Zeitler et al. Supp.

Information

A Toolbox Approach to Construct Broadly Applicable Metal-Free

Catalysts for Photoredox Chemistry – Deliberate Tuning of Redox
Potentials and Importance of Halogens in Donor-Acceptor Cyanoarenes
Elisabeth Speckmeier§, Tillmann G. Fischer§, Kirsten Zeitler*
Fakultät für Chemie und Mineralogie, Universität Leipzig,
Johannisallee 29, D-04103 Leipzig, Germany
E-mail: kzeitler@uni-leipzig.de

Supporting Information
Table of Contents
1 GENERAL METHODS................................................................................................................ 2

2 ABBREVIATIONS AND NOMENCLATURE .......................................................................... 3

3 GENERAL PROCEDURES FOR THE SYNTHESIS OF THE PHOTOCATALYSTS ....... 4

4 EXPERIMENTAL DATA OF THE PHOTOCATALYSTS..................................................... 5

5 GENERAL PROCEDURES FOR TEST REACTIONS............................................................ 8

5.1 DECARBOXYLATIVE ADDITION OF CBZ-PROLINE TO DIETHYLMALEATE ................................................. 8
5.2 PHOTOCATALYTIC BROMINATION OF ANISOLE ........................................................................................ 9
5.3 SEQUENTIAL C-O BOND CLEAVAGE WITH SUBSEQUENT PINACOL COUPLING ....................................... 10
5.4 REDUCTIVE DETRIFLATION OF NAPHTHOLTRIFLATE.............................................................................. 12

6 CYCLIC VOLTAMMOGRAMS OF ELECTRON DONORS............................................... 15

7 PHOTOPHYSICAL PROPERTIES OF PHOTOCATALYSTS ........................................... 17

8 PHOTOREDOX CHARACTERISTICS FOR EACH PHOTOCATALYST ....................... 18

8.1 4CZIPN (D3-A2) .................................................................................................................................. 18
8.2 3DPAFIPN (D2-A1F) ........................................................................................................................... 20
8.3 5CZBN (D3-A4).................................................................................................................................... 22
8.4 3DPA2FBN (D2-A3) ........................................................................................................................... 24
8.5 3CZCLIPN (D3-A1CL)........................................................................................................................... 26
8.6 3DPACLIPN (D2-A1CL) ....................................................................................................................... 28
8.7 4MEOCZIPN (D1-A2).......................................................................................................................... 30
8.8 5MEOCZBN (D1-A4)........................................................................................................................... 32

9 ABSORPTION AND FLUORESCENCE OVERLAYS ...................................................... 34

10 ADDITIONAL SPECTRAL DATA FOR FLUORINE CONTAINING PHOTOCATALYSTS35

19
10.1 F NMR AND HR MS SPECTRA OF 3DPAFIPN (D2-A1F) ................................................................... 35
19
10.2 F NMR, 13C NMR SPECTRA DETAILS AND HR MS SPECTRA OF 3DPA2FBN (D2-A3)................................... 36

11 REFERENCES ........................................................................................................................ 40

12 NMR SPECTRA OF SUBSTRATES AND PRODUCTS.................................................... 41

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1 General Methods

Unless otherwise noted, all commercially available compounds were used as received without further
purification. Tetrahydrofuran was distilled from sodium/benzophenone. All reactions were carried out under
an atmosphere of dry nitrogen using oven-dried glassware unless otherwise stated.

NMR spectra were recorded on a VARIAN Mercury plus 300 (300.8 MHz), VARIAN Mercury plus
400 (399.95 MHz) and BRUKER Avance III HD (400.13 MHz) using the solvent peaks as internal reference
for the chemicals shifts δ of the reported 1H and 13
C nuclei (CDCl3: δ(1H) = 7.26 , δ(13C) = 77.16 ;
DMSO-d6: δ(1H) = 2.50 , δ(13C) = 39.52 ; acetone-d6: δ(1H) = 2.05 , δ(13C) = 29.84 and DCM-d2:
δ( H) = 5.32 , δ( C) = 53.84 ). Chemical shifts of
1 13 1 19
F nuclei were externally referenced to trifluoroacetic
acid. Multiplicities of signals are reported as s (singlet), d (doublet), t (triplet), q (quartet), quint (quintet),
sept (septet), m (multiplet) and combinations of these multiplicities. Coupling constants J are reported in Hz,
rounded on half of whole numbers. All coupling constants J reported refer to JHH couplings, if not stated
13
otherwise. Spectra of C nuclei were recorded 1H-decoupled. The applied solvents are specified in the
descriptions of the corresponding experiments.

ESI-MS spectra were recorded on a BRUKER DALTONICS Esquire 3000 Plus ESI-Ion Trap mass
spectrometer or BRUKER DALTONICS Impact II ESI-TOF mass spectrometer with a mass accuracy of 5 ppm.
Ionization modes are specified in the descriptions of the corresponding experiments.

All reactions were monitored by thin-layer chromatography using MERCK silica gel plates 60 F254
(aluminium sheets, 200 µm layer thickness) or MACHERY NAGEL Alugram® Xtra SIL G/UV254 (aluminium
sheets, 200 µm layer thickness). Spots were visualized utilizing UV light and/or appropriate staining solutions
of vanillin, ninhydrin, permanganate or molybdophosphoric acid. Flash chromatography was performed on a
BIOTAGE® Isolera One using 10 g or 50 g Biotage® SNAP cartridge KP-Sil columns filled with MACHEREY
NAGEL silica gel 60 (size 40−63 µm).

GC-FID spectra were recorded on a THERMO SCIENTIFIC Trace 1310 gas chromatograph equipped
with a THERMO SCIENTIFIC TG-5MS column (5% diphenyl- and 95% dimethylpolysiloxane, 0.25 mm ID,
0.25 µm film thickness, length 30 m) using hydrogen as carrier gas and nitrogen as make-up gas.

