100 Time / ps 350 DCE (460 nm) 300 Counts 250 ATBD F B F 200 150 0 20 40 60 80 100 Time / ps S23. Femtosecond up-conversion profiles recorded at two different wavelengths following excitation of ATBD in DCE at 380 nm with a 70 fs laser pulse. Least-squares fit to data points ( ) is shown by red line.
S24. Overlap integral (J F ) calculation result showing the area for the Bodipy-based S 0 -S 1 overlap (blue) and S 0 -S 2 overlap (green).
0.0007 Intensity 0.0006 0.0005 0.0004 0.0003 0.0002 0.0001 Area = 1 Area = 1 0.0000 20000 24000 Wavenumber / cm -1 1.2x10-8 1.0x10-8 Area = 3.17 x 10-5 cm Intensity 8.0x10-9 6.0x10-9 4.0x10-9 2.0x10-9 0.0 18000 20000 22000 24000 26000 Wavenumber / cm -1 S25. Overlap integral (J DA ) calculation result showing the area for the Bodipy-based S 0 -S 1 overlap and S 0 -S 2 overlap.
S26. Illustration of generated planes and the corresponding κ 2 values for ATBD.
0.2 circle = τ TA triangle = τ 545 star = τ 460 1/τ 10 12 s -1 0.2 0.1 0.1 Black = toluene Red = DCE Blue = MeTHF 0.19 0.20 0.21 0.22 0.23 0.24 0.25 0.26 0.27 1/n 4 S27. Plots showing the relationships between k EET and 1/n 4 for ATBD.