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Electronic Supplementary Information (ESI)
New insight on intramolecular conjugation in the design of efficient blue
materials: from the control of emission to absorption
Jie Yang†,#, Qingxun Guo‡,#, Zichun Ren†, Xuming Gao†, Qian Peng§, Qianqian Li†, Dongge Ma‡,*,
and Zhen Li†,*
†Department of Chemistry, Hubei Key Lab on Organic and Polymeric Opto-Electronic Materials,
Wuhan University, Wuhan 430072, China. Fax: (86)27-68756757. E-mail: lizhen@whu.edu.cn;
lichemlab@163.com. ‡Changchun Institute of Applied Chemistry, The Chinese Academy of Sciences Changchun
130022, China. E-mail: mdg1014@ciac.jl.cn. §Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Science (BNLMS),
Institute of Chemistry, Chinese Academy of Sciences, 100190 Beijing, China. # These authors contributed equally to this work.
Table of Contents Experimental Section
Figure S1 The effect of chromophore effect and auxochrome effect on adjusting the maximum
absorption wavelength (λabs).
Scheme S1 The synthetic routes to Cz-3tPE, TPA-3TPP and Cz-3TPP.
Figure S2 TGA curves (A) and DSC curves (B, C, D) for Cz-3tPE, TPA-3TPP and Cz-3TPP recorded
under N2 at a heating rate of 15 °C/min. Figure S3 UV-vis spectra of CzPh, TPA and tPE in THF solution (concentration ≈ 10 µM).
Figure S4 The chemical structures and the corresponding maximum absorption wavelengths
(λabs) for CzPh, TPA, TPP and tPE.
Figure S5 (A) UV-vis spectra of Cz-3tPE in different solutions, concentration ≈ 10 µM; (B) UV-vis
spectra of TPA-3TPP in different solutions, concentration ≈ 10 µM; (C) The UV spectra of
Cz-3TPP in different solutions, concentration ≈ 10 µM.
Figure S6 PL spectra in different solutions and the corresponding quantum yields for Cz-3tPE,
concentration ≈ 10 µM.
Figure S7 Linear correlation of orientation polarization (f) of solvent media with the Stokes shift
for Cz-3tPE (A), TPA-3TPP (B) and Cz-3TPP (C).
Table S1 Detailed absorption and emission peak positions of Cz-3tPE, TPA-3TPP and Cz-3TPP in
different solvents and the calculated ground-state dipole moment (μg), excited state dipole
moment (μe).
Figure S8 PL spectra of films and EL spectra for Cz-3tPE (A), TPA-3TPP (B) and Cz-3TPP (C), respectively.
Figure S9 The chemical structures, maximum absorption wavelengths (λabs), EL emission peaks
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2017
2
(λEL), external quantum yields (EQE) of TPA-3TPP, TTPECaP, Cz-3tPE, Cz-3TPP and the responding
different λabs and λEL effects.
Figure S10 The PL spectra in THF/n-hexane mixtures with different n-hexane fractions: (A) Cz-3tPE, concentration ≈ 10 µM; excitation wavelength 330 nm; (B) TPA-3TPP, concentration ≈
10 µM; excitation wavelength 340 nm; (C) Cz-3TPP, concentration ≈ 10 µM; excitation
wavelength 310 nm.
Figure S11 Calculated molecular orbital amplitude plots of HOMO and LUMO levels and
optimized molecular structures of Cz-3tPE, TPA-3TPP and Cz-3TPP.
Figure S12 The cyclic voltammograms of Cz-3tPE, TPA-3TPP and Cz-3TPP recorded in
dichloromethane.
Figure S13 The changes in power efficiency with the current density.
Figure S14 MALDI-TOF of Cz-3tPE.
Figure S15 MALDI-TOF of TPA-3TPP.
Figure S16 MALDI-TOF of Cz-3TPP.
