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S1
Supporting information
Polymorphism of derivatives of tert-butyl substituted acridan and
perfluorobiphenyl as sky-blue OLED emitters exhibiting aggregation
b)Figure S2. The thermal characterization of synthesized compounds: TGA (a) and DSC (b) curves
Figure S3. Theoretical calculations for synthesized compounds
-3.0 -2.5 -2.0 -1.5 0.0 0.5 1.0
-2.0x10-5
-1.0x10-5
0.0
1.0x10-5
2.0x10-5
3.0x10-5
I, m
kA
E, V
PFBP-1a PFBP-1b PFBP-2a PFBP-2b
5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.80.0
0.2
0.4
0.6
0.8
1.0
1.2
x5
PFBF-1a PFBF-1b PFBF-2a PFBF-2b
Photon energy (eV)
i0.5 (a
.u.)
x20
(a) (b)Figure S4. CV and photoelectrical measurements of synthesized compounds
S14
300 350 400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d In
tens
ity, a
.u.
Wavelength, nm
PFBP-1a PFBP-1b PFBP-2a PFBP-2b
THF
350 400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d In
tens
ity, a
.u.
Wavelength, nm
PFBP-1a PFBP-1b PFBP-2a PFBP-2b
Toluene
200 250 300 350 400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d In
tens
ity, a
.u.
Wavelength, nm
/ PFBP-1a / PFBP-1b / PFBP-2a / PFBP-2b
Film 1 / Film 2
Figure S5. UV and photoluminescence spectra of synthesized compounds in different media
S15
Figure S6. Non-treated (the left side) and mechanically + temperature (<80 °C) treated (the right side) film based on the compound PFBP-2a under UV excitation. The film was fabricated by the spin-
coating.
400 500 600 700 8000.0
0.2
0.4
0.6
0.8
1.0
400 500 600 700 8000.0
0.2
0.4
0.6
0.8
1.0
400 500 600 700 8000.0
0.2
0.4
0.6
0.8
1.0
400 500 600 700 8000.0
0.2
0.4
0.6
0.8
1.0
Nor
mal
ized
Inte
nsity
, A.U
.
, nm
PL PH
PFBP-1aN
orm
aliz
ed In
tens
ity, A
.U.
Nor
mal
ized
Inte
nsity
, A.U
.
, nm
PL PH
PFBP-1b
Nor
mal
ized
Inte
nsity
, A.U
.
, nm
PL PH
PFBP-2a
, nm
PL PH
PFBP-2b
Figure S7. Photoluminescence and phosphorescence spectra and 77K for obtained compounds
S16
400 450 500 550 600 650 7000
5000
10000
15000
20000
25000
30000
35000
40000
45000
Inte
nsity
, a.u
.
Wavelength, nm
waterfraction, %
0 10 30 50 60 80 90 93 99
PFBP-1a, ex=350nm
400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0 PFBP-1a, ex=350nm
Wavelength, nm
Nor
mal
ized
inte
nsity
, a.u
.
0 10 30 50 60 80 90 93 99
waterfraction, %
0 20 40 60 80 1000
10000
20000
30000
40000
50000
PFBP-1a, ex=350nm
Inten
sity,
%
Volume fraction of water, %
400 450 500 550 600 650 7000
5000
10000
15000
20000
25000
30000
35000
40000
waterfraction, %
0 10 30 50 80 90 93 99
PFBP-1b, ex=350nm
Inte
nsity
, a.u
.
Wavelength, nm400 450 500 550 600 650 700
0.0
0.2
0.4
0.6
0.8
1.0 PFBP-1b, ex=350nm waterfraction, %
0 10 30 50 80 90 93 99
Norm
aliz
ed in
tens
ity, a
.u.
Wavelength, nm
0 20 40 60 80 100
5000
10000
15000
20000
25000
30000
35000
40000
PFBP-1b, ex=350nm
Inte
nsity
, a.u
.
