Supporting Information:
Blue LED Light-Sensitive Benzo Pyrazolo (or Imidazo)
Isoquinolinone Derivatives in High Performance Photoinitiating
Systems for Polymerization Reactions.
Pu Xiao,a Frédéric Dumur,b Bernadette Graff,a Jing Zhang,a Fabrice Morlet-Savary,a Didier
Gigmes,b Jean Pierre Fouassier1 and Jacques Lalevée*,a
a
Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, ENSCMu-UHA,
15, rue Jean Starcky, 68057 Mulhouse Cedex, France.
b
Aix-Marseille Université, CNRS, ICR, UMR 7273, F-13397 Marseille, France.
Corresponding Authors: jacques.lalevee@uha.fr
All reagents and solvents were purchased from Aldrich or Alfa Aesar and used as
received without further purification. Mass spectroscopy was performed by the Spectropole of
Aix-Marseille University. ESI mass spectral analyses were recorded with a 3200 QTRAP
(Applied Biosystems SCIEX) mass spectrometer. The HRMS mass spectral analysis was
performed with a QStar Elite (Applied Biosystems SCIEX) mass spectrometer. Elemental
analyses were recorded with a Thermo Finnigan EA 1112 elemental analysis apparatus driven
by the Eager 300 software. 1H and 13C NMR spectra were determined at room temperature in
5 mm o.d. tubes on a Bruker Avance 400 spectrometer of the Spectropole: 1H (400 MHz) and
13
C (100 MHz). The 1H chemical shifts were referenced to the solvent peak CDCl3 (7.26 ppm),
DMSO (2.49 ppm) and the 13C chemical shifts were referenced to the solvent peak CDCl3 (77
ppm), DMSO (49.5 ppm). All these dyes were prepared with analytical purity up to accepted
1
Formerly, ENSCMu-UHA, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France.
standards for new organic compounds (>98%) which was checked by high field NMR
analysis.
For IQ1 and IQ3, the mixture of isomers has been separated for identification.
Synthesis of 3-(hexylamino)-7H-benzo[de]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one IQ1
and 4-(hexylamino)-7H-benzo[de]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one IQ2
To a stirred solution of 3-bromo-7H-benzo[de]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one
IQ3 (1.74 g, 5.00 mmol) in DMF (15 mL) was added hexylamine (1.97 mL, 1.52 g, 15.00
mmol). The mixture was then refluxed overnight. After completion, the reaction mixture was
cooled to room temperature and concentrated under vacuum until most of the solvent was
removed. Addition of pentane precipitated a solid identified as one of the two initial isomers
(IQ1) (0.52 g, 28% yield). The residue was purified by column chromatography (SiO2) using
DCM as the eluent. After evaporation of the volatiles, addition of acetonitrile precipitated an
orange solid which was filtered off and dried under vacuum. The second precipitate was
identified as being the second isomer IQ2 (0.63 g, 34 % yield).
IQ1 : 1H NMR (CDCl3) δ (ppm): 0.87-0.92 (m, 6H), 1.28-1.41 (m, 12H), 1.47-1.55 (m, 2H),
1.63-1.66 (m, 2H), 3.28 (t, 2H, J = 6.6 Hz, NH-CH2), 3.30 (t, 2H, J = 6.6 Hz, NH-CH2), 5.345.37 (m, 2H), 6.47 (d, 1H, J = 8.4 Hz), 7.00 (d, 1H, J = 8.2 Hz), 7.44-7.48 (m, 5H), 7.59 (t,
1H, J = 7.8 Hz), 7.76 (d, 1H, J = Hz), 7.84 (d, 2H, J = 8.2 Hz), 8.17 (s, 1H), 8.24 (d, 1H, J =
8.3 Hz), 8.35 (d, 1H, J = 8.5 Hz), 8.49-8.53 (m, 4H), 8.60 (d, 1H, J = 7.0 Hz), 8.69 (d, 1H, J =
7.1 Hz);
13
C NMR (CDCl3) δ (ppm): 13.93, 13.98, 22.46, 22.53, 26.44, 26.76, 28.8, 29.4,
31.3, 31.5, 38.1, 43.6, 44.7, 104.3, 109.8, 113.0, 114.5, 115.8, 115.9, 119.4, 119.5, 120.1,
120.3, 120.5, 123.2, 123.4, 124.7, 124.9, 125.0, 125.23, 125.25, 126.8, 129.0, 131.8, 131.9,
133.1, 134.8, 143.6, 143.7, 149.5, 149.6, 150.2, 157.8, 160.4, 160.5, 161.1; HRMS (ESI MS)
m/z: theor: 369.1841 found: 369.1844 (M+. detected).
