Supporting Information Comparison of Charge-Transfer Dynamics of ...
Supporting Information
Comparison of Charge-Transfer Dynamics of Naphthalenediimide Triads in Solution and π-Stack Architectures on Solid Surfaces Oleksandr Yushchenko, Diego Villamaina, Naomi Sakai, Stefan Matile,* and Eric Vauthey* School of Chemistry and Biochemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211 Geneva 4.
S1
1) Synthesis of the triad A solution of pNDI (4.5 mg, 4.4 µmol)27 in DCM/TFA (1 mL, 1:1 v/v) mixture was stirred at rt for 10 min. To this solution was added rNDI (5.5 mg, 8.9 µmol).27 The mixture was stirred for 10 more min, and then concentrated in vacuo. The residue was purified by PTLC (DCM/MeOH 9:1, Rf = 0.47) to give the product as a red solid (7 mg, 82%).
1
H NMR
(CDCl3): 10.15–9.80 (m, 2H), 9.30–8.50 (m, 8H), 8.15–7.70 (m, 2H), 7.50–7.28 (m, 10H), 6.06–5.63 (m, 8H), 5.46–4.83 (m, 8H), 4.75–3.85 (m, 14H), 3.75–3.42 (m, 4H), 3.33–3.08 (m, 4H), 2.83–2.25 (m, 4H), 2.00–1.19 (m, 20H); ESI-MS (MeOH; the most intense isotopic peaks): m/z (%): 1950 (20) [M+Na]+, 1929 (100) [M+H]+, 1884 (32) [M+H–Allyl]+.
O
O NH
O
NH O O O HN N
O N NH O O O HN O
O HN O
O O HN O O
pNDI
Br
N O
O
O N NH
O
N OO HN N O
O HN O O
HN
Br
O
N
N
O
OO
NH
O
O
O NH
O N OO
NH N
HN O
O
N O
N Br
O
NH O
O
O
rNDI
Scheme S1. Synthesis of the rNDI-pNDI-rNDI trimer.
S2
2) Additional results
fluorescence
triad rNDI
350
400
450
500
wavelength / nm
residuals
Figure S1: Fluorescence excitation spectra at 570 nm recorded with the triad and rNDI in DCM.
fluorescence
10
0
10
-1
10
-2
10
-3
triad rNDI
0
20
40
60
80
time / ns
Figure S2: Fluorescence dynamics at 570 nm measured with the triad and rNDI in ACN upon 470 nm excitation and best monoexponential (rNDI) and biexponential fit (triad).
S3
1.0
fluorescence
0.8 0.6 0.4
385 nm excitation 520 nm excitation
0.2 0.0 -1
0
1
2
3
4
5
time delay /ps
Figure S3: Early fluorescence dynamics measured at 570 nm with the triad in DCM upon 520 nm (local rNDI S1←S0) and 385 nm (local pNDI S1←S0) excitation and best multiexponential fit.
2
370 ps 10 ns 560 ns 1.5 µs 4.6 µs
A
1
2 ns 210 ns 1 µs 2.4 µs 7.5 µs
ΔA x 10
3
0
2
B
A (2.4 ns) B (1.6 µs)
1
0
400
450
500
550
600
650
wavelength / nm
Figure S4: Transient absorption spectra measured with the triad in DCM upon 355 nm excitation (A) and species associated difference absorption spectra obtained from target analysis assuming sequential exponential steps (B).
S4
1.0 SOSIP film
fluorescence
0.8
λex = 385 nm λem = 570 nm
0.6 0.4 0.2 0.0 0
2
4
6
8
time delay / ps
Figure S5: Fluorescence dynamics of the SOSIP film measured at 570 nm upon 385 nm (local pNDI S1←S0) excitation and best multiexponential fit.
S5
Comparison of Charge-Transfer Dynamics of Naphthalenediimide Triads in Solution and π-Stack Architectures on Solid Surfaces Oleksandr Yushchenko, Diego Villamaina, Naomi Sakai, Stefan Matile,* and Eric Vauthey* School of Chemistry and Biochemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211 Geneva 4.
S1
1) Synthesis of the triad A solution of pNDI (4.5 mg, 4.4 µmol)27 in DCM/TFA (1 mL, 1:1 v/v) mixture was stirred at rt for 10 min. To this solution was added rNDI (5.5 mg, 8.9 µmol).27 The mixture was stirred for 10 more min, and then concentrated in vacuo. The residue was purified by PTLC (DCM/MeOH 9:1, Rf = 0.47) to give the product as a red solid (7 mg, 82%).
1
H NMR
(CDCl3): 10.15–9.80 (m, 2H), 9.30–8.50 (m, 8H), 8.15–7.70 (m, 2H), 7.50–7.28 (m, 10H), 6.06–5.63 (m, 8H), 5.46–4.83 (m, 8H), 4.75–3.85 (m, 14H), 3.75–3.42 (m, 4H), 3.33–3.08 (m, 4H), 2.83–2.25 (m, 4H), 2.00–1.19 (m, 20H); ESI-MS (MeOH; the most intense isotopic peaks): m/z (%): 1950 (20) [M+Na]+, 1929 (100) [M+H]+, 1884 (32) [M+H–Allyl]+.
O
O NH
O
NH O O O HN N
O N NH O O O HN O
O HN O
O O HN O O
pNDI
Br
N O
O
O N NH
O
N OO HN N O
O HN O O
HN
Br
O
N
N
O
OO
NH
O
O
O NH
O N OO
NH N
HN O
O
N O
N Br
O
NH O
O
O
rNDI
Scheme S1. Synthesis of the rNDI-pNDI-rNDI trimer.
S2
2) Additional results
fluorescence
triad rNDI
350
400
450
500
wavelength / nm
residuals
Figure S1: Fluorescence excitation spectra at 570 nm recorded with the triad and rNDI in DCM.
fluorescence
10
0
10
-1
10
-2
10
-3
triad rNDI
0
20
40
60
80
time / ns
Figure S2: Fluorescence dynamics at 570 nm measured with the triad and rNDI in ACN upon 470 nm excitation and best monoexponential (rNDI) and biexponential fit (triad).
S3
1.0
fluorescence
0.8 0.6 0.4
385 nm excitation 520 nm excitation
0.2 0.0 -1
0
1
2
3
4
5
time delay /ps
Figure S3: Early fluorescence dynamics measured at 570 nm with the triad in DCM upon 520 nm (local rNDI S1←S0) and 385 nm (local pNDI S1←S0) excitation and best multiexponential fit.
2
370 ps 10 ns 560 ns 1.5 µs 4.6 µs
A
1
2 ns 210 ns 1 µs 2.4 µs 7.5 µs
ΔA x 10
3
0
2
B
A (2.4 ns) B (1.6 µs)
1
0
400
450
500
550
600
650
wavelength / nm
Figure S4: Transient absorption spectra measured with the triad in DCM upon 355 nm excitation (A) and species associated difference absorption spectra obtained from target analysis assuming sequential exponential steps (B).
S4
1.0 SOSIP film
fluorescence
0.8
λex = 385 nm λem = 570 nm
0.6 0.4 0.2 0.0 0
2
4
6
8
time delay / ps
Figure S5: Fluorescence dynamics of the SOSIP film measured at 570 nm upon 385 nm (local pNDI S1←S0) excitation and best multiexponential fit.
S5