Irradiation was performed with twelve OSRAM Oslon SSL royal blue (455 nm) LEDs attached to an
aluminium heat sink. The LEDs were operated at approx. 700 mA per LED.
Cyclic voltammetry measurements were done with a METROHM Autolab PGSTAT302N,
respectively an EMSTAT3 Standard PalmSens ES316X965 equipped with a glassy carbon electrode as

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working electrode and platinum wire as counter electrode. Silver wire was used as pseudo reference
electrode and 0.1 M solution of tetrabutylammonium tetrafluoroborate was applied as supporting electrolyte.
Scan rate was set to 100 mV/s. Solutions were degassed with argon prior to measurements and experiments
were performed under an protective atmosphere of argon. Ferrocene was used as an internal reference
(Fc/Fc+) to determine the reduction and oxidation potentials. The applied solvents are specified in the
descriptions of the corresponding experiments.

Absorption spectra were obtained on a JASCO V-650 UV/Vis spectrophotometer and on a Shimadzu
UV-1280 UV/Vis spectrometer. All spectra were recorded in MeCN (5 µ M) in a 1 cm quartz cuvette.

Fluorescence spectra were obtained with a Shimadzu RF-6000 spectrofluorophotometer in MeCN

(5 µ M) in 1 cm quartz cuvettes.

The zero-zero vibrational state excitation energy E0,0 was estimated by the corresponding energy of
the wavelength at which emission and absorption overlap. This wavelength was determined setting the
intensity of emission λmax to the absorbance at excitation wavelength (400 nm, for 4MeOCzIPN 450 nm).
Excited state oxidation and reduction potentials were calculated by the following approximating formulas:
E1/2(PC*/PC●−) = E1/2(PC/PC●−) + E0,0 and E1/2(PC●+/PC*) = E1/2(PC●+/PC) − E0,0.

Lifetimes were obtained on a PICOQUANT MicroTime 200 with an OLYMPUS IX 71 microscope. A

COUGAR Nd:YVO4 laser was used as excitation source. An excitation wavelength of 266 nm and a pulse
length of 10 ps at 5 nJ was applied by passing the laser light through two β-barium borate crystals. The laser
beam was passed through a half-wave plate and a polarizer before being expanded via quartz lenses. The
emitted light was collected by a PARTEC 40x, 0.8 NA fused silica objective lens. A confocal pin hole with
150 µm diameter was applied before the emission was detected by a PICOQUANT PMA 165-N-M
photomultiplier. All lifetimes (representing kp‒1 [ns] of the prompt part of the photoluminescence) were
recorded in non-degassed MeCN (5 µ M).

2 Abbreviations and Nomenclature

General (selected). A: acceptor; conPET: consecutive photoinduced electron transfer; CT: charge transfer;
D: donor; ET: energy transfer; HAT: hydrogen atom transfer; ISC: intersystem crossing; MLCT: metal-to-
ligand chargetransfer; OLED: organic light emitting diode; PC: photocatalyst; ppy: 2-phenylpyridine; RSIC:
reversed intersystem crosssing; SenI-ET: sensitization-initiated electron transfer; SET: single electron
transfer; TADF: thermally activated delayed fluorescence; TTA: triplet-triplet annihilation.

Names and Nomenclature. BN: benzonitrile (A4); ClIPN: 5-chloro isophthalonitrile (A1Cl); Cz: carbazole
(D3); DPA: diphenylamine (D2); 2FBN: 3,5-difluoro benzonitrile = meta,meta´-difluoro benzonitrile (A3);
FIPN: 5-fluoro isophthalonitrile (A1F); IPN: isophthalonitrile (A2); MeOCz: 3,6-dimethoxy-9H-carbazole
(D1); Mes-Acr-Me+: 9-Mesityl-10-methylacridinium; PDI: perylene bisimide; Rh-6-G: rhodamine-6G.

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3 General Procedures for the Synthesis of the Photocatalysts

A) In a flame dried Schlenk flask equipped with a magnetic stir bar 1.25 equiv (per halogen of the
benzene carbonitrile) carbazole or 3,6-dimethoxy-9H-carbazole were dissolved in dry THF (0.05 M,
relating to 1.0 equiv of the corresponding benzonitrile) under an atmosphere of nitrogen. Then,
1.88 equiv (per halogen of the benzene carbonitrile) NaH (60% in mineral oil) were added and the
suspension was stirred at room temperature for 30 minutes. Finally, 1.00 equiv of the corresponding
benzene carbonitrile was added and the resulting mixture was stirred at room temperature for 24 h.
The reaction mixture was quenched by the addition of water. After removal of THF, the residue was
dissolved in DCM and washed with water. The organic phase was dried over Na2SO4 and the
solvent was removed under reduced pressure. The crude product was purified by flash
chromatography on silica gel.

B) In a flame dried Schlenk flask equipped with a magnetic stir bar 1.25 equiv (per halogen of the
benzene carbonitrile) diphenylamine were dissolved in dry THF (0.05 M, relating to 1.0 equiv of the
corresponding benzonitrile) under an atmosphere of argon. Then, 1.88 equiv (per halogen of the
benzene carbonitrile) NaH (60% in oil) were added and the suspension was stirred at 50 °C for
30 minutes. Finally, 1.00 equiv of the corresponding benzene carbonitrile was added and the
resulting mixture was stirred at room temperature for 24 h. The reaction mixture was quenched by
the addition of water. After removal of THF, the residue was dissolved in DCM and washed with
water. The organic phase was dried over Na2SO4 and the solvent was removed under reduced
pressure. The crude product was purified by flash chromatography on silica gel.