Experimental Section
Characterizations 1H and 13C NMR spectra were conducted on a Mecuryvx300 or Ascend 400 MHz
spectrometer. Elemental analyses of carbon, hydrogen and nitrogen were taken on a
Carlo-Erba-1106 microanalyzer. Mass spectra were measured on a Voyager DESTR MALDI-TOF
mass spectrometer. UV-Vis absorption spectra were measured on a Shimadzu UV-2500
recording spectrophotometer. Photoluminescence spectra were recorded on a Hitachi F-4600
fluorescence spectrophotometer. Differential scanning calorimetry (DSC) was performed on a
NETZSCHDSC 200 PC instrument from room temperature to 300 oC at a heating rate of 15 oC
min-1 under argon. Thermogravimetric analysis (TGA) was measured on a NETZSCH STA 449C
instrument. The thermal stabilities of the samples under a nitrogen atmosphere were
determined by measuring their weight loss while heating from room temperature to 700 oC at a
rate of 15 oC min-1. Cyclic voltammetry (CV) was carried out on a CHI voltammetric analyzer in
three electrode cells with a platinum counter electrode, an Ag/AgCl reference electrode, and a
glassy carbon working electrode at a scan rate of 100 mV s-1 in anhydrous dichloromethane
solution with 0.1 M tetrabutylammonium perchlorate as the supporting electrolyte and purged
with nitrogen. The potentials obtained in reference to the Ag/Ag+ electrode were converted
into values versus the saturated calomel electrode (SCE) by means of ferrocenium/ferrocene
(Fc+/Fc) standard. Fluorescence quantum yields of powders and THF solutions were determined
with a HamamatsuC11347 Quantaurus-QY absolute fluorescence quantum yield spectrometer.
Solvatochromic effect The influence of solvent environment on the optical property of our compounds can be
understood using the Lippert-Mataga equation:
𝑣𝑎 − 𝑣𝑓 =1
4𝜋𝜀0∗2𝛥𝜇2
ℎ𝑐𝑎3𝛥𝑓 + 𝐶𝑜𝑛𝑠𝑡.
where a = √3𝑀
4𝜋𝑑𝑁𝑎
3
3
In the above equations, va-vf is the Stokes shift, ε0 is the vacuum permittivity, h is Planck’s
constant, c is the velocity of light, a is the Onsager radius of fluorophore, Δμ = μe - μg is the
difference in the dipole moment of fluorophore between the excited (μe) and the ground (μg)
states, e and n are the static dielectronic constant and the refractive index of the solvent,
respectively, Δf is the orientation polarizability, M is the molecular weight, d is the density of
molecule, and Na is Avogadro’s number. Therefore, based on equation, the change in dipole
moment, Δμ = μe - μg, can simply be estimated from the slope of a plot of va-vf against Δf.
Computational details
The molecular structures, orbital distributions of HOMO and LUMO energy levels and the
ground state dipole moments (μg) were optimized at B3LYP/6-31g* level using Gaussian 09
program.
The hole-only devices and measurement
The hole-only devices were fabricated on glass substrates. Prior to deposition, the substrate
was thoroughly cleaned in an ultrasonic bath using subsequently detergents and deionized
water. The structures of devices were ITO/MoO3/Cz-3tPE or TPA-3TPP or Cz-3TPP (110
nm)/MoO3/Al, and layers, Cz-3tPE, TPA-3TPP and Cz-3TPP, were grown in succession by thermal
evaporation without breaking vacuum (10-5 Pa). Here, the interfacial layer MoO3 worked as
hole-injection and electron-blocking layers. The Al electrodes were deposited on the substrates
through shadow masks. The current-voltage (I–V) characteristics were carried out using a
Keithley 2400 sourcemeter integrated with a vacuum cryostat (Optistat DN-V, Oxford
Instruments). The admittance was measured at room temperature by using an Agilent E4980A
precision LCR meter in the frequency range of 20 Hz–13 MHz with the oscillation amplitude of
the ac voltage kept at 100 mV.
OLED devices and measurement
The hole-transporting material of NPB (1,4-bis(1-naphthylphenylamino)-biphenyl), electron
blocking material of 1,3-Di-9-carbazolylbenzene (MCP) and electron transporting materials of
1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBi) and
1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (TmPyPB) were obtained from a commercial source. The
EL devices were fabricated by vacuum deposition of the materials at a base pressure of 10−5
Torr onto glass pre-coated with a layer of indium tin oxide (ITO) with a sheet resistance of 25 Ω
per square. Before deposition of an organic layer, the clear ITO substrates were treated with
oxygen plasma for 2 min. The deposition rate of organic compounds was 1–2 Å s −1. Finally, a
cathode composed of lithium fluoride (1 nm) and aluminium (100 nm) was sequentially
deposited onto the substrate in the vacuum of 10−5 Torr. The L–V–J of the devices was
measured with a Keithey 2400 Source meter and a Keithey 2000 Source multimeter equipped
with a calibrated silicon photodiode. The EL spectra were measured by JY SPEX CCD3000
spectrometer. All measurements were carried out at room temperature under ambient
conditions.
4
Figure S1 A new sight on the intramolecular conjugation in the design of efficient blue
materials―from the control of emission to absorption: the chromophore effect (the maximum
absorption wavelengths increase with the addition of double bond, nearly 30 nm per double
bond) and auxochrome effect (the maximum absorption wavelengths increase with the
enhanced electron donating ability for auxochrome) on adjusting the maximum absorption
wavelength (λabs).