IQ2 : 1H NMR (CDCl3) δ (ppm): 0.93 (t, 3H, J = 7.1 Hz), 1.36-1.38 (m, 6H), 1.71-1.74 (m,
4H), 3.23-3.28 (m, 2H), 5.37 (t, 1H, J = 6.5 Hz), 6.61 (d, 1H, J = 8.5 Hz), 7.44-7.46 (m, 2H),
7.57 (t, 1H, J = 7.4 Hz), 7.86 (d, 1H, J = 7.4 Hz), 8.49 (d, 1H, J = 8.5 Hz), 8.56-8.59 (m, 1H),
8.72 (d, 1H, J = 7.3 Hz); 13C NMR (CDCl3) δ (ppm): 14.0, 22.6, 26.8, 28.9, 31.5, 43.7, 104.5,
110.2, 116.0, 119.5, 120.3, 120.7, 123.3, 124.6, 125.0, 125.1, 127.0, 128.5, 132.0, 135.1,
143.7, 149.6, 150.2, 160.6; HRMS (ESI MS) m/z: theor: 369.1841 found: 369.1839 (M+.
detected).
Synthesis of 3-bromo-7H-benzo[de]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one IQ3
6-Bromobenzo[de]isochromene-1,3-dione (1.85 g, 6.68 mmol) and o-phenylenediamine (0.72
g, 6.68 mmol) was suspended in acetic acid (50 mL) and the solution was refluxed overnight.
During reflux, a yellow precipitate formed. After cooling, the solvent was removed under
reduced pressure. The residue was suspended in pentane, washed several times with pentane
and dried under vacuum. The product was obtained under the form of a mixture of isomers in
nearly quantitative yield. After several recrystallization in a mixture of DMF/toluene, the title
molecule could be isolated pure (0.82 g, 35% yield). 1H NMR (CDCl3) δ (ppm): 7.48-7.50 (m,
2H), 7.86-7.89 (m, 1H), 7.92 (d, 1H, J = 7.9 Hz), 8.08 (d, 1H, J = 7.9 Hz), 8.52-8.54 (m, 1H),
8.65 (t, 1H, J = 8.3 Hz), 8.53 (d, 1H, J = 7.2 Hz);
13
C NMR (CDCl3) δ (ppm): 115.8, 120.0,
120.3, 123.6, 125.7, 126.0, 127.0, 127.5, 128.0, 128.1, 131.2, 131.5, 131.8, 132.4, 134.5,
143.8, 148.6, 160.0; 1H NMR (DMSO d6) δ (ppm): 7.51-7.53 (m, 2H), 7.90-7.91 (m, 1H),
8.10 (t, 1H, J = 7.9 Hz), 8.28 (d, 1H, J = 7.8 Hz), 8.43 (d, 1H, J = 7.9 Hz), 8.62 (d, 1H, J = 8.4
Hz), 8.67 (d, 1H, J = 8.4 Hz), 8.80 (d, 1H, J = 7.2 Hz); HRMS (ESI MS) m/z: theor: 348.9971
found: 348.9975 ((M+H)+ detected).
Figure S1. The emission spectrum of the halogen lamp.
1,0
0,8
I (a.u.)
0,6
0,4
0,2
0,0
380
400
420
440
460
480
500
 (nm)
Figure S2. The emission spectrum of the blue LED centered at 477 nm.
200
160
2
I (A/cm )
120
80
40
0
-40
0.0
0.5
1.0
1.5
2.0
E (V)
Figure S3. Cyclic voltammogram of IQ1 (measured in acetonitrile with tetrabutylammonium
hexafluorophosphate as a supporting electrolyte).