Volume fraction of water, %
S17
400 450 500 550 600 650 7000
5000
10000
15000
20000
25000
30000waterfraction, %
99 90 80 60 50 30 10 0
PFBP-2a, ex=350nm
Inte
nsity
, a.u
.
Wavelength, nm 400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
Norm
alize
d in
tensit
y, a.
u.
Wavelength, nm
PFBP-1a, ex=350nm 99 90 80 60 50 30 10 0
waterfraction, %
0 20 40 60 80 100
0
5000
10000
15000
20000
25000
30000
PFBP-2a, ex=350nm
Inten
sity,
a.u.
Volume fraction of water, %
400 450 500 550 600 650 7000
10000
20000
30000
40000
50000
99 90 93 80 60 50 30 10 0
PFBP-2b, ex=350nm
Inte
nsity
, a.u
.
Wavelength, nm
waterfraction, %
400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0 99 90 93 80 60 50 30 10 0
Norm
alize
d in
tensit
y, a.
u.
waterfraction, %
PFBP-2b, ex=350nm
Wavelength, nm
0 20 40 60 80 100
0
10000
20000
30000
40000
50000
PFBP-2b, ex=350nm
Inten
sity,
a.u.
Volume fraction of water, %
Figure S8. PL spectra of PFBPs and PL intensity of the dispersions obtained derivatives in water–THF mixtures with the different water fractions (fw, vol%)
S18
1000 2000 3000 4000 50001
10
100
1000
PFBP-1b/nondoped film
77K 140K 180K 220K 260K 300K
Ex: 374 nmEm: 430nm
Coun
ts
Time, ns2000 4000
1
10
100
1000
PFBP-2a/nondoped film/Crystalline
77K 140K 180K 220K 260K 300K
Ex: 374 nmEm: 460nm
Coun
ts
Time, ns
TADF
2000 4000
1
10
100
1000
PFBP-2a/nondoped film/Amorphous
77K 140K 180K 220K 260K 300K
Ex: 374 nmEm: 490nm
Coun
ts
Time, ns2000 4000
1
10
100
1000
PFBP-2b/nondoped film
77K 140K 180K 220K 260K 300K
Ex: 374 nmEm: 490nm
Coun
ts
Time, nsa)
1000 2000 3000 4000 5000
10
100
1000
10000
Coun
ts
Time, ns
crystalA crystalB
b)
Figure S9. PL decay curves of vacuum deposited layers of PFBPs at different temperatures (a) and PL decay curves of crystalline samples of PFBP-2a_crystaA and PFBP-2a_crystaB (b).
S19
400 450 500 550
0.0
0.2
0.4
0.6
0.8
1.0 PL at 77K Ph at 77K
PL in
tensit
y, a.
u.
Wavelength, nm
PFBP-1aS1= 3.29 eVT1= 3.13 eVEST= 0.16 eV
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0 PL at 77K Ph at 77K
PL in
tensit
y, a.
u.
Wavelength, nm
PFBP-1bS1= 2.92 eVT1= 2.86 eVEST= 0.06 eV
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0PFBP-2a:Crystalline
PL at 77K Ph at 77K
PFBP-2a:Amorphous PL at 77K Ph at 77K
PL in
tensit
y, a.
u.
Wavelength, nm
PFBP-2a:CrystallineS1= 2.97 eVT1= 2.96 eVEST= 0.01 eV
PFBP-2a:AmorphousS1= 2.90 eVT1= 2.87 eVEST= 0.03 eV
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0 PL at 77K Ph at 77K
PL in
tensit
y, a.
u.
Wavelength, nm
PFBP-2bS1= 2.86 eVT1= 2.80 eVEST= 0.06 eV
Figure S10. PL and Ph spectra of PFBPs films (Ph recorded after 100 μs after excitation).
