Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.

This journal is © The Royal Society of Chemistry 2018

Supporting information

Polymorphism of derivatives of tert-butyl substituted acridan and

perfluorobiphenyl as sky-blue OLED emitters exhibiting aggregation

induced thermally activated delayed fluorescence

Iryna Hladka1, Dmytro Volyniuk1, Oleksandr Bezvikonnyi1, Vasyl Kinzhybalo2, Tamara Bednarchuk2, Yan

Danyliv1, Roman Lytvyn1,3, Algirdas Lazauskas4, Juozas V. Grazulevicius1,*

1Department of Polymer Chemistry and Technology, Kaunas University of Technology, Radvilenu

pl. 19, LT-50254, Kaunas, Lithuania; e-mail: [email protected].

2Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-

422 Wrocław, Poland

3Department of Organic Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodia St.

6, 79005 Lviv, Ukraine.

4Institute of Materials Science, Kaunas University of Technology, K. Baršausko St. 59, LT51423

Kaunas, Lithuania

* Corresponding author. E-mail address: [email protected] (Juozas Vidas Grazulevicius)

S1
Instrumentation

1H, 13C and 19F nuclear magnetic resonance (NMR) spectra of the solutions in deuterated chloroform

(CDCl3) were obtained using Bruker DRX 400 spectrometer (400 MHz (1H), 100 MHz (13C), 375 MHz

(19F)). Chemical shifts (δ) are reported in ppm referenced to tetramethylsilane (TMS). Mass spectra were

obtained by the electrospray ionization mass spectrometry (ESI-MS) method on Esquire-LC 00084 mass

spectrometer. Elemental analysis data were obtained on a EuroEA Elemental Analyser. For X-ray

crystallography analysis diffraction data were collected on a Bruker-Nonius KappaCCD single

diffractometer using graphite monochromated Mo-Kα radiation (λ = 0.71073 Å). The crystal structure was

solved by direct method [SIR-97] and refined by full-matrix least squares [SHELXL-97].

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.

S2
 Details on the single crystal X-ray data collection, reduction and structure parameters for all

compounds are given in Tables S2-S5.

The crystallographic nature of PFBP-1a, PFBP-1b, PFBP-2a and PFBP-2b powders was

determined using D8 Discover X-ray diffractometer (Bruker AXS GmbH) with Cu Kα (λ= 1.54 Å) X-ray

source. Parallel beam geometry with 60 mm Göbel mirror (i.e. X-ray mirror on a high precision parabolic

surface) was used. This configuration enables transforming the divergent incident X-ray beam from a line

focus of the X-ray tube into a parallel beam that is free of Kβ radiation. Primary side also had a Soller slit

with an axial divergence of 2.5 º and divergence slit of 1.0 mm. The secondary side had a LYNXEYE (0D

mode) detector with an opening angle of 2.160 º and slit opening of 6.0 mm. X-ray generator voltage and

current was 40.0 kV and 40 mA, respectively. Coupled 2θ/θ scans were performed in the range of 4.0-135.0 º

with a step size of 0.065 º, time per step of 19.2 s and auto-repeat function enabled. Processing of the

resultant diffractograms was performed with DIFFRAC.EVA software. For the X-ray diffraction

measurements at grazing incidence (XRDGI) the divergence slit of 0.6 mm was used on the primary side.

The XRDGI scans for thin films of PFBP-1a, PFBP-1a:TCz1, PFBP-1b, PFBP-1b:TCz1, PFBP-2a,

PFBP-2a:TCz1, PFBP-2b and PFBP-2b:TCz1 were performed at incidence angle of 1.50 º, in the range of

4.-134.0 º with a step size of 0.065 º, time per step of 19.2 s and auto-repeat function enabled.

Macromolecular orientation texture analysis of PFBP-2a (sample prepared using drop casting method) was

performed to describe the variation in the pole density (i.e. determined by the intensity of diffracted X-ray

beam) with pole orientation for crystalline component reflection at 7.21º in 2θ. Data were collected using a

standard mode (unlocked coupled) with 5º of δ measured for full circle 0-360 incr. 5º in Phi (φ) and 0-10

incr. 10º in Psi (ψ) range. Measured data were corrected for background scattering and the defocusing of the

beam using Diffracplus MULTEX 3 software package.

