Supporting Information
Naphthalic Anhydride Derivatives: Structural Effects on Their
Initiating Abilities in Radical and/or Cationic Photopolymerizations
under Visible Light.
Pu Xiao,a Frédéric Dumur,b Jing Zhang,a Bernadette Graff,a Jean Pierre Fouassier,1 Didier
Gigmesb and Jacques Lalevée*,a
a
Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15, rue Jean
Starcky, 68057 Mulhouse Cedex, France.
b
Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, F-13397
Marseille, Cedex 20, 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 13C (100
MHz). The 1H chemical shifts were referenced to the solvent peak CDCl3 (7.26 ppm), DMSO
(2.49 ppm) and the
1
13
C chemical shifts were referenced to the solvent peak CDCl3 (77 ppm),
Formerly, ENSCMu-UHA, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France.
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DMSO (49.5 ppm). All these dyes were prepared with analytical purity up to accepted standards
for new organic compounds (>98%) which was checked by high field NMR analysis.
4-Nitro-1,8-naphthalic anhydride ANH1 and 5-dinitro-1,8-naphthalic anhydride ANH3 [a) M.
Zhu, J. Zhang, G. Yu, H. Chen, J. Huang, Y. Liu, Chem. Asian J. 2012, 10, 2208; b) M. Dong,
Y.-W. Wang, Y. Peng, Org. Lett. 2010, 12, 5310], 3-nitro-1,8-naphthalic acid anhydride ANH2
[J.-J. Lee, B. C. Noll, B. D. Smith, Org. Lett. 2008, 10, 1735], 3,6-dinitro-1,8-naphthalic
anhydride ANH4 [S. Girouard, M.-H. Houle, A. Grandbois, J. W. Keillor, S. W. Michnick, J.
Am. Chem. Soc. 2005, 127, 559], 3-amino-1,8-naphthalic acid anhydride ANH5 [J. Wang, L.
Yang, C. Hou, H. Cao, Org. Biomol. Chem. 2012, 10, 6271], 3,6-diamino-1,8-naphthalic
anhydride ANH6 [S. Ferrari, M. Ingrami, F. Soragni, R. C. Wade, M. P. Costi, Bioorg. Med.
Chem. Lett. 2013, 23, 663] were synthesized as previously reported, without modifications and
obtained with similar yields.
Synthesis of 4-octylsulfanyl-1,8-naphthalic acid anhydride ANH7
To a stirred solution of 4-bromo-1,8-naphthalic acid anhydride (1.60 g, 5.77 mmol) and
potassium carbonate (0.51 g) in DMF (15 mL) was added 1-octanethiol (1.0 mL, 0.88 g, 5.99
mmol). The mixture was heated at 50°C overnight. After cooling, the suspension was poured into
40 mL of distilled water, the precipitate was collected by filtration, washed with distilled water,
and dried under vacuum (1.74 g, 88% yield). 1H NMR (CDCl3) δ (ppm): 0.89 (t, 3H, J = 6.2 Hz),
1.20-1.40 (m, 8H), 1.52-1.54 (m, 2H), 1.82-1.84 (m, 2H), 3.19 (t, 2H, J = 7.1 Hz), 7.55 (d, 1H, J
= 7.7 Hz), 7.79 (t, 1H, J = 7.7 Hz), 8.47 (d, 1H, J = 7.6 Hz), 8.63 (d, 2H, J = 7.7 Hz); 13C NMR
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(CDCl3) δ (ppm): 14.1, 22.6, 28.1, 29.0, 29.08, 29.10, 31.7, 32.7, 114.3, 119.3, 122.3, 126.9,
129.5, 130.4, 131.4, 132.9, 133.6; HRMS (ESI MS) m/z: theor: 342.1290 found: 342.1292 (M+.
detected).
Synthesis of 2-(1,3-dioxo-1,3-dihydrobenzo[de]isochromen-5-yl)isoindoline-1,3-dione ANH8
This molecule was synthesized by adapting a literature procedure [P. Mahato, S. Saha, E. Suresh,
R. Di Liddo, P. P. Parnigotto, M. T. Conconi, M. K. Kesharwani, B. Ganguly, A. Das, Inorg.
Chem. 2012, 51, 1769]. 3-Amino-1,8-naphthalic acid anhydride ANH5 (1 g, 4.69 mmol) and
phthalic anhydride (0.76 g, 5.16 mmol, 1.1 eq.) was suspended in acetonitrile (50 mL) and the
solution was refluxed for 2 days. After that the reaction mixture was cooled to room temperature
and evaporated to dryness. Then, to the reaction mixture 30 mL of ethanol was added and stirred
for about 3 h. A precipitate appeared which was filtered through G-4 crucible. The residue was
washed several times with ethanol, ether and dried under vacuum (1.19 g, 74% yield). 1H NMR
(DMSO d6) δ (ppm): 7.61-7.74 (m, 3H), 7.84 (t, 1H, J = 7.8 Hz), 7.94 (d, 1H, J = 7.5 Hz),
8.39-8.43 (m, 2H), 8.76 (s, 1H), 8.85 (s, 1H);
13
C NMR (DMSO d6) δ (ppm): 121.3, 121.4,
122.2, 122.7, 124.2, 127.6, 127.9, 129.1, 129.6, 129.7, 129.9, 131.9, 132.0, 133.9, 138.26,
138.32, 160.2, 160.5, 167.3, 168.1; HRMS (ESI MS) m/z: theor: 343.0481 found: 343.0478 (M+.
detected).
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Table S1. Extinction coefficients and maximum absorption wavelengths for the investigated
compounds; extinction coefficients for the wavelengths of the used lights.
PI
max
ANH1
ANH2
ANH3
ANH4
ANH5
ANH6
ANH7
ANH8
343
327
393
326
417
423
389
338
max
405nm
455nm
(M-1cm-1) (M-1cm-1) (M-1cm-1)
11000
150
8700
50
10500
9800
1600
6300
60
4700
4300
1200
5100
4200
2200
10200
7900
200
10100
3200
130
1.00
I (a.u.)
0.75
0.50
0.25
0.00
380
400
420
440
460 480
 (nm)
500
520
540
Figure S1. The emission spectrum of blue LED centered at 455 nm.
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Figure S2. Transient absorption spectra recorded 440 ns after the laser excitation (at 355 nm) of
(a) ANH3 [inset: triplet state decay of ANH3 at 460 nm (after smooth treatment) immediately
after the laser excitation at 355 nm; lifetime: 1.2 s] and (b) ANH6 in nitrogen-saturated
acetonitrile (inset: triplet state decay of ANH6 at 440 nm (after smooth treatment) immediately
after the laser excitation at 355 nm; lifetime: 1.1 s).
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