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0
PFBP-1b/nondoped film
77K 140K 180K 220K 260K 300K
PL in
tensit
y, a.
u.
Wavelength, nm400 450 500 550 600
0.0
0.2
0.4
0.6
0.8
1.0Amor.
PFBP-2a/nondoped film
Cryst. 77K 140K 180K 220K 260K 300K
PL in
tens
ity, a
.u.
Wavelength, nm
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0
PFBP-2b/nondoped film
77K 140K 180K 220K 260K 300K
PL in
tensit
y, a.
u.
Wavelength, nmFigure S11. PL of PFBPs films recorded at different temperatures under nitrogen atmosphere
S20
400 450 500 550 600 650 700 7500.0
4.0x105
8.0x105
400 450 500 550 600 650 700 7500.0
2.0x105
4.0x105400 450 500 550 600 650 700 750
0.0
4.0x105
8.0x105400 450 500 550 600 650 700 750
0.0
8.0x105
1.6x106
PFBP-2bId/In-d=1.37
PL in
tensit
y, p
oint
s
Wavelength, nm
PFBP-2aId/In-d=1.36
PFBP-1bId/In-d=1.8
PFBP-1aId/In-d=2.07 degassed non-degassed
500 1000 1500 20001
10100
100010000
500 1000 1500 20001
10100
100010000
500 1000 1500 20001
10100
100010000
500 1000 1500 20001
10100
100010000 non-degassed
degassed
PFBP-2b
Coun
ts
Time, ns
PFBP-2a
PFBP-1b
PFBP-1a
(a) (b)Figure S12. PL spectra (a) and PL decay curves (b) of the solutions of studied derivatives in non-
deoxygenated and deoxygenated toluene.
400 450 500 550
0.0
0.2
0.4
0.6
0.8
1.0 non delayed 5s delayed
Inten
sity,
a.u.
Wavelength, nm
PFBP-1a at 300K
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0 non delayed 5s delayed
Inte
nsity
, a.u
.
Wavelength, nm
PFBP-1b at 300K
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0 non delayed 5s delayed non delayed 5s delayed
Wavelength, nm
PFBP-2a at 300K
Inten
sity,
a.u.
400 450 500 550 6000.0
0.2
0.4
0.6
0.8
1.0
Wavelength, nm
PFBP-2b at 300K non delayed 5s delayed
Inte
nsity
, a.u
.
Figure S13. Prompt and delayed PL of PFBPs films recorded at 300 K.
Table S1. Hydrogen-bond geometry for compounds PFBP-1a, PFBP-1b, PFBP-2a_crystalA and PFBP-2a_crystalB (Å, º)
Figure S14. (Left) The molecular arrangement in the PFBP-1a compound viewed along [100]. Orange/cyan and blue dashed lines represent C‒H∙∙∙F hydrogen bonds and C‒F∙∙∙π interactions, respectively. (Right) A
cluster of four molecules, forming by two unique C‒H∙∙∙F interactions.
Figure S15. The π-π interactions between neighbouring DMAC-PFBP molecules in the PFBP-1a compound.
S22
Figure S16. The asymmetric unit of PFBP-1b compound, showing the atom-numbering scheme for molecule A. Displacement ellipsoids are drawn at the 50 % probability level.
Figure S17. The part of crystal packing of PFBP-1b viewed along [100]. The colorful thick bonds represent four independent DMAC-PFBP molecules. Cyan, violet and blue dashed lines represent π-π interactions.
S23
Figure S18. Hirshfeld surface of two neighbouring molecules in compound PFBP-1a.
Figure S19. Hirshfeld surface of two neighbouring molecules in compound PFBP-1b.
S24
Figure S20. a) Two-dimensional fingerprint plots of DMAC-PFBP molecules and b) fingerprint plots of contribution of H…F contacts in compound PFBP-1a. c) Two-dimensional fingerprint plots of DMAC-
PFBP molecules and d) fingerprint plots of contribution of H…F contacts in compound PFBP-1b.
