1
Electronic Supplementary Information
New AIEgens containing dibenzothiophene-S,S-dioxide and tetraphenylethene
moieties: similar structures but much different hole/electron transport properties
Xuejun Zhan,1,4
Zhongbin Wu,2,4
Yuxuan Lin,1
Sheng Tang,1 Jie Yang,
1 Jie Hu,
1 Qian Peng,
3 Dongge
Ma,*2 and Qianqian Li,
1 Zhen Li*
1
1Department of Chemistry, Hubei Key Lab on Organic and Polymeric Opto-Electronic Materials,
Wuhan University, Wuhan, 430072, China.
E-mail: [email protected] or [email protected]
2 Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022,
China
E-mail: [email protected]
3 Institute of Chemistry, The Chinese Academy of Sciences, Beijing, China.
4The authors contributed equally to this paper.
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2015
2
Table of Contents
1. Chart S1. Several molecules disclosing various approaches to suppress intramolecular charge
transfer.
2. Figure S1. TGA curves recorded under N2 at a heating rate of 10 oC/min.
3. Figure S2. DSC curves recorded under N2 at a heating rate of 10 oC/min.
4. Figure S3. UV spectra in THF solution (10 μM) (A) and in the film state (B).
5. Figure S4. PL spectra in the film state.
6. Figure S5. (A) PL spectra of DBTO-pTPE in THF/H2O mixtures with different water fractions
(fw). Concentration (): 10excitation wavelength (nm): 370. (B) Plots of fluorescence
quantum yields determined in THF/H2O solutions using 9,10-diphenylanthracene (Ф = 90% in
cyclohexane) as standard versus water fractions. Inset in (B): photos in THF/water mixtures (fw
= 0 and 99%) taken under the illumination of a 365 nm UV lamp.
7. Figure S6. (A) PL spectra of DBTO-MeTPE in THF/H2O mixtures with different water
fractions (fw). Concentration (): 10excitation wavelength (nm): 350. (B) Plots of
fluorescence quantum yields determined in THF/H2O solutions using 9,10-diphenylanthracene
(Ф = 90% in cyclohexane) as standard versus water fractions. Inset in (B): photos in THF/water
mixtures (fw = 0 and 99%) taken under the illumination of a 365 nm UV lamp.
8. Figure S7. (A) PL spectra of DBTO-mTPE in THF/H2O mixtures with different water fractions
(fw). Concentration (): 10excitation wavelength (nm): 320. (B) Plots of fluorescence
quantum yields determined in THF/H2O solutions using 9,10-diphenylanthracene (Ф = 90% in
cyclohexane) as standard versus water fractions. Inset in (B): photos in THF/water mixtures (fw
= 0 and 99%) taken under the illumination of a 365 nm UV lamp.
9. Figure S8. Calculated molecular orbital amplitude plots of HOMO and LUMO levels and
optimized molecular structures.
10. Figure S9. (a) Current density-voltage-luminance characteristics, (b) Change in current
efficiency with the current density in multilayer EL devices and (c-e) EL spectra of the AIEgens
DBTO-pTPE (device A, c), DBTO-MeTPE (device B, d) and DBTO-mTPE (device C, e) at
different voltages. Device configurations: ITO / MoO3 (10 nm) / NPB (60 nm) / mCP (10 nm) /
EML (15 nm) / TPBi (30 nm) / LiF (1.5 nm) /Al.
11. Figure S10. (a) Luminance-current density characteristics, (b) Power efficiency- current density
characteristics, (c) External quantum efficiency- current density characteristics and (d) Current
efficiency-luminance characteristics of the AIEgens DBTO-pTPE (device A), DBTO-MeTPE
(device B) and DBTO-mTPE (device C). Device configurations: ITO / MoO3 (10 nm) / NPB
(60 nm) / mCP (10 nm) / EML (15 nm) / TPBi (30 nm) / LiF (1.5 nm) /Al.
3
12. Figure S11. Energy level diagram of the multilayer devices.
13. Figure S12-17. NMR spectra of DBTO-pTPE, DBTO-MeTPE and DBTO-mTPE.
N
N
N
CH3
H3C
N CH3
H3C
CH3
CH3
N
N
NN
N
N
N N
NN
N
NN
O
N
N O
NN
PP
OO
N
N CH2O
NN
Chart S1. Several molecules disclosing various approaches to suppress intramolecular charge
transfer.
