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Olivier Poizate and Stephan Knopf b a School of ... c Institut de Chimie et des Matériaux Paris-Est, UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais. Université ...

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is © The Royal Society of Chemistry 2014

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Two-Photon Lithography in Visible and NIR Ranges Using Multibranched-based Sensitizers For Efficient Acid Generation Ming Jin*,a, Jianchao Xie a, Jean-Pierre Malval*, b, Arnaud Spangenbergb, Olivier Soppera b, DavyLouis Versace c, Tiffanie Leclerc b, Haiyan Pan a, Decheng Wan a, Hongting Pua, Patrice Baldeck d, Olivier Poizate and Stephan Knopf b

a School

of Materials Science and Engineering, Tongji University, Shanghai 201804, P.R. China. Institut de Science des Matériaux de Mulhouse, UMR CNRS 7361, Université de Haute-Alsace, 15 rue Jean Starcky, 68057 Mulhouse, France. c Institut de Chimie et des Matériaux Paris-Est, UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais. Université Paris-Est Créteil Val de Marne, France. d Laboratoire de Spectrométrie Physique, UMR CNRS 5588. Université Joseph Fourier, 38402 Saint Martin d’Hères, France. e Laboratoire de Spectrochimie Infrarouge et Raman, UMR CNRS 8516. Université des Sciences et Technologies de Lille. 59655 Villeneuve d'Ascq Cedex b

Contact: [email protected] or [email protected]

CONTENTS Figure S1.

Figure S2. Figure S3. Figure S4. Figure S5. Figure S6. Figure S7. Figure S8.

2PEF spectra of 1 (9  10-5 M in ACN, exc: 760 nm) using two distinctive detection configurations. A. The excitation focal point is located in the middle of the cell (1 cm quartz cuvette); B. The excitation focal point is positioned very close to the detection window. In both cases, the 1PEF spectrum was measured using the classical method with a spectrofluorimeter (10-6 M in ACN, exc: 370 nm). Evolution of the absorption spectrum of 1 (2.4  10-4 M in degassed ACN) in presence of Ph2I+,PF6- (1.5  10-3 M) during irradiation at 365 nm. Rhodamine B base (1  10-5 M) is added as acid indicator. Representation of frontier molecular orbitals involved in the lowest energy electronic transitions of the chromophores. Solvatochromic plots of Stokes shift for the chromophores. Time fluorescence decays of the chromophores recorded at their respective fluoMAX; instrumental response function (IRF). Residual graphs relative to single- or bi-exponential fits. (solvent: Hexane). Plots of logIfluo (fluo: 475 nm) vs. log[excitation power] at 500 nm for 3. (THF, c: 1.5  10-4 M). Fluorescence spectra of 1 in dichloromethane upon addition of PAG. Inset: Stern-Volmer plots as observed by steady state fluorescence intensities and emission lifetimes. Comparison of the conversion vs. time curves for cationic photopolymerization of diepoxide films under aerated and laminated conditions. (resin: PAG (1.5 wt %) / 3 (0.15 wt %). exc: 365 nm , Irradiance: 45 mW cm-2).

1

A

Fluo. (norm.)

1

2PEF 1PEF

0 400

500

600

700

800

900

1000

B

Fluo. (norm.)

1

2PEF 1PEF

0 400

500

600

700

800

Wavelength (nm)

Figure S1.

2

900

1000

3.0

A555 nm

0.8

2.4

Abs.

1.8

0.4

0.0

0

1.2

3

6

9

time (s)

12

0.6

0.0

300

400

500

Wavelength (nm)

Figure S2.

3

600

15

HOMO

LUMO

Figure S3. 4

7500

1

Stokes Shift, abs-fluo / cm-1

5000 2500

7500

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.00

0.05

0.10

0.15

0.20

0.25

0.30

2

5000 2500

7500

3

5000 2500

 1 n 1  2  1 2n 2  1 2

Figure S4.

5

104

1 = 1.02 ns 2 = 1.20

Residuals

Counts

1

3 0 -3

0

104

5

10

Time / ns

A1= 0.80 1 = 1.02 ns 2 = 1.07 A2= 0.20 2 = 1.66 ns

Residuals

Counts

2

3 0 -3

0

104

5

10

Time / ns

A1= 0.65 1 = 1.25 ns 2 = 1.03 A2= 0.35 2 = 1.38 ns

Residuals

Counts

3

3 0 -3

0

2

4

6

Time / ns

8

Figure S5.

6

10

12

Log Ifluo / a.u.

10000

1000

2.01 ± 0.05 100

10

100

log P / mW

Figure S6.

7

[PAG] : 0 M

0/ or 0/

Fluo. (a.u.)

0/ 0/

1.65

150

0.012 M

100

1.50

1.35

1.20

1.05

0.000

0.002

0.004

0.006

0.008

0.010

0.012

[PAG] (M) 50

0 400

450

500

550

Wavelength (nm)

Figure S7.

8

600

650

laminated

Conversion (%)

50

aerated

40 30 20 10 0

0

50

100

150

Irradiation time (s)

Figure S8.

9

200