Figure S21. a) Two-dimensional fingerprint plots of DMAC-PFBP molecules and b) fingerprint plots of contribution of H…F contacts in compound PFBP-2a_crystalA and c) Two-dimensional fingerprint plots of
DMAC-PFBP molecules and d) fingerprint plots of contribution of H…F contacts in compound PFBP-2a_crystaB.
Figure S23. PL spectra (a) and PL decay curves (b) of doped films.
Table S2. PL characteristics of doped films of PFBPs
N/N PFBP-1a PFBP-1b PFBP-2a PFBP-2b
λmax(mCP), nm 455 472 477 490
(mCP) 0.15 0.45 0.15 0.22
λmax(TCz1), nm 501 497 498 501
TCz1 0.37 0.47 0.47 0.73
Owing to donor-acceptor structure of the compounds, bipolar charge carrier transport was
expected. To study the impact of donor substituents on charge-transporting properties of the
vacuum-deposited films, time-of-flight (ToF) measurements we performed generating holes or
electrons on the ITO/film interfaces by light excitation through the ITO electrode using a pulsed
laser (λ = 355 nm) and different polarity of applied voltages (plus on ITO for holes, minus for
electrons). Thus, the photogenerated either holes or electrons were transported through the layer
from ITO electrode to the opposite Al electrode under different external electric fields.
Very dispersive charge transport was observed by TOF experiment. It was very difficult to
take the transit times (ttr) for the studied samples at different applied electric fields (voltages (U))
for holes and electrons from the corresponding photocurrent transients in log-log scales for the all
tested samples. This resulted in considerable errors. (Figure S24). We tried to define the ttr for
PFBP-2b as it is shown in Figure S4. Hole mobility (µh) of ca. 1.0×10-4 cm2V-1s-1 at electric field of
6×105 Vcm-1 for PFBP-2b was estimated using equation µh(µe)=d2/(U×ttr) (Figure S25).
S27
10-5 10-4 10-3
10-3
10-2
10-1
100
101
PFBP 1bholesd=2.8 m
150V 130V 110V 90V 70V 50V 30V
Time, s
Curre
nt d
ensit
y, m
A/cm
2
10-5 10-4 10-3
10-3
10-2
10-1
100
101
PFBP 1belectronsd=2.8 m
-150V -130V -110V -90V -70V -50V -30V
Time, s
Curre
nt d
ensit
y, m
A/cm
2
10-6 10-5 10-4
10-3
10-2
10-1
100
101
PFBP 2aholesd=2.65 m
150V 130V 110V 90V
Time, s
Curre
nt d
ensit
y, m
A/cm
2
10-6 10-5
10-1
100
101
PFBP 2aelectronsd=2.65 m
-150V -130V -70V -90V
Time, s
Curre
nt d
ensit
y, m
A/cm
2
10-6 10-5 10-4
10-1
100
101
102
PFBP 2belectronsd=1.15 m
-80V -70V -60V -50V
Time, s
Curre
nt d
ensit
y, m
A/cm
2
10-6 10-5 10-4
10-1
100
101
PFBP 2bholesd=1.15 m
80V 70V 60V 50V
Time, s
Curre
nt d
ensit
y, m
A/cm
2
Figure S24. Electron and hole time-of-flight current transients for the studied samples PFBP-1b, PFBP-2a, and PFBP-2b.
S28
400 600 800 100010-5
10-4
10-3
PFBP 2b:holes
Mob
ility
(cm
2 /Vs)
E1/2 (V1/2/cm1/2)Figure S25. Hole mobility versus electric fields for the PFBP-2b.
400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0DeviceA
5V 6V 7V 8V 9V 10V
Norm
alize
d in
tens
ity, a
.u.
Wavelength, nm400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0 Device B 5V 6V 7V 8V 9V 10V
Nor
mal
ized
inte
nsity
, a.u
.