Scheme S1 The synthetic routes to Cz-3tPE, TPA-3TPP and Cz-3TPP.
5
50 100 150 200 250 300
-20
-10
0
10
20
<exo H
ea
t F
low
en
do>
Temperature (oC)
Cz-3tPE
Tg=186
oCT
c=198
oC
(B)
Figure S2 TGA curves (A) and DSC curves (B, C, D) for Cz-3tPE, TPA-3TPP and Cz-3TPP recorded
under N2 at a heating rate of 15 °C/min.
250 300 350 400 450
0.0
0.1
0.2
0.3
Ab
so
rban
ce (
au
)
Wavelength (nm)
CzPh
TPA
tPE
Figure S3 UV-vis spectra of CzPh, TPA and tPE in THF solution (concentration ≈ 10 µM).
100 200 300 400 500 600 700
20
40
60
80
100
Weig
ht
(%)
Temperature (oC)
Cz-3tPE
TPA-3TPP
Cz-3TPP
(A)
75 125 175 225 275
-14
-12
-10
-8
-6
-4
-2
0
2
4
6
8
10
<exo H
eat
Flo
w e
nd
o>
Temperature (oC)
TPA-3TPP
(C)
50 100 150 200 250 300
-40
-20
0
20
40
<exo H
eat
Flo
w e
ndo>
Temperature (oC)
Cz-3TPP
Tg=194
oC
(D)
6
Figure S4 The chemical structures and the corresponding maximum absorption wavelengths
(λabs) for CzPh, TPA, TPP and tPE.1
280 330 380 430 480
0.0
0.2
0.4
0.6
0.8
Ab
so
rban
ce (
au
)
Wavelength (nm)
Toluene
THF
DCM
DMF
(A)
280 330 380 430 480
0.0
0.3
0.6
0.9
Ab
so
rban
ce (
au
)
Wavelength (nm)
Toluene
THF
DCM
DMF
(B)
280 330 380 430
0.0
0.2
0.4
0.6
0.8
Ab
so
rba
nc
e (
au
)
Wavelength (nm)
Toluene
THF
DCM
DMF
(C)
Figure S5 (A) UV-vis spectra of Cz-3tPE in different solutions, concentration ≈ 10 µM; (B) UV-vis
spectra of TPA-3TPP in different solutions, concentration ≈ 10 µM; (C) UV-vis spectra of Cz-3TPP
in different solutions, concentration ≈ 10 µM.
Figure S6 PL spectra in different solutions and the corresponding quantum yields for Cz-3tPE,
concentration ≈ 10 µM.
7
0.0 0.1 0.2 0.3
5900
6100
6300
6500
6700
va-v
f (c
m-1)
f
(A)
0.0 0.1 0.2 0.3
3400
3800
4200
4600
5000
5400
5800
va-v
f (c
m-1)
f
(B)
0.0 0.1 0.2 0.3
5500
6000
6500
7000
7500
8000
8500
va-v
f (c
m-1)
f
Figure S7 Linear correlation of orientation polarization (f) of solvent media with the Stokes shift
(υa−υf; a: absorbed light; f: fluorescence) for Cz-3tPE (A), TPA-3TPP (B) and Cz-3TPP (C).
Table S1 Detailed absorption and emission peak positions of Cz-3tPE, TPA-3TPP and Cz-3TPP in
different solvents and the calculated ground-state dipole moment (μg), excited state dipole
moment (μe).
Compounds Solvents f λa (nm) λf (nm) va-vf (cm-1) μga (D) μe
b (D)
Cz-3tPE
PhMe 0.014 351 445 6018
3.3 12.9 THF 0.210 351 450 6268
DCM 0.217 348 451 6563
DMF 0.276 352 460 6670
TPA-3TPP
PhMe 0.014 363 417 3567
0.1 18.8 THF 0.210 362 435 4636
DCM 0.217 363 445 5076
DMF 0.276 364 460 5733
Cz-3TPP
PhMe 0.014 312 383 5942
2.9 22.3 THF 0.210 313 398 6823
DCM 0.217 311 405 7643
DMF 0.276 312 423 8411
400 450 500 550 600
No
rmalize
d P
L/E
L In
ten
sit
y (
au
)
Wavelength (nm)
Film
EL (A)
EL (B)
(A)
400 450 500 550 600
No
rma
lize
d P
L/E
L I
nte
ns
ity
(a
u)
Wavelength (nm)
Film
EL(C)
EL(D)
(B)
350 400 450 500 550
No
rmalize
d P
L/E
L In
ten
sit
y (
au
)
Wavelength (nm)
Film
EL (E)
EL (F)
(C)
Figure S8 PL spectra of films and EL spectra for Cz-3tPE (A), TPA-3TPP (B) and Cz-3TPP (C), respectively. Device configurations for EL (A) and EL (C): ITO/MoO3/NPB (50 nm)/MCP (10
8
nm)/Cz-3tPE or TPA-3TPP (15 nm )/TPBi (35 nm)/LiF/Al; Device configurations for EL (B), EL (D)
and EL (E): ITO/MoO3/Cz-3tPE or TPA-3TPP or Cz-3TPP (75 nm)/TPBi (35 nm )/LiF/Al; Device
configuration for EL (F): ITO/MoO3/Cz-3TPP (75 nm)/TmPyPB (35 nm )/LiF/Al.
