Supporting information- Journal of Polymer Science Part A: Polymer Chemistry
Hyperbranched Framework of Interrupted π-Conjugated
Polymers End-capped with High Carrier-mobility Moieties for
Stable Light-emitting Materials with Low Driving Voltage
Feng Liu,1 Ju-Qing Liu,1 Ran-Ran Liu,1 Xiao-Ya Hou,1 Ling-Hai Xie,1,*
Hong-Bin Wu,2 Chao Tang,1 Wei Wei,1 Yong Cao,2
1
1, *
Jiangsu Key Laboratory for Organic Electronics & Information Displays
and Institute of Advanced Materials (IAM), Nanjing University of Posts and
Telecommunications, 9 Wenyuan Road, Nanjing 2100046, China
2
Institute of Polymer Optoelectronic Materials and Devices, South China
University of Technology, Guangzhou 510640, China
*
To whom correspondence should be addressed. Tel: +86 25 8588 2333; Fax: +86 25
8349 2333; E-mail: iamlhxie@njupt.edu.cn; iamwhuang@njupt.edu.cn.
1
Figure S1. The 1H-NMR spectrum of tris(4-(2-bromo-9-phenyl-fluoren-9yl)phenyl)amine.
Figure S2.The 13C-NMR spectrum of tris(4-(2-bromo-9-phenyl-fluoren-9yl)phenyl)amine.
2
14.299
22.832
24.155
29.454
30.270
31.162
Figure S4. The C13 NMR spectrum of CDAF1.
0.816
1.140
32.023
40.621
53.644
55.570
120.184
121.715
126.377
126.951
127.367
127.400
128.381
128.998
129.147
140.239
140.716
3
1.559
1.562
2.115
2.124
6.954
7.114
7.260
7.374
7.524
152.028
ppm (f1)
0
50
100
150
7.678
7.834
Figure S3. The H1 NMR spectrum of CDAF1.
0.50
0.00
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
5.00
5.50
6.00
6.50
7.00
7.50
8.00
9.00
8.50
ppm (t1)
14.307
22.838
24.154
29.459
Figure S6. The C13 NMR spectrum of CDAF2.
0.822
30.271
32.029
40.634
55.574
120.198
121.721
121.825
126.385
127.435
128.458
129.007
140.254
140.725
ppm (f1)
1.147
1.572
2.123
6.961
7.122
7.258
7.380
7.522
152.040
4
0.0
2.5
5.0
7.5
0
50
100
150
7.687
7.839
ppm (t1)
Figure S5. The H1 NMR spectrum of CDAF2.
0.829
1.153
14.309
22.843
24.165
29.464
30.279
32.035
40.638
55.581
120.199
121.725
121.834
126.393
127.436
128.528
129.008
5
1.595
1.609
2.129
2.134
6.978
7.127
7.258
7.382
140.259
140.735
Figure S8. The C13 NMR spectrum of CDAF3.
0
50
100
150
7.497
7.693
7.846
7.865
152.043
ppm (f1)
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
ppm (t1)
Figure S7. The H1 NMR spectrum of CDAF3.
Figure S9. The MALDI-TOF-MS spectrum of CDAF2.
We use MALDI-TOF-MS to analysis the hyperbranched polymers. For CDAF2, the
linear mode mass spectrum is listed (Figure S9). In the mass spectrum, three series of
peaks could be observed, and we assigned A, B, C to them. For each group, the adjacent
two peaks show a mass difference near 777, that is the mass of bifluorene, the repeating
unit in the polymer. The hyperbranched polymer composed of three major building
blocks, the core, dialkylfluorene and pyrene. The mass difference between adjacent B and
C peaks is 200.5, based on structure analysis and mass calculation; we believe this is the
signals that indicate the difference between B and C is the lack of a pyrene unit.
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a) CDAF1
unannealed
12h under N2
b) CDAF2
unannealed
12h under N2
1h in air
3h in air
6h in air
12h in air
Intensity (a. u.)
1h in air
3h in air
6h in air
12h in air
c) CDAF3
unannealed
12h under N2
CDAF1 unanealed
CDAF2 unanealed
CDAF3 unanealed
CDAF1 12h in air
CDAF2 12h in air
CDAF3 12h in air
d)
1h in air
3h in air
6h in air
12h in air
375
450
525
600
675 375
450
525
600
675
Wavelength (nm)
Figure S10. PL spectra of polymer films annealed under nitrogen and in air with
different time at 200 °C. a) CDAF1; b) CDAF2; c) CDAF3; d) comparison of the three
polymers before annealing and annealed in air for 12 h.
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Relative Intensity
20 mA
10 mA
5 mA
2 mA
350
400
450
500
550
600
Wavelength (nm)
Figure S11. Normalized electroluminescent spectra of CDAF1 in the device: (a)
ITO/PEDOT: PSS (50nm)/PVK (40nm)/ CDAF1 (70nm)/Ba (4nm)/Al (120nm); (b)
ITO/PEDOT: PSS (50nm)/ MEHPPV (0.25%)/CDAF-co-F1 (70nm)/Ba (4nm)/Al
(120nm). CIE 1931 x, y color coordinates of EL emission at different current are shown
in the inset.
8