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4 Experimental Data of the Photocatalysts

2,4,6Tris(diphenylamino)-5-fluoroisophthalonitrile (3DPAFIPN, D2-A1F)

According to general procedure B using 400 mg tetrafluoro-

isophthalonitrile (2.0 mmol, 1.0 equiv). Yield after flash chromatography
(hexanes/DCM, 12-85% DCM): 1.20 g (1.85 mmol, 93%), yellow solid.
N
NC CN
1
H NMR (400 MHz, CDCl3): δ = 7.27 - 7.24 (m, 12H), 7.08 - 7.03 (m,
6H), 7.01 - 6.97 (m, 12H). 19F NMR (377 MHz, CDCl3): δ = −121.32 (s,
N N 1F). 13
C NMR (100 MHz, CDCl3): δ = 152.4a (CF, 1JC,F = 259.5 Hz),
F
151.8 (CNPh2, 4JC,F = 4.0 Hz), 145.5, 145.3 (4 NCPh, 4JC,F = 1.0 Hz),
143.1 (2 CNPh2, 2JC,F = 11.0 Hz), 129.4, 129.3, 124.6, 124.0, 122.73,
C44H30FN5 122.68, 112.6 (2 CCN), 109.0 (2 CCN, 3
JC,F = 3.0 Hz).
647.76 g/mol
HR MS (ESI+, MeCN): m/z = 670.2378 [M+Na]+, calc.: 670.2378.

2,3,4,5,6-Penta(9H-carbazol-9-yl)benzonitrile (5CzBN, D3-A4)

According to general procedure A using 193 mg

CN pentafluorobenzonitrile (1.0 mmol, 1.0 equiv). Yield after

N N flash chromatography (hexanes/DCM, 12-100% DCM):
885 mg (0.95 mmol, 95%), yellow solid.
1
H NMR (400 MHz, DMSO-d6): δ = 7.88 - 7.85 (m, 8H), 7.77
N N N
- 7.71 (m, 6H), 7.42 - 7.37 (m, 4H), 7.36 - 7.31 (m, 2H), 7.18 -
7.12 (m, 4H), 7.12 - 7.05 (m, 4H), 6.79 - 6.64 (m, 10H), 6.62 -
6.58 (m, 2H). 13
C NMR (100 MHz, DMSO-d6): δ = 143.0,
C67H40N6
929.10 g/mol 141.6, 139.8, 138.8, 138.5, 125.4, 124.01, 123.99, 123.3,
123.0, 122.9, 121.1, 121.0, 120.5, 120.4, 119.6, 119.4, 117.7, 116.7, 113.6, 112.6, 112.3, 112.1. HR MS
(ESI+, DCM/MeCN): m/z = 951.3197 [M+Na]+, calc. 951.3207.

a
The corresponding signals of this doublet are found at 153.7 and 151.1, hence the signal (151.8) of the carbon para to
the fluorine substituted carbon is positioned in between.

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2,4,6-Tris(diphenylamino)-3,5-difluorobenzonitrile (3DPA2FBN, D2-A3)

According to general procedure B using 193 mg pentafluorobenzonitrile

(1.0 mmol, 1.0 equiv). Yield after flash chromatography (hexanes/DCM,

CN 7-60% DCM): 670 mg (0.77 mmol, 77%), yellow solid.

N N
1
H NMR (400 MHz, DCM-d2): δ = 7.32 - 7.26 (m, 16H), 7.10 - 7.04 (m,
8H), 7.03 - 6.98 (m, 16H). 19F NMR (377 MHz, DMSO-d6): δ = −121.62
F F
(s, 2F). 13
C NMR (100 MHz, DCM-d2): δ = 154.7 (dd, CF, 1JC,F =
N
257.9 Hz, 3JC,F = 5.5 Hz), 145.7, 145.4, 135.2 (dd, CNPh2, 2JC,F = 11.5 Hz,
3
JC,F = 5.0 Hz), 130.2 (t, CNPh2, 2JC,F = 12.1 Hz), 129.31, 129.30 123.9,
C43H30 F2 N4 123.3, 121.7, 121.6, 113.2 (t, CCN, 3JC,F = 4.0 Hz), 110.5 (t, CN,
640.72 g/mol
4
JC,F = 4.0 Hz). HR MS (ESI+, DCM/MeCN): m/z = 663.2329, [M+Na]+,
calc. 663.2331.

2,4,6-Tri(9H-carbazol-9-yl)-5-chloroisophthalonitrile (3CzClIPN, D3-A1Cl)

According to general procedure A using 266 mg

N 2,4,5,6-tetrachloroisophthalonitrile (1.0 mmol, 1.0 equiv). Yield after
NC CN flash chromatography (hexanes/DCM, 12-81% DCM): 376 mg
(0.57 mmol, 57%), yellow solid.
N N
Cl
1
H NMR (400 MHz, CDCl3): δ = 8.18 - 8.16 (m, 6H), 7.60 - 7.55 (m,
6H), 7.45 - 7.40 (m, 6H), 7.38 - 7.36 (m, 2H), 7.27 - 7.24 (m, 4H).
13
C NMR (100 MHz, CDCl3): δ = 145.1, 144.2, 139.7, 139.2, 137.1,
C44H24ClN5
658.16 g/mol 126.92, 126.89, 124.8, 124.6, 122.4, 122.2, 121.3, 121.2, 117.6, 110.7,
109.5, 109.3. HR MS (ESI+, MeCN): m/z = 680.1630 [M+Na]+, calc. 680.1612.

5-Chloro-2,4,6-tris(diphenylamino)isophthalonitrile (3DPAClIPN, D2-A1Cl)

According to general procedure B using 266 mg

N 2,4,5,6-tetrachloroisophthalonitrile (1.0 mmol, 1.0 equiv). Yield after flash
NC CN
chromatography (hexanes/DCM, 12-100% DCM): 620 mg (0.93 mmol,
93%), yellow solid. 1H NMR (400 MHz, DCM-d2): δ = 7.36 - 7.31 (m,
N N
13
Cl 12H), 7.14 - 7.10 (m, 6H), 7.06 - 7.01 (m, 12H). C NMR (100 MHz,
DCM-d2): δ = 153.9, 153.0, 145.5, 145.0, 131.6, 129.45, 129.42, 124.3,
124.0, 122.9, 122.2, 113.1, 112.7. HR MS (ESI+, MeCN): m/z = 686.2084
C44H30ClN5
664.21 g/mol [M+Na]+, calc. 686.2082.