Surface morphology of PFBP-1a, PFBP-1a:TCz1, PFBP-1b, PFBP-1b:TCz1, PFBP-2a, PFBP-

2a:TCz1, PFBP-2b and PFBP-2b:TCz1 thin films was investigated using atomic force microscopy (AFM).

AFM experiments were carried out in air at room temperature using a NanoWizardIII atomic force

microscope (JPK Instruments), while data was analysed using SurfaceXplorer and JPKSPM Data Processing

software. The AFM images were collected using a V-shaped silicon cantilever (spring constant of 3 N/m, tip

curvature radius of 10.0 nm and the cone angle of 20º) operating in a contact mode.

S3
 Theoretical calculations of the PFBP derivatives were performed using density-functional theory via

Spartan’14 software package. UV/Vis spectra of 10-4 M solutions of the compounds were recorded in quartz

cells using Perkin Elmer Lambda 35 spectrometer. Photoluminescence (PL) spectra of 10-5 M solutions of

the compounds were recorded using Edinburgh Instruments' FLS980 Fluorescence Spectrometer. Thin solid

films for recording UV/Vis and PL spectra were prepared by spin-coating technique utilizing SPS-Europe

Spin150 Spin processor using 2.5 mg/ml solutions of the compounds in THF on the pre-cleaned quartz

substrates. Photoluminescence quantum yields of the solutions and oh the solid films were determined using

the integrated sphere (Edinburgh Instruments) coupled to the FLS980 spectrometer, calibrated with two

standards: quinine sulphate in 0.1 H2SO4 and rhodamine 6G in ethanol).1

Differential scanning calorimetry (DSC) measurements were done with a TA Instruments “DSC

Q100” calorimeter. The samples were heated at a scan rate of 10 °C/min under nitrogen atmosphere.

Thermogravimetric analysis (TGA) was performed on a “Mettler TGA/SDTA851e/LF/1100” at a heating

rate of 20 °C/min under nitrogen atmosphere. Electrochemical measurements were done using μAutolab

Type III (EcoChemie, Netherlands) potentiostat, glassy carbon electrode (diam. 2 mm), platinum coil and

silver wire as working, auxiliary and reference electrode, respectively and the scan rate of 2.5 mV/s with

concentration of compounds 1.0×10-4 mol/dm3. Potentials are referenced with respect to ferrocene (Fc),

which was used as the internal standard. Cyclic voltammetry (CV) experiments were conducted in the dry

solvent solution containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the electrolyte at

room temperature under nitrogen atmosphere. For all synthesized compounds, measurements were done in

DMF solution. Deaeration of the solution was achieved by a nitrogen bubbling for about 10 min before

measurement.

Photoelectron emission spectra for vacuum deposited layers of the studied compounds were

recorded to obtain the solid-state ionization potentials (IpPE) of the compounds as reported previously.2,3

Fluorine doped tin oxide (FTO) coated glass slides were used as substrates for the preparation of samples

for photoelectron emission spectrometry. The layers of the compounds were fabricated by thermal vacuum

evaporation onto the substrates. Photoelectron emission spectra were recorded in air using ASBN-D130-

CM deep UV deuterium light source, CM110 1/8m monochromator and 6517B Keithley electrometer.

Device fabrications

S4
 The following devices were fabricated and characterized as it was described earlier.4

Device A: ITO/MoO3(4nm)/NPB(45nm)/ PFBP-1b:mCP(10-90%,30nm)/TPBi(45nm)/Ca/Al

Device B: ITO/MoO3(4nm)/NPB(70nm)/ PFBP-2a:TCz1(15-85%,20nm)/TPBi(30nm)/Ca/Al

Device C: ITO/MoO3(4nm)/NPB(45nm)/ PFBP-2b (30nm)/TPBi(50nm)/Ca/Al

Device D: ITO/MoO3(4nm)/NPB(45nm)/ PFBP-2b:TCz1(15-85%,30nm)/TPBi(45nm)/Ca/Al

Materials

The starting compounds i.e. decafluorobiphenyl and potassium hydroxide (KOH) were purchased

from Sigma-Aldrich; 9,9-dimethyl-9,10-dihydro-acridine and 2,7-di-tert-butyl-9,9-dimethyl-9,10-dihydro-

acridine were obtained from Center for physical sciences and technology (Vilnius) and used as received.
7.57
7.57
7.55
7.55
7.16
7.16
7.14
7.14
7.11
7.11
7.09
6.42
6.42
6.40
6.40