Wavelength, nm
400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0Device C
9V 11V 13V 15V
Norm
alize
d in
tens
ity, a
.u.
Wavelength, nm400 450 500 550 600 650
0.0
0.2
0.4
0.6
0.8
1.0 Device D 4V 5V 6V 7V 8V 9V 10V
Norm
alize
d in
tens
ity, a
.u.
Wavelength, nm
Figure S26. EL spectra of the studied devices at different voltages.
S29
10 1000.1
1
10
Device A Device B Device C Device D
Current density, mA cm2
Curre
nt e
fficie
ncy,
cd/
A
10 100
0.1
1
10
Device A Device B Device C Device D
Current density, mA cm2
Powe
r effi
cienc
y, lm
/W
Figure S27. Current and power efficiencies of the studied devices.
Supporting information
1. Experimental details
1.1 Instrumentation
(before Powder X-ray diffraction)
The intensity data for compounds PFBP-1a, PFBP-1b and PFBP-2b_crystalB were collected at 100 K on an Oxford Diffraction Xcalibur diffractometer equipped with graphite-monochromated Mo Ka radiation (λ = 0.71073 Å). The instrument was equipped with an Oxford Cryosystems 800 series cryocooler. Data collection and reduction were made using CrysAlisCCD and CrysAlis RED programs (Rigaku, 2015). The crystallographic measurement for compound PFBP-2b_crystalA was performed at 295 K on a XtaLAB Mini (ROW) diffractometer. A numerical absorption correction based on the shape of the crystals was performed. The crystal structures were solved by direct methods and all non-hydrogen atoms were refined anisotropically with full-matrix least-squares techniques on F2 by SHELXL with the following graphical user interfaces of OLEX2 (Sheldrick, 2015; Dolomanov et al., 2009). For all structures H-atom parameters were constrained. In compound PFBP-2a_crystalA one of two tert-butyl groups is disordered over two positions with site occupancies of 0.645(15) and 0.355(15). In order to avoid the distortion of the disordered tert-butyl group, SHELXL (SADI, DELU and SIMU) instructions were used. In compound PFBP-2a_crystalB both tert-butyl functional groups are disordered over two sets of sites, with occupancy ratio of 0.538(5):0.462(5) and 0.937(3):0.063(3). The second disordered tert-butyl group was refined with distance and angles restraints, and the minor component atoms C33-C35 were refined isotropically.
Details on the single crystal X-ray data collection, reduction and structure parameters for all compounds are given in Tables S2-S5.
(To the end of the Supporting information)
Tables S2. Experimental details for compound PFBP-1a
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Absolute structure parameter
0.3 (3)
Computer programs: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015), ShelXT (Sheldrick, 2015), SHELXL (Sheldrick, 2015), Olex2 (Dolomanov et al., 2009).
Tables S4. Experimental details for compound PFBP-2b_crystalA
Crystal data
Chemical formula C35H30F9N
Mr 635.60
Crystal system, space group
Monoclinic, P21/c
Temperature (K) 293
a, b, c (Å) 10.870 (4), 24.126 (6), 12.550 (4)
β (°) 105.57 (3)
V (Å3) 3170.5 (18)
Z 4
Radiation type Mo Kα
µ (mm−1) 0.11
Crystal size (mm) 0.38 × 0.35 × 0.05
Data collection
Diffractometer XtaLAB Mini (ROW)
Absorption correction
Analytical CrysAlis PRO 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
Tmin, Tmax 0.968, 0.994
No. of measured, independent andobserved [I > 2σ(I)] reflections
Computer programs: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015), ShelXT (Sheldrick, 2015), SHELXL (Sheldrick, 2015), Olex2 (Dolomanov et al., 2009).
Rigaku Oxford Diffraction, CrysAlisPro Software System, Version 1.171, Rigaku Corporation, Oxford, UK, 2015.Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8.Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.