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2,4,5,6-Tetrakis(3,6-dimethoxy-9H-carbazol-9-yl)isophthalonitrile (4MeOCzIPN, D1-A2)

According to general procedure A using 200 mg

MeO OMe
tetrafluoroisophathalonitrile (1.0 mmol, 1.0 equiv). Yield
after flash chromatography (hexanes/DCM, 50-100%
N
DCM): 897 mg (0.87 mmol, 87%), red solid.
NC CN 1
H NMR (400 MHz, CDCl3): δ = 7.60 - 7.59 (m, 2H), 7.53
MeO OMe
N N - 7.51 (m, 2H), 7.29 - 7.27 (m, 2H), 7.15 (m, 4H) 7.05 -
7.03 (m, 4H), 6.83 - 6.82 (m, 2H), 6.70 - 6.66 (m, 6H), 6.31
- 6.28 (m, 2H), 3.99 (s, 6H), 3.79 (s, 12H), 3.69 (s, 6H).

MeO OMe
13
C NMR (100 MHz, CDCl3): δ = 155.6, 155.1, 154.4,
N
145.1, 144.5, 135.6, 135.3, 133.6, 132.5, 125.7, 125.3,
124.6, 115.7, 115.0, 114.5, 113.6, 112.0, 110.8, 110.5,
MeO OMe
110.1, 104.1, 103.5, 102.8, 56.1, 55.9, 55.8. HR MS (ESI+,
C64H48N6O8
1029.12 g/mol MeCN): m/z = 1051.3436 [M+Na]+, calc. 1051.3426.

2,3,4,5,6-Pentakis(3,6-dimethoxy-9H-carbazol-9-yl)benzonitrile (5MeOCzBN, D1-A4)

vvv According to general procedure A

MeO OMe
using 193 mg pentafluorobenzonit-
rile (1.0 mmol, 1.0 equiv). Yield
CN after flash chromatography
N N
(hexanes/DCM, 12-100% DCM):
MeO OMe
839 mg (0.68 mmol, 68%), yellow
MeO N OMe solid.
N N 1
H NMR (400 MHz, CDCl3):
δ = 7.16 (m, 4H) 7.06 - 7.04 (m,
MeO OMe
4H), 6.93 - 6.91 (m, 2H), 6.83 -
MeO OMe 6.81 (m, 4H), 6.78 (m, 4H), 6.75 -
C77H60N6O10 6.74 (m, 2H), 6.68 - 6.65 (m, 4H),
1229.36 g/mol
6.27 - 6.24 (m, 4H), 6.23 - 6.20 (m,
2H), 3.80 (s, 12H), 3.66 (s, 12H), 3.61 (s, 6H). 13C NMR (100 MHz, CDCl3): δ = 154.5, 154.1, 154.0, 141.1,
140.0, 135.9, 134.4, 133.2, 133.1, 124.6, 124.21, 124.20, 115.8, 114.2, 113.14, 113.11, 113.0, 111.3, 111.1, 110.9,
103.2, 102.53, 102.48, 55.9, 55.7, 55.6. HR MS (ESI+, MeCN): m/z = 1251.4258 [M+Na]+, calc. 1251.4263.

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5 General Procedures for Test Reactions

5.1 Decarboxylative Addition of Cbz-Proline to Diethylmaleate

entry photocatalyst yielda of 3

1 4CzIPN 80%b
2 3DPAFIPN 16%
3 5CzBN 37%
4 3DPA2FBN 20%
5 3CzClIPN 77%b
6 3DPAClIPN 12%
7 4MeOCzIPN 3%
8 5MeOCzBN 1%
9 Mes-4MeOAcr-2MeOPh+ 73%b
a
yield determined by GC-FID analyses using mesitylene as internal standard. b isolated yield.

Diethyl 2-(1-((benzyloxy)carbonyl)pyrrolidin-2-yl)succinate (3)

According to literature procedure.2

O In a Schlenk tube 37.4 mg N-carbobenzyloxy-(S)-proline (0.15 mmol, 1.0 equiv),
O
O 31.4 mg K2HPO4 (0.18 mmol, 1.1 equiv) and 2 mol % photocatalyst were dissolved
in 3.75 mL acetonitrile. 28.4 mg diethyl maleate (0.17 mmol, 1.1 equiv) was added
O
N O and the mixture was degassed by freeze-pump-thaw cycles (3×). After irradiation
for 20 h the mixture was poured into water and extracted with DCM (3×). The
O
C20H27NO6 combined organic phases were dried over Na2SO4 and filtered. The solvent was
377.44 g/mol
removed under reduced pressure and the residue was purified by flash
chromatography on silica gel (hexanes/ethyl acetate; 3-20% ethyl acetate) to afford product 3 as a colorless
solid. 1H NMR (400 MHz, CDCl3): δ = 7.49 - 7.31 (m, 5H), 5.30 - 5.03 (m, 2H), 4.38 - 4.28 (m, 1H), 4.24 -
4.02 (m, 4H), 3.77 - 3.46 (m, 2H), 3.44 - 3.20 (m, 1H), 2.88 - 2.66 (m, 1H), 2.57 - 2.24 (m, 1H), 2.01 - 1.72
(m, 4H), 1.32 - 1.16 (m, 6H).

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5.2 Photocatalytic Bromination of Anisole

entry catalyst reaction time yielda of 5

1 Mes-Acr-Me+ 16 h 87%

2 3CzClIPN 16 h 89%
a
yield determined by GC-FID analyses with mesitylene as internal standard.

1-Bromo-4-methoxybenzene (5)

According to literature procedure.3

In an oven dried Schlenk flask equipped with a magnetic stir bar 5 mol % photocatalyst were
dissolved in 5 mL MeCN. Then, 6.6 mg anisole (6.6 µL, 60 µmol, 1.0 equiv) (0.012 M) was
added and the solution was purged with oxygen for 10 minutes. Finally, 51 mg HBr (34 µL,
0.30 mmol, 5.0 equiv; 48% aqueous solution) were added and the solution was irradiated with blue light
(455 nm) for 16 h. Mesitylene was added as internal standard and yields were determined by GC-FID
analyses.