4
50 150 250 350 450 550 65020
40
60
80
100
DBTO-pTPE
DBTO-MeTPE
DBTO-mTPE
Weig
ht
(%)
Temperature (oC)
Figure S1. TGA curves recorded under N2 at a heating rate of 10 oC/min.
40 60 80 100 120 140 160 180
1 st
1 st
2 nd
110 oC
130 oC
DBTO-pTPE
DBTO-MeTPE
DBTO-mTPE
<en
do
H
eat
flo
w ex
o>
Temperature (oC)
139 oC
Figure S2. DSC curves recorded under N2 at a heating rate of 10 oC/min.
5
Figure S3. UV-vis spectra in THF solution (~10 μM) (A) and in the thin solid film (B).
370 470 570 6700.0
0.2
0.4
0.6
0.8
1.0 DBTO-pTPE
DBTO-MeTPE
DBTO-mTPE
PL
In
ten
sit
y (
au
)
Wavelength (nm)
Figure S4. PL spectra in the solid films.
300 350 400 450 500 550
0.0
0.2
0.4
0.6
DBTO-pTPE
DBTO-MeTPE
DBTO-mTPE
Ab
so
rban
ce (
a.u
.)
Wavelength (nm)
A
300 350 400 450 500 550
B
DBTO-pTPE
DBTO-MeTPE
DBTO-mTPE
Ab
so
rba
nc
e (
a.u
.)
Wavelength (nm)
6
Figure S5. (A) PL spectra of DBTO-pTPE in THF/H2O mixtures with different water fractions (fw).
Concentration (): 10excitation wavelength (nm): 370. (B) Plots of fluorescence quantum yields
determined in THF/H2O solutions using 9,10-diphenylanthracene (Ф = 90% in cyclohexane) as
standard versus water fractions. Inset in (B): photos of SFTPE in THF/water mixtures (fw = 0 and
99%) taken under the illumination of a 365 nm UV lamp.
Figure S6. (A) PL spectra of DBTO-MeTPE in THF/H2O mixtures with different water fractions
(fw). Concentration (): 10excitation wavelength (nm): 350. (B) Plots of fluorescence quantum
yields determined in THF/H2O solutions using 9,10-diphenylanthracene (Ф = 90% in cyclohexane)
as standard versus water fractions. Inset in (B): photos of SFTPE in THF/water mixtures (fw = 0 and
99%) taken under the illumination of a 365 nm UV lamp.
420 470 520 570 620 670
0
10
20
30
40
50
60
70
80
90
95
99
PL
In
ten
sit
y (
a.u
.)
Wavelength (nm)
fw (vol %)A
420 470 520 570 620 670
0
10
20
30
40
50
60
70
80
90
95
99
PL
In
ten
sit
y (
au
)
Wavelength (nm)
fw (vol %)A
0 20 40 60 80 100
0
5
10
15
20
25
30
35
40
B
Qu
an
tum
yie
ld (
%)
Water fraction (vol%)
0 20 40 60 80 100
0
5
10
15
20
25
30
35
40
B
Qu
an
tum
yie
ld (
%)
Water fraction (vol%)
7
Figure S7. (A) PL spectra of DBTO-mTPE in THF/H2O mixtures with different water fractions (fw).
Concentration (): 10excitation wavelength (nm): 320. (B) Plots of fluorescence quantum yields
determined in THF/H2O solutions using 9,10-diphenylanthracene (Ф = 90% in cyclohexane) as
standard versus water fractions. Inset in (B): photos of SFTPE in THF/water mixtures (fw = 0 and
99%) taken under the illumination of a 365 nm UV lamp.
Figure S8. Calculated molecular orbital amplitude plots of HOMO and LUMO levels and optimized
molecular structures.
420 470 520 570 620 670
0
10
20
30
40
50
60
70
80
90
95
99
PL
In
ten
sit
y (
a.u
.)