Figure S9 The chemical structures, maximum absorption wavelengths (λabs), EL emission peaks
(λEL), external quantum efficiencies (EQE) of TPA-3TPP, TTPECaP, Cz-3tPE, Cz-3TPP and the
corresponding different λabs and λEL effects (Note: Cz-3tPE, Cz-3TPP and TPA-3TPP were
reported in this paper, and TPA3HTPE was reported in reference 2 ).
350 400 450 500 550 600
0
500
1000
1500
2000
2500
PL
In
ten
sit
y (
au
)
Wavelength (nm)
0
20
40
60
80
99
fn (vol%)
(A)
350 400 450 500 550 600
0
2000
4000
6000
8000
10000
PL
In
ten
sit
y (
au
)
Wavelength (nm)
0
20
40
60
80
99
fn (vol%)
(B)
350 400 450 500 550
0
3000
6000
9000
PL
In
ten
sit
y (
au
)
Wavelength (nm)
0
20
40
60
80
99
fn (vol%)
(C)
Figure S10 PL spectra in THF/n-hexane mixtures with different n-hexane fractions: (A) Cz-3tPE,
concentration ≈ 10 µM; excitation wavelength 330 nm; (B) TPA-3TPP, concentration ≈ 10 µM;
excitation wavelength 340 nm; (C) Cz-3TPP, concentration ≈ 10 µM; excitation wavelength 310
nm.
9
Figure S11 Calculated molecular orbital amplitude plots of HOMO and LUMO levels and
optimized molecular structures of Cz-3tPE, TPA-3TPP and Cz-3TPP.
-0.4 0.1 0.6 1.1 1.6
0.00000
-0.00001
-0.00002
Cu
rre
nt
(A)
Potential vs SCE (V)
Cz-3TPP
Cz-3tPE
TPA-3TPP
Figure S12 The cyclic voltammograms of Cz-3tPE, TPA-3TPP and Cz-3TPP recorded in
dichloromethane.
0.1 1 10 100 1000
0.01
0.1
1
10
Po
wer
Eff
icie
ncy (
lm/W
)
Current Density (mA/cm2)
device A device B
device C device D
device E device F
Figure S13 The changes in power efficiency with the current density. Device configurations for
A and C: ITO/MoO3/NPB (50 nm)/MCP (10 nm)/Cz-3tPE or TPA-3TPP (15 nm )/TPBi (35
nm)/LiF/Al; Device configurations for B, D and E: ITO/MoO3/Cz-3tPE or TPA-3TPP or Cz-3TPP (75
nm)/TPBi (35 nm )/LiF/Al; Device configuration for F: ITO/MoO3/Cz-3TPP (75 nm)/TmPyPB (35
nm )/LiF/Al.
10
800 900 1000 1100 1200 1300 1400
0
1000
2000
3000
4000
5000
6000
Inte
ns
ity
M/Z
Cz-3tPE
1005.0559
Figure S14 MALDI-TOF of Cz-3tPE.
800 900 1000 1100 1200 1300 1400
0
2000
4000
6000
8000
10000
12000
14000
Inte
ns
ity
M/Z
TPA-3TPP1157.1414
Figure S15 MALDI-TOF of TPA-3TPP.
11
800 900 1000 1100 1200 1300 1400
0
10000
20000
30000
40000
50000
60000
Inte
nsit
y
M/Z
Cz-3TPP 1155.2246
Figure S16 MALDI-TOF of Cz-3TPP.
Reference
1 V. Vergadou, G. Pistolis, A. Michaelides, G. Varvounis, M. Siskos, N. Boukos and S. Skoulika,
Cryst. Growth Des., 2006, 6, 2486.
2 G. Chen, W. Li, T. Zhou, Q. Peng, D. Zhai, H. Li, W. Yuan, Y. Zhang and B. Z. Tang, Adv. Mater., 2015, 27, 4496.
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