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5.3 Sequential C-O Bond Cleavage with Subsequent Pinacol Coupling

time to full conversion of

entry photocatalyst yieldb of 8
6a
1 4CzIPN 3h 61%

2 3DPAFIPN 1h 64%

3 5CzBN 1h 69%

4 3DPA2FBN 2h 77%

5 3CzClIPN 3h 0%

6 3DPAClIPN 45 min 64%

7 4MeOCzIPN 5h 0%

8 5MeOCzBN 5h 0%

9 [Ir(ppy)2(dtbpy)](PF6) 1h 56%

10 Eosin Y -c 0%

a
conversion and yield of 7 determined by GC-FID analyses with mesitylene as internal standard. b isolated yield after 18 h of
irradiation. c after 24 h only traces of acetophenone 7 could be detected.

2,3-Bis(4-methoxyphenyl)butane-2,3-diol (8)

According to literature procedure.4,5

In a reaction tube 68.1 mg 2-(2-methoxyphenoxy)-1-(4-
methoxyphenyl)ethan-1-one 6 (0.25 mmol, 1.0 equiv) and 1 mol %
photocatalyst were dissolved in 1.25 mL acetonitrile. 96.9 mg DIPEA
(0.75 mmol, 3.0 equiv) and 35.5 mg formic acid (0.75 mmol, 3.0 equiv)
were added to the solution. 1.0 equiv mesitylene was added as internal
standard and the mixture was irradiated for the time indicated. The conversion to the acetophenone 7 was
monitored by GC-FID analyses. After 18 h of irradiation the reaction mixture was poured into water and

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extracted with DCM (3×). The combined organic phases were dried over Na2SO4 and filtered. The solvent
was removed under reduced pressure and the residue was purified by flash chromatography on silica gel
(hexanes/ethyl acetate; 3-20% ethyl acetate) to afford the final pinacol-type product 8 as a colorless solid.

1
H NMR (400 MHz, CDCl3) δ 7.18 – 7.10 (m, 4H), 6.82 – 6.79 (m, 4H), 3.84 – 3.81 (m, 6H), 2.50 (s, 1H),
2.23 (s, 1H), 1.56 (s, 3H), 1.50 (s, 3H).

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5.4 Reductive Detriflation of Naphtholtriflate

method photocatalyst PC conditions reaction time yielda of 10 │ 11

3DPA2FBN
1 mol %
3 equiv DIPEA
8h 21% │ 60%
A 3 equiv HCO2H
c(PC) = 2 mM
MeCN Σ 81%
c = 0.2 M

fac-Ir(ppy)3
1 mol %
3 equiv DIPEA
8h 22% │ 59%
A 3 equiv HCO2H
c(PC) = 2 mM Σ 81%
MeCN
c = 0.2 M

3DPA2FBN
1 mol %
3 equiv DIPEA
12 h 23% │ 63%
Adiluted 3 equiv HCO2H
c(PC) = 0.4 mM
MeCN Σ 86%
c = 0.04 M

fac-Ir(ppy)3
1 mol %
3 equiv DIPEA
8h 26% │ 64%
Adiluted 3 equiv HCO2H
c(PC) = 0.4 mM Σ 90%
MeCN
c = 0.04 M

20% │ 58%
8h
3DPA2FBN Σ 78%
3 equiv DIPEA
2 mol %
Adiluted/2×cat 3 equiv HCO2H 12 h
c(PC) = 0.8 mM
MeCN
c = 0.04 M 23% │ 64%

Σ 87%

23% │ 65%
6h
3DPA2FBN Σ 88%
3 equiv DIPEA
2 mol %
A2×cat 3 equiv HCO2H 8h
c(PC) = 4 mM
MeCN
c = 0.2 M 24% │ 67%

Σ 91%

Rh-6G
2.2 equiv DIPEA 0% │ 0%
B DMSO 24 h
10 mol %
degassed Σ 0%

Ru(bpy)3Cl2
1 mol %,
1.4 equiv DIPEA
12 h 8% │ 34%
C DMSO
pyrene Σ 42%
degassed
5 mol %
a
yield determined by GC-FID analyses with mesitylene as internal standard.

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Figure S1: Reaction progress for different conditions of aryl sulfonate detriflation (see table) displayed in a kinetic diagram. Given
concentrations refer to the corresponding concentration of the photocatalyst in the reaction mixture. Yields are determined by GC-
FID with mesitylene as internal standard.

Naphthalene (10) and 2-Naphthol (11)

Method A:
In an oven dried Schlenk tube equipped with a magnetic stir bar 1 mol % (0.0025 mmol) photocatalyst (PC)6
and 69.1 mg 2-naphthol trifluoromethanesulfonate (9) (0.25 mmol, 1.0 equiv) were dissolved in 1.25 mL
MeCN (c(PC) = 2.0 mM) or in 6.0 ml MeCN (c(PC) = 0.4 mM). Then, 96.9 mg diisopropylethylamine
(0.75 mmol, 3.0 equiv) and 34.5 mg formic acid (0.75 mmol, 3.0 equiv) were added and the solution was
irradiated with blue light (455 nm) for 8 h to 16 h (as indicated). Mesitylene was added as internal standard
and yields were determined by GC-FID analyses.

Method B:7
An oven dried Schlenk tube equipped with a magnetic stir bar was charged with 10 mol % rhodamine 6G
and 27.6 mg 2-naphthol trifluoromethanesulfonate (9) (0.1 mmol, 1.0 equiv). The Schlenk tube was
evacuated and backfilled with nitrogen (3×). Then, 1 mL dry DMSO and 28.4 mg diisopropylethylamine
(0.22 mmol, 2.2 equiv) were added under nitrogen. The solution was degassed by freeze-pump-thaw cycles
(3×) and irradiated with blue light (455 nm) for 24 h. Mesitylene was added as internal standard and yields
were determined by GC-FID analyses.

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Method C:8
In an oven dried Schlenk tube equipped with a magnetic stir bar 1 mol % Ru(bpy)3Cl2, 5 mol % pyrene and
55.2 mg 2-naphthol trifluoromethanesulfonate (9) (0.2 mmol, 1.0 equiv) were dissolved in 1 mL DMSO
under nitrogen. 36.2 mg diisopropylethylamine (0.28 mmol, 1.4 equiv) were added. The solution was
degassed by freeze-pump-thaw cycles (3×) and irradiated with blue light (455 nm) for 12 h. Mesitylene was
added as internal standard and yields were determined by GC-FID analyses.

