Supporting Information for
Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation Martin Weiser1, Sergej Hermann1, Alexander Penner1 and Hans-Achim Wagenknecht*1
Address: 1Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
Email: Hans-Achim Wagenknecht -
[email protected] * Corresponding author
Spectral data: Cyclic voltammogram of PDI, determination of E00 of PDI, Stern–Volmer plots of PDI in the presence of substrate 1, spectroelectrochemistry of PDI, pictures of the mesoflow setups.
Contents 1. 2. 3. 4. 5.
Cyclic voltammogram of PDI .............................................................................. S2 Determination of E00 of PDI ................................................................................ S3 Stern–Volmer plots of PDI in presence of substrate 1........................................ S4 Spectroelectrochemistry of PDI .......................................................................... S5 Setup of mesoflow reactors ................................................................................ S6
S1
1. Cyclic voltammogram of PDI
15
PDI vs. Fc/Fc
+
10
current [µA]
5
0
-5
-10
-15 -2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
voltage [V]
Figure S1: Cyclic voltammogram of PDI (vs Fc/Fc+), 20 mV/s, 0.1 M in TBAHFP in CH2Cl2, Ered(PDI/PDI●−) = −0.66 V (vs Fc/Fc+); Ered(PDI/PDI●−) = −0.28 V (vs SCE) [1].
S2
2. Determination of E00 of PDI
1.0
normalized absorption 528 nm normalized emission
normalized intensity
0.8
0.6
0.4
0.2
0.0 450
500
550
600
wavelength [nm]
Figure S2: normalized absorption (black) and emission (red) spectra of PDI in CH2Cl2. λabs = 525 nm, λem = 530 nm, λint = 528 nm, E00 = 2.35 eV.
S3
3. Stern–Volmer plots of PDI in presence of substrate 1
7
1x10
2.5 M PDI 5 mM 1 10 mM 1 20 mM 1
6
9x10
6
8x10
6
7x10
6
F.I. [a.u.]
6x10
6
5x10
6
4x10
6
3x10
6
2x10
6
1x10
0 500
550
600
650
700
750
800
wavelength [nm]
Figure S3: Emission spectra of PDI (2.5 µM) without (red) and with concentrations of 5 (orange), 10 (green) and 20 mM (blue) of 1 in CH2Cl2; λexc = 487 nm.
S4
4. Spectroelectrochemistry of PDI
1.0
0mV -100mV -200mV -300mV -350mV -375mV -400mV -425mV -450mV -500mV -550mV -600mV
absorption
0.8
0.6
0.4
0.2
0.0 200
250
300
350
400
450
500
550
600
wavelength [nm]
Figure S4: Spectroelectrochemistry of PDI in CH2Cl2.
S5
650
700
750
800
5. Setup of mesoflow reactors
Mesoflow reactor 1 is the commercially available borosilicate glass reactor LTF-VS, purchased from the little things factory (http://www.ltfgmbh.com/produkte/mr_lab.html) with an inner diameter of 1 mm and dimension of 115 × 60 × 6 mm (L, B, H).
Mesoflow reactor 2 is made of PTFE tubing with an inner diameter of 1.0 mm wrapped around a cooling finger. Pressure was controlled with an argon balloon.
S6
References 1. Pavlishchuk, V. V.; Addison, A. W., Inorg. Chim. Acta 2000, 298, 97-102.
S7