1.73
2.02

2.12
2.04

2.00

6.75

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

S5
 0
140
138.34

-10
135
131.45

-20
130
126.99
125.61

125

-30
122.46

120

-40
115
112.88

-50
110

-60
105

-70
100

-80
95

-90
90
-136.27
-136.28
-136.29
-136.30
85

-100
-136.31
-136.33
-136.36
80

-110
-136.39
-136.39
-136.41
75

-136.42

-120
-136.43
-141.74
-141.76
70

-141.76

-130
-141.79
1.98 -141.82
65

2.08 -141.84
2.23 -141.85

-140
-141.86
60

1.00 -149.36

-150
-149.36
-149.37
55

-159.98
-159.99
2.28
-160.01

-160
-160.04
50

-160.05
-160.07

-170
-160.08
45

-160.10
-160.12
-160.13

-180
40

36.15
35

-190
30.52
30

-200
25

-210

S6
 8.0

150
7.59

145
7.59
4.09
7.57

7.5
7.57

140
138.38
7.19
4.10
7.17

135
4.17
7.17
131.50
7.14

7.0
7.13

130
7.12
127.04
7.11
125.63

125
7.10
122.50 6.47
4.00

6.5
6.45
6.45

120
115
112.92

6.0

110
105
5.5

100
95
5.0

90
85
4.5

80
75
4.0

70
3.5

65
60
3.0

55
50
2.5

45
40
2.0

36.18

35
12.19 1.76
30.53

30
1.5

25
20
1.0

15
0.5

S7
 -30
7.56
1.00
7.56

7.17

-40
7.17
1.00
7.15
7.14

7.8 7.6 7.4 7.2 7.0

-50

6.6
-60
1.00 6.34
6.32

6.2
-70
-80

5.8
-90

5.4
-100

5.0
-110

4.6
-120

4.2
-135.82
-135.84
-130

-135.85
-135.87

3.8
0.98
-135.89
-141.62
-140

1.00 -141.65
-141.68
-141.71

3.4
-150

3.0
-160

2.6
-170

2.2
-180

1.8
3.05 1.76
-190

1.4
9.11 1.36
-200

S8
 150

-30
144.79

145

-35
140

-40
136.11

135

-45
130.75

130

-50
-55
125
123.71
122.46

-60
120

-65
115
112.23

-70
110

-75
105

-80
-85
100

-90
95
90

-95 -100
85
80

-110
75

-120
70

-136.69
-136.71
65

-136.74
-136.77

-130
-136.85
60

-136.88
2.02 -136.91
2.03 -136.93
55

-141.58

-140
2.09 -141.61
-141.64
-141.67
50

-149.49
1.00 -149.55

-150
-149.61
45

-160.07
-160.09
-160.10
40

-160.14
2.06
-160.16

-160
-160.19 36.55
35

-160.21 34.36
-160.22 31.50
30.79
30

-170
25

S9
 150
144.81

145
8.0

140
7.58
136.17 1.98 7.58

7.5

135
7.20
130.78 7.19
1.98
7.18

130
7.17

7.0

125
123.75
122.46

6.5

120
6.39
2.00 6.37

115
112.29

6.0

110
5.5

105
100
5.0

95
4.5

90
85
4.0

80
3.5

75
70
3.0

65
2.5

60
55
2.0

5.93 1.78

50
1.5

45
18.21 1.37

40
1.0

36.58

35
34.38
31.52
30.78
0.5

30
25

S10
 -136.25
-136.27
-136.28
-136.30
-136.31
-141.55
-141.58
-141.61
-141.64
4.00

4.17
-40 -50 -60 -70 -80 -90 -100 -110 -120 -130 -140 -150 -160 -170 -180 -190
f1 (ppm)

Figure S1. 1H, 13C and 19F NMR spectra of PFBPs recorded in CDCl3.