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6 Cyclic Voltammograms of Electron Donors

Figure S2: Cyclic voltammogram of 3,6-dimethoxy-carbazole D1 in MeCN and ferrocene as internal standard.

E1/2(D●+/D) = 0.90 V (vs. SCE)

Figure S3: Cyclic voltammogram of diphenylamine D2 in MeCN and ferrocene as internal standard.

E1/2(D●+/D) = 1.02 V (vs. SCE)

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Figure S4: Cyclic voltammogram of carbazole D3 in MeCN and ferrocene as internal standard.

E1/2(D●+/D) = 1.25 V (vs. SCE)

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7 Photophysical Properties of Photocatalysts

E1/2 E1/2 E1/2 E1/2

●+ ●− ●+ ●−
Emission λmax E0-0a Lifetimeb
Photocatalyst (PC /PC*) (PC*/PC ) (PC /PC) (PC/PC )
[nm] [eV] kp‒1 [ns]
[V] [V] [V] [V]

4CzIPN −1.18 1.43 1.49 −1.24 539 2.67 12.7

3DPAFIPN −1.38 1.09 1.30 −1.59 525 2.68 4.2

5CzBN −1.42 1.31 1.41 −1.52 511 2.83 16.3

3DPA2FBNc −1.60 0.92 1.24 −1.92 491 2.84 4.2

3CzClIPN −0.93 1.56 1.79 −1.16 545 2.72 6.9

3DPAClIPN −1.34 1.24 1.31 −1.41 537 2.65 11.5

4MeOCzIPNd −1.50 1.27 1.11 −1.34 482 2.61 -e

5MeOCzBNb −1.79 1.15 1.02 −1.66 462 2.81 -e

Table S1: All potentials in Volts vs. SCE. Measurements were performed in MeCN using ferrocene as internal standard unless
otherwise noted (Fc+/Fc → SCE: +0.380 V9). a For method of determination: see ‘General Methods’ section (p. S2) for more details.
b
Measurement in no-degassed MeCN as polar solvent provides the lifetime kp‒1 of the prompt part of the photoluminescence only;
kd‒1 [µs] of the delayed photoluminescence was not determined. c CV measurement performed in DCM to enhance solubility. d CV
measurement performed in MeCN/DCM 5:1 v/v to enhance solubility. e Not determined due to weak emission intensity.

Abbreviations
Donors:
Cz (carbazole, D3), DPA (diphenylamine, D2), MeOCz (3,6-dimethoxy-9H-carbazole, D1)
Given numbers refer to the actual quantity of the respective donor in the molecule.

Acceptors:
BN (benzonitrile, A4), ClIPN (5-chloro isophthalonitrile, A1Cl), 2FBN (3,5-difluoro benzonitrile = meta,meta´-
difluoro benzonitrile, A3), FIPN (5-fluoro isophthalonitrile, A1F), IPN (isophthalonitrile, A2)

A1Cl A1F A2 A3 A4
R R R CN CN
NC CN NC CN NC CN R R R R

R R R R R R F F R R
Cl F R R R

ClIPN FIPN IPN 2FBN BN

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8 Photoredox Characteristics for each Photocatalyst

8.1 4CzIPN (D3-A2)

N
NC CN

N N

C56H32N6
788.91 g/mol

5,00E+02

4,00E+02

3,00E+02
Current/µA

2,00E+02

1,00E+02

0,00E+00
-2,000 -1,500 -1,000 -0,500 0,000 0,500 1,000 1,500 2,000

-1,00E+02
Potential/V

Figure S5: Cyclic voltammogram of 4CzIPN in MeCN and ferrocene as internal standard.

E1/2(PC●+/PC*) = −1.18 V, E1/2(PC*/PC●−) = 1.43 V, E1/2(PC●+/PC) = 1.49 V, E1/2(PC/PC●−) = −1.24 V

All potentials are given vs. SCE.9

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Figure S6: UV/Vis absorption and emission spectrum of 4CzIPN in MeCN (5 µM).

Emission λmax in MeCN: 539 nm

E0-0: 2.67 eV

Figure S7: Fluorescence decay curve of 4CzIPN in MeCN (5 µM).

Lifetime τ in MeCN: 12.7 ns

χ2=1.062

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8.2 3DPAFIPN (D2-A1F)

N
NC CN

N N
F

C44H30FN5
647.76 g/mol

Figure S8: Cyclic voltammogram of 3DPAFIPN in MeCN and ferrocene as internal standard.

E1/2(PC●+/PC*) = −1.38 V, E1/2(PC*/PC●−) = 1.09 V, E1/2(PC●+/PC) = 1.30 V, E1/2(PC/PC●−) = −1.59 V

All potentials are given vs. SCE.9

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Figure S9: UV/Vis absorption and emission spectrum of 3DPAFIPN in MeCN (5 µM).

Emission λmax in MeCN: 525 nm

E0-0: 2.68 eV

Figure S10: Fluorescence decay curve of 3DPAFIPN in MeCN (5 µM).

Lifetime τ in MeCN: 4.2 ns

χ2=1.062

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8.3 5CzBn (D3-A4)

3,50E+02

3,00E+02

2,50E+02

2,00E+02
Current/µA

1,50E+02

1,00E+02

5,00E+01

0,00E+00
-2,000 -1,500 -1,000 -0,500 0,000 0,500 1,000 1,500 2,000
-5,00E+01
Potential/V

Figure S11: Cyclic voltammogram of 5CzBN in MeCN and ferrocene as internal standard.

E1/2(PC●+/PC*) = −1.42 V, E1/2(PC*/PC●−) = 1.31 V, E1/2(PC●+/PC) = 1.41 V, E1/2(PC/PC●−) = −1.52 V

All potentials are given vs. SCE.9

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Figure S12: UV/Vis absorption and emission spectrum of 5CzBN in MeCN (5 µM).

