Support Information
Green Photocatalysis with Oxygen Sensitive BODIPYs under
Visible Light
Li Quan, Wenhai Lin, Tingting Sun, Zhigang Xie,* Yubin Huang and Xiabin Jing
State Key Labortory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese
Academy of Sciences, 5625 Renmin Street, Changchun, Jilin 130022, P. R. China. Fax: +86 431 85262779; Tel:
+86 431 85262773; E-mail: xiez@ciac.jl.cn
Supporting information (SI):
Table of Contents
Instrumentation................................................................................................................................2
Synthesis of BODIPY.......................................................................................................................2
Scheme 1. Synthesis of BODIPY 1..................................................................................................2
General procedure for photocatalytic oxidation of thioanisole...................................................2
Table S1 Control experiments of oxidation of thioanisole............................................................2
Table S2. List of data about linear relationship according to Figure S1.....................................3
Figure S1.1H NMR of BODIPY 1...................................................................................................3
Figure S2.MS of BODIPY 1............................................................................................................3
Figure S3. 1H NMR of crude mixture for oxidation of thioanisole..............................................4
Figure S4. 1H NMR of crude mixture for oxidation of thioanisole with NaN3...........................4
References.........................................................................................................................................4
1
Instrumentation. All starting materials were purchased from Aldrich and Fisher, unless otherwise
noted. 1H-NMR spectra were recorded on a Bruker NMR 400 DRX Spectrometer at 400 MHz and
referenced to the proton resonance resulting from incomplete deuteration of deuterated chloroform
(δ 7.26). UV-Vis absorption spectra were obtained using a Shimadzu UV-2450 PC UV-Vis
Spectrophotometer. Strengthening experiments were performed using Perkin ElmerLS-55
Spectrofluorophotometer and Hitachi Fluorescence spectrophotometer-F-7000. Fluorescence
lifetime was determined by Edinburgh Analytical Instrument F-900. The phosphorescence
spectrum at 77 K was obtained using Hitachi Fluorescence spectrophotometer-F-4500.
Synthesis of BODIPY
The BODIPY 2, 3 and 4 were synthesized according to the literature procedure [1,2] (Structures
were shown in Table 1). BODIPY 1 was prepared as follows: To a mixture of
N-(4-formylphenyl)acetamide (2.50 g, 15.30 mmol), 2,4-dimethypyrrole (3.15 g, 30.65 mmol) in
CH2Cl2 (500 mL) was added trifluoroacetic acid (0.19 ml, 2.47 mmol) under nitrogen. The
reaction
mixture
was
stirred
for
4h
at
room
temperature,
then
2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 3.40 g, 15.30 mmol) in the mixed solvents of
CH2Cl2 (25 mL) and tetrahydrofuran (25 mL) was added and stirred for 1h. Et3N (12 mL) and
BF3Et2O (12 mL) were dropped under ice-cold conditions, the mixture was stirred for 30 min
before warming up to room temperature, and was stirred for additional 3h at room temperature.
The reaction mixture was washed with water (3  200 mL), and the organic layers were combined
and dried over anhydrous MgSO4. The solvent was evaporated in vacuum, and the residue was
purified by column chromatography (Silica gel, eluent: CH2Cl2) to afford red powder (1.34 g,
23%). Anal. Calc. for C21H22BF2N3O: C, 66.16; H, 5.82; B, 2.84; F, 9.96; N, 11.02; O, 4.20. Found:
C, 66.23; H, 6.01; B, 2.58; F, 9.75; N, 10.98; O, 4.45. 1H NMR (CDCl3):  1.42 (s, 6H); 2.22 (s,
6H); 2.55 (s, 6H); 5.97 (s, 2H); 7.23 (d, 2H, J = 8.36 Hz); 7.35 (S, 1H); 7.68 (d, 2H, J = 8.24 Hz).
MS (ESI): m/z (%): 381 M.
General procedure for photocatalytic oxidation of thioanisole
The same conditions were taken for photocatalytic oxidation of thioanisole [3]. In a short, to a 10
mL vial equipped with a magnetic stir bar were added BODIPY catalysts (2.50 mol, 0.005 equiv),
thioanisole (62 µL, 0.50 mmol, 1.0 equiv), solvent (0.50 mL). In some case, the trifluoroacetic
acid (TFA, 10-3mol L-1 in methanol, 200 μl) was added to the above mixture. The reaction mixture
was stirred at room temperature in air at a distance of ~5 cm from a 24 W fluorescent lamp with a
filter (λ = 395 nm). 1H NMR spectra used to calculate the conversion yields (Supplementary data).
Measurement of phosphorescence
Phosphorescence at room temperature (RTP): The emission was excited using 460 nm
wavelength at room temperature under different O2 concentration (0 of O2 (argon), 21% of O2 (air),
100% of O2 (O2)) with slit of 2.5, 2.5. Phosphorescence at 77K: The emission was excited
using 460 nm wavelength at liquid nitrogen environment in air with slit of 5.0, 5.0.
Table S1. List of data about linear relationship according to Figure 4.
Emission
No.
P
Slope
BODIPY 1
BODIPY 3
BODIPY 3-H
BODIPY 2
BODIPY 2
in methanol
in methanol
in methanol
in methanol
in toluene
-0.17
0
-0.11
0
-0.07
2
Intercept
49.07
1.99
44.82
1.37
18.59
R2
0.99
0.99
0.96
0.99
0.99
-14.70
-0.26
-23.74
-0.07
-4.47
5867.38
74.77
68565.34
35.58
1622.46
0.96
0.97
0.95
0.97
0.99
-13.89
-0.09
-8.73
-0.02
-2.04
Intercept
1.42
0.01
0.92
0
0.10
R2
0.98
0.98
0.99
0.99
0.99
Slope
L
Intercept
R2
Slope
F
Table S2. Control experiments of oxi dation of thioanisolea.
Entry
Condition
Conversionb
1
no light
0%
2
no BODIPY
0%
3
no O2
<1%
aAll
the reactions were run at room temperature for 24 h. Test 1 and 3 under BODIPY 1 photocatalyst.
bConversion
was determined by 1H NMR.
Fig. S1.1H NMR of BODIPY 1
Fig. S2.MS of BODIPY 1
3
Fig. S3. 1H NMR of crude mixture for oxidation of thioanisole
Fig. S4. 1H NMR of crude mixture for oxidation of thioanisole with NaN3.
References
1.
2.
3.
Li WL, Xie ZG, Jing XB (2011) Catal Commu 16:94
Urano Y, Asanuma D, Hama Y, Koyama Y, Barrett T, Kamiya M, Nagano T, Watanabe T,
Hasegawa A, Choyke PL, Kobayashi H (2009) Nat Med 15:104
Hoogendoorn S, Blom AEM, Willems LI, van der Marel GA, Overkleeft HS, (2011) Org Lett
13:5656
4