100 PFBP-1a
PFBP-1b
PFBP-2a
80 PFBP-2b

60
Weight, %

40

20

200 400 600 800


Temperature, C
a)

S11
 PFBP-1a

cooling

endo/exo
2nd heating
120 °C

1st heating

T m.p. = 189 °C

20 40 60 80 100 120 140 160 180 200

Temperature, (°C)

PFBP-1b

2nd heating
T g= 98 °C 157 °C cooling
endo/exo

1st heating

T m.p. = 217 °C

20 40 60 80 100 120 140 160 180 200 220 240

Temperature, (°C)

PFBP-2b 288 °C

2nd heating
endo/exo

cooling

1st heating

T m.p. = 310 °C

20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
Temperature, (°C)

S12
 b)
Figure S2. The thermal characterization of synthesized compounds: TGA (a) and DSC (b) curves

Figure S3. Theoretical calculations for synthesized compounds

1.2
3.0x10-5 PFBF-1a
PFBF-1b
1.0 PFBF-2a
2.0x10-5 PFBF-2b
0.8
i0.5(a.u.)

1.0x10-5
x5
0.6
I, mkA

0.0

0.4
-1.0x10-5
PFBP-1a
PFBP-1b 0.2 x20
-2.0x10-5 PFBP-2a
PFBP-2b
0.0
-3.0 -2.5 -2.0 -1.5 0.0 0.5 1.0 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8
E, V Photon energy (eV)
(a) (b)
Figure S4. CV and photoelectrical measurements of synthesized compounds

S13
 1.0

PFBP-1a
0.8 PFBP-1b
PFBP-2a

Normalized Intensity, a.u.

PFBP-2b
THF

0.6

0.4

0.2

0.0
300 350 400 450 500 550 600 650 700
Wavelength, nm
1.0
PFBP-1a
PFBP-1b
PFBP-2a
PFBP-2b
0.8 Toluene
Normalized Intensity, a.u.

0.6

0.4

0.2

0.0
350 400 450 500 550 600 650 700
Wavelength, nm
1.0
/ PFBP-1a
/ PFBP-1b
/ PFBP-2a
/ PFBP-2b
0.8 Film 1 / Film 2
Normalized Intensity, a.u.

0.6

0.4

0.2

0.0
200 250 300 350 400 450 500 550 600 650 700
Wavelength, nm
Figure S5. UV and photoluminescence spectra of synthesized compounds in different media

S14
 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.

1.0
PL 1.0 PL
PH PH
0.8 PFBP-1a PFBP-1b
Normalized Intensity, A.U.

0.8
Normalized Intensity, A.U.

0.6
0.6

0.4
0.4

0.2 0.2

0.0 0.0
400 500 600 700 800 400 500 600 700 800
, nm , nm

1.0 PL 1.0 PL
PH PH
PFBP-2a PFBP-2b
Normalized Intensity, A.U.

0.8 0.8
Normalized Intensity, A.U.

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
400 500 600 700 800 400 500 600 700 800
, nm , nm
Figure S7. Photoluminescence and phosphorescence spectra and 77K for obtained compounds

S15
 45000 water PFBP-1a, ex=350nm
PFBP-1a, ex=350nm 1.0
water 0
fraction, % 10
40000 0 fraction, %
30
10
35000 0.8 50

Normalized intensity, a.u.

30
50 60
30000
60 80
Intensity, a.u.

25000 80 0.6 90
90 93
20000 93 99
99 0.4
15000

10000
0.2
5000

0
400 450 500 550 600 650 700 0.0
400 450 500 550 600 650 700
Wavelength, nm Wavelength, nm

50000

40000 PFBP-1a, ex=350nm

30000
Intensity, %

20000

10000

0
0 20 40 60 80 100
Volume fraction of water, %

PFBP-1b, ex=350nm water

40000 PFBP-1b, ex=350nm 1.0 fraction, %
water 0
35000
fraction, % 10
0 0.8 30
Normalized intensity, a.u.

30000
10 50
25000
30 80
Intensity, a.u.