Emission λmax in MeCN: 512 nm

E0-0: 2.83 eV

Figure S13: Fluorescence decay curve of 5CzBN in MeCN (5 µM).

Lifetime τ in MeCN: 16.3 ns

χ2=0.964

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8.4 3DPA2FBN (D2-A3)

Figure S14: Cyclic voltammogram of 3DPA2FBN in DCM and ferrocene as internal standard.

E1/2(PC●+/PC*) = −1.60 V, E1/2(PC*/PC●−) = 0.92 V, E1/2(PC●+/PC) = 1.24 V, E1/2(PC/PC●−) = −1.92 V

All potentials are given vs. SCE.9

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Figure S15: UV/Vis absorption and emission spectrum of 3DPA2FBN in MeCN (5 µM).

Emission λmax in MeCN: 491 nm

E0-0: 2.84 eV

Figure S16: Fluorescence decay curve of 3DPA2FBN in MeCN (5 µM).

Lifetime τ in MeCN: 4.2 ns

χ2=1.104

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8.5 3CzClIPN (D3-A1Cl)

5,00E+02

4,00E+02

3,00E+02
Current/µA

2,00E+02

1,00E+02

0,00E+00
-1,800 -1,300 -0,800 -0,300 0,200 0,700 1,200 1,700 2,200

-1,00E+02
Potential/V

Figure S17: Cyclic voltammogram of 3CzClIPN in MeCN and ferrocene as internal standard.

E1/2(PC●+/PC*) = −0.93 V, E1/2(PC*/PC●−) = 1.56 V, E1/2(PC●+/PC) = 1.79 V, E1/2(PC/PC●−) = −1.16 V

All potentials are given vs. SCE.9

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Figure S18: UV/Vis absorption and emission spectrum of 3CzClIPN in MeCN (5 µM).

Emission λmax in MeCN: 545 nm

E0-0: 2.72 eV

Figure S19: Fluorescence decay curve of 3CzClIPN in MeCN (5 µM).

Lifetime τ in MeCN: 6.9 ns

χ2=1.033

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8.6 3DPAClIPN (D2-A1Cl)

Figure S20: Cyclic voltammogram of 3DPAClIPN in MeCN and ferrocene as internal standard.

E1/2(PC●+/PC*) = −1.34 V, E1/2(PC*/PC●−) = 1.24 V, E1/2(PC●+/PC) = 1.31 V, E1/2(PC/PC●−) = −1.41 V

All potentials are given vs. SCE.9

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Figure S21: UV/Vis absorption and emission spectrum of 3DPAClIPN in MeCN (5 µM).

Emission λmax in MeCN: 537 nm

E0-0: 2.65 eV

Figure S22: Fluorescence decay curve of 3DPAClIPN in MeCN (5 µM).

Lifetime τ in MeCN: 11.5 ns

χ2=1.080

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8.7 4MeOCzIPN (D1-A2)

Figure S23: Cyclic voltammogram of 4MeOCzIPN in MeCN/DCM 5:1 v/v and ferrocene as internal standard.

E1/2(PC●+/PC*) = −1.50 V, E1/2(PC*/PC●−) = 1.27 V, E1/2(PC●+/PC) = 1.11 V, E1/2(PC/PC●−) = −1.34 V

All potentials are given vs. SCE.9

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Figure S24: UV/Vis absorption and emission spectrum of 4MeOCzIPN in MeCN (5 µM).

Emission λmax in MeCN: 482 nm

E0-0: 2.61 eV

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8.8 5MeOCzBN (D1-A4)

Figure S25: Cyclic voltammogram of 5MeOCzBN in DCM and ferrocene as internal standard.

E1/2(PC●+/PC*) = −1.79 V, E1/2(PC*/PC●−) = 1.15 V, E1/2(PC●+/PC) = 1.02 V, E1/2(PC/PC●−) = −1.66 V

All potentials are given vs. SCE.9

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Figure S26: UV/Vis absorption and emission spectrum of 5MeOCzBN in MeCN (5 µM).

Emission λmax in MeCN: 462 nm

E0-0: 2.81 eV

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9 Absorption and Fluorescence Overlays

Figure S27: UV/Vis absorption spectra overlay of all photocatalysts (5 µM in MeCN).

Figure S28: Emission spectra overlay of all photocatalysts (5 µM in MeCN).

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10 Additional Spectral Data for Fluorine Containing Photocatalysts

10.1 19F NMR and HR MS Spectra of 3DPAFIPN (D2-A1F)

Figure S29: 19F NMR spectrum of 3DPAFIPN in CDCl3, 8.0 mg 3DPAFIPN (0.01 mmol), 11 mg p-fluoro toluene (0.1 mmol) as
internal standard, integral of standard set to 10.00, integral of F in 3DPAFIPN = 1.01 = 1 F.

1 13
H and C NMR spectra (shown below, pages S36 and S37) resemble those reported by Zhang and co-
workers. Note the 259.5 Hz 1JC,F coupling at 152.4 (153.7/151.1) ppm in the 13C NMR spectrum
10

[M+Na]+

[M+NH4]+
[M+K]+

[M+H]+

Figure S30: Overview HR MS (ESI+, MeCN) spectrum of 3DPAFIPN ([M+Na]+, calc.: 670.2378) up to m/z 885.

Please note that only traces of a putative structure 4DPAIPN ([M+Na]+, calc. 819.3207)10 may have been formed.b

b +
Reported and calculated mass data for a putative compound 4DPAIPN in ref. 10 (“m/z calcd. for C56H40N6Na
+
([M + Na] ) 817.3212, found: 817.3147.“) differ from the correct value and may stem from typos as
819.3212 refers to the uncharged [M+Na] m/z value: 819.3212).
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[M+Na]+

[M+H]+
[M+NH4]+ [M+K]+

Figure S31: Detailed HR MS (ESI+, MeCN, m/z 640 to 690) spectrum of 3DPAFIPN , m/z = 648.2558 [M+H]+, calc. 648.2558;
665.2826 [M+NH4]+, calc. 655.2823; 670.2378 [M+Na]+, calc. 670.2377;
686.2111 [M+K]+, calc. 686.2117.