Wavelength (nm)
fw (vol %)A
0 20 40 60 80 100
0
5
10
15
20
25
30
35
40
B
Qu
an
tum
yie
ld (
%)
Water fraction (vol%)
8
2 4 6 8 10 12 14 160
100
200
300
400
500
600
700
800
100
101
102
103
104(a) Device A
Device B
Device C
Cu
rre
nt
Den
sit
y (
mA
/cm
2)
Voltage (V)
Bri
gh
tness (
cd
/m2)
0.1 1 10 100 10000
2
4
6
8
10
(b) Device A
Device B
Device C
Cu
rren
t E
ffic
ien
cy (
cd
/A)
Current Density (mA/cm2)
9
350 400 450 500 550 600 650 700 750 8000.0
0.2
0.4
0.6
0.8
1.0
1.2
(c) 6V
7V
8V
9V
10V
No
rmalized
in
ten
sit
y (
a.u
.)
Wavelength (nm)
350 400 450 500 550 600 650 700 750 8000.0
0.2
0.4
0.6
0.8
1.0
1.2
(d) 6V
7V
8V
9V
10V
No
rmalized
in
ten
sit
y (
a.u
.)
Wavelength (nm)
10
350 400 450 500 550 600 650 700 750 8000.0
0.2
0.4
0.6
0.8
1.0
1.2
(e) 6V
7V
8V
9V
10V
No
rmalized
in
ten
sit
y (
a.u
.)
Wavelength (nm)
Figure S9. (a) Current density-voltage-luminance characteristics, (b) Change in current efficiency
with the current density in multilayer EL devices and (c-e) EL spectra of the AIEgens DBTO-pTPE
(device A, c), DBTO-MeTPE (device B, d) and DBTO-mTPE (device C, e) at different voltages.
Device configurations: ITO / MoO3 (10 nm) / NPB (60 nm) / mCP (10 nm) / EML (15 nm) / TPBi
(30 nm) / LiF (1.5 nm) /Al.
0.01 0.1 1 10 10010
0
101
102
103
104
(a)
Device A
Device B
Device C
Bri
gh
tness (
cd
/m2)
Current Density (mA/cm2)
11
0.1 1 10 100 10000
1
2
3
4
5
6
(b) Device A
Device B
Device C
Po
wer
Eff
icie
ncy (
lm/W
)
Current Density (mA/cm2)
0.1 1 10 100 10000.00
0.01
0.02
0.03
0.04
0.05
(c) Device A
Device B
Device C
Exte
rnal Q
uan
tum
Eff
icie
ncy
Current Density (mA/cm2)
12
101
102
103
104
0
2
4
6
8
10
(d) Device A
Device B
Device C
Cu
rre
nt
Eff
icie
ncy (
cd
/A)
Luminescence (cd/m2)
Figure S10. (a) Luminance-current density characteristics, (b) Power efficiency- current density
characteristics, (c) External quantum efficiency- current density characteristics and (d) Current
efficiency-luminance characteristics of the AIEgens DBTO-pTPE (device A), DBTO-MeTPE
(device B) and DBTO-mTPE (device C). Device configurations: ITO / MoO3 (10 nm) / NPB (60
nm) / mCP (10 nm) / EML (15 nm) / TPBi (30 nm) / LiF (1.5 nm) /Al.
2.3 2.32.7
5.3 5.3
6.2
4.7
3.1
ITO
LiF/Al
Mo
O3
NP
B
TP
Bi
mC
P
2.3
5.8
2.7
5.6
DB
TO
-pT
PE
2.5
5.6
2.4
5.6
DB
TO
-Me
TP
E
DB
TO
-mT
PE
Figure S11. Energy level diagram of the multilayer devices.
13
Figure S12. 1H NMR spectrum of the DBTO-pTPE in CDCl3.
Figure S13. 13
C NMR spectrum of the DBTO-pTPE in CDCl3.
14
Figure S14. 1H NMR spectrum of the DBTO-MeTPE in CDCl3.
.
Figure S15. 13
C NMR spectrum of the DBTO-MeTPE in CDCl3.
15
Figure S16. 1H NMR spectrum of the DBTO-mTPE in CDCl3.
Figure S17. 13
C NMR spectrum of the DBTO-mTPE in CDCl3.