50 0.6 90
20000
80 93
90 99
15000 93 0.4
99
10000
0.2
5000

0 0.0
400 450 500 550 600 650 700 400 450 500 550 600 650 700
Wavelength, nm Wavelength, nm

40000

35000
PFBP-1b, ex=350nm
30000

25000
Intensity, a.u.

20000

15000

10000

5000

0 20 40 60 80 100
Volume fraction of water, %

S16
 30000
PFBP-2a, ex=350nm water PFBP-1a, ex=350nm water 99
1.0
fraction, % fraction, % 90
25000 99 80
90 60
80 0.8

Normalized intensity, a.u.

20000
50
60 30
50
Intensity, a.u.
10
30 0.6
15000 0
10
0
10000 0.4

5000 0.2

0 0.0
400 450 500 550 600 650 700 400 450 500 550 600 650 700
Wavelength, nm Wavelength, nm
30000

25000 PFBP-2a, ex=350nm

20000
Intensity, a.u.

15000

10000

5000

0 20 40 60 80 100
Volume fraction of water, %
50000
PFBP-2b, ex=350nm
PFBP-2b, ex=350nm water 99
99 1.0 fraction, %
water 90
40000 90
fraction, % 93
93 80
80 0.8 60
Normalized intensity, a.u.

60 50
30000
Intensity, a.u.

50 30
30 0.6 10
10 0
20000 0
0.4

10000
0.2

0 0.0
400 450 500 550 600 650 700 400 450 500 550 600 650 700
Wavelength, nm Wavelength, nm
50000
PFBP-2b, ex=350nm
40000

30000
Intensity, a.u.

20000

10000

0 20 40 60 80 100
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%)

S17
 Ex: 374 nm 77K Ex: 374 nm 77K
Em: 430nm 140K Em: 460nm 140K
1000 1000
180K 180K
220K 220K
PFBP-1b/nondoped film 260K 260K
300K 300K

Counts
Counts

100 100
TADF

PFBP-2a/nondoped film/Crystalline
10 10

1 1
1000 2000 3000 4000 5000 2000 4000

Time, ns Time, ns
Ex: 374 nm 77K
Ex: 374 nm 77K Em: 490nm 140K
1000 Em: 490nm 140K 1000
180K
180K 220K
220K PFBP-2b/nondoped film 260K
260K 300K
300K
Counts
Counts

100 100
PFBP-2a/nondoped film/Amorphous

10 10

1 1
2000 4000 2000 4000

Time, ns Time, ns
a)
10000
crystalA
crystalB

1000
Counts

100

10

1000 2000 3000 4000 5000

Time, ns

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).

S18
 1.0
PL at 77K 1.0
PL at 77K
Ph at 77K Ph at 77K

PL intensity, a.u.

PL intensity, a.u.
0.8 0.8

0.6
0.6

0.4
PFBP-1a 0.4 PFBP-1b
S1= 3.29 eV S1= 2.92 eV
T1= 3.13 eV T1= 2.86 eV
0.2
0.2 EST= 0.16 eV EST= 0.06 eV

0.0
0.0 400 450 500 550 600
400 450 500 550
Wavelength, nm Wavelength, nm
PFBP-2a:Crystalline
1.0 PL at 77K
PL at 77K 1.0
Ph at 77K
Ph at 77K
PFBP-2a:Amorphous

PL intensity, a.u.
PL intensity, a.u.

0.8 PL at 77K 0.8

Ph at 77K
0.6 0.6

0.4 0.4 PFBP-2b

S1= 2.86 eV
PFBP-2a:Crystalline PFBP-2a:Amorphous
S1= 2.97 eV S1= 2.90 eV T1= 2.80 eV
0.2 0.2
T1= 2.96 eV T1= 2.87 eV EST= 0.06 eV
EST= 0.01 eV EST= 0.03 eV
0.0 0.0
400 450 500 550 600 400 450 500 550 600

Wavelength, nm Wavelength, nm
Figure S10. PL and Ph spectra of PFBPs films (Ph recorded after 100 μs after excitation).

1.0 77K Amor. Cryst.

140K 1.0 77K
180K 140K
PL intensity, a.u.

0.8 220K 180K

PL intensity, a.u.

260K 0.8 220K

300K 260K
0.6 300K
0.6

0.4 0.4

0.2 PFBP-1b/nondoped film 0.2

PFBP-2a/nondoped film
0.0 