10.2 19F NMR, 13C NMR Spectra Details and HR MS Spectra of 3DPA2FBN (D2-A3)

Figure S32: 19F NMR spectrum of 3DPA2FBN in CDCl3.

Figure S33: Zoomed overview 13C NMR spectrum of 3DPA2FBN in CDCl3 (157 -109 ppm).

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Figure S34: Zoomed detailed of 13C NMR spectrum of 3DPA2FBN in CDCl3 showing JCF couplings (157-152 ppm).

Figure S35: Zoomed detail of 13C NMR spectrum of 3DPA2FBN in CDCl3 showing JCF couplings (136-134 ppm).

Figure S36: Zoomed detail of 13C NMR spectrum of 3DPA2FBN in CDCl3 showing JCF couplings (131-123 ppm).

Figure S37: Zoomed detail of 13C NMR spectrum of 3DPA2FBN in CDCl3 showing JCF couplings (115-108 ppm).

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[M+Na]+

[M+H]+

[M+K]+

Figure S38: Overview HR MS (ESI+, MeCN) spectrum of 3DPA2FBN ([M+Na]+, calc.: 663.2331) up to m/z 970.

[M+Na]+

[2M+Na]+

Figure S39: Overview HR MS (ESI+, MeCN + Na formiate) spectrum of 3DPA2FBN ([M+Na]+, calc.: 663.2331) up to m/z 1350

[M+H]+

Figure S40: Overview HR MS (ESI+, MeCN + HCOOH) spectrum of 3DPA2FBN ([M+H]+, calc.: 641.2511) up to m/z 1425.

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[M+Na]+

[M+H]+

[M+K]+

Figure S41: Detailed HR MS (ESI+, MeCN, m/z 640 to 685) spectrum of 3DPA2FBN , m/z = 641.2519 [M+H]+, calc. 641.2511;
663.2329 [M+Na]+, calc. 663.2331; 679.2081 [M+K]+, calc. 679.2070.

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11 References
1) Fulmer, G. R.; Miller, A. J. M.; Sherden, N. H.; Gottlieb, H. E.; Nudelman, A.; Stoltz, B. M.; Bercaw,
J. E.; Goldberg, K. I., Organometallics, 2010, 29, 2176-2179.
2) Joshi-Pangu, A.; Lévesque, F.; Roth, H. G.; Oliver, S. F.; Campeau, L. -C.; Nicewicz, D. A.; DiRocco, D.
A., J. Org. Chem. 2016, 81, 7244-7249.
3) Ohkubo, K.; Mizushima, K.; Iwata, R.; Fukuzumi, S. Chem. Sci. 2011, 2, 715-722.
4) Nguyen, J. D.; Matsuura, B. S.; Stephenson, C. R. J. Am. Chem. Soc. 2014, 136, 1218-1221.
5) Nakajima, M.; Fava, E.; Loescher, S.; Jiang, Z.; Rueping, M. Angew. Chem. Int. Ed. 2015, 54, 8828-8832.
6) For the experiment with 2 mol % catalyst 0.005 mmol photocatalyst were dissolved in 1.25 ml MeCN.
7) Shaikh, R. S.; Düsel, S. J. S.; König, B. ACS Catal. 2016, 6, 8410-8414.
8) Ghosh, I.; Shaikh, R. S.; König, B. Angew. Chem. Int. Ed. 2017, 56, 8544-8549.
9) Pavlishchuk, V. V.; Addison, A. W. Inorg. Chim. Acta 2000, 298, 97-102.
10) Luo, J.; Zhang, J., ACS Catal. 2016, 6, 873-877.

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12 NMR Spectra of Substrates and Products

12 NMR Spectra of Substrates and Products

3DPAFIPN D2-A1F

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3DPAFIPN D2-A1F

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3DPAFIPN D2-A1F

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5CzBN D3-A4

S44
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5CzBN D3-A4

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3DPA2FBN D2-A3

S46
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3DPA2FBN D2-A3

S47
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3DPA2FBN D2-A3

S48
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3CzClIPN D3-A1Cl

S49
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3CzClIPN D3-A1Cl

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N
NC CN

N N
Cl

3DPAClIPN D2-A1Cl

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N
NC CN

N N
Cl

3DPAClIPN D2-A1Cl

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4MeOCzIPN D1-A2

S53
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4MeOCzIPN D1-A2

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5MeOCzBN D1-A4

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5MeOCzBN D1-A4

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O
O
O

O
N O

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1
Fulmer, G. R.; Miller, A. J. M.; Sherden, N. H.; Gottlieb, H. E.; Nudelman, A.; Stoltz, B. M.; Bercaw, J. E.; Goldberg, K. I., Organometallics, 2010, 29, 2176-2179.
2
Joshi-Pangu, A.; Lévesque, F.; Roth, H. G.; Oliver, S. F.; Campeau, L. -C.; Nicewicz, D. A.; DiRocco, D. A., J. Org. Chem. 2016, 81, 7244-7249.
3
Ohkubo, K.; Mizushima, K.; Iwata, R.; Fukuzumi, S. Chem. Sci. 2011, 2, 715-722.
4
Nguyen, J. D.; Matsuura, B. S.; Stephenson, C. R. J. Am. Chem. Soc. 2014, 136, 1218-1221.
5
Nakajima, M.; Fava, E.; Loescher, S.; Jiang, Z.; Rueping, M. Angew. Chem. Int. Ed. 2015, 54, 8828-8832.
6
For the experiment with 2 mol % catalyst 0.005 mmol photocatalyst were dissolved in 1.25 ml MeCN.
7
Shaikh, R. S.; Düsel, S. J. S.; König, B. ACS Catal. 2016, 6, 8410-8414.
8
Ghosh, I.; Shaikh, R. S.; König, B. Angew. Chem. Int. Ed. 2017, 56, 8544-8549.
9
Pavlishchuk, V. V.; Addison, A. W. Inorg. Chim. Acta 2000, 298, 97-102.
10
Luo, J.; Zhang, J., ACS Catal. 2016, 6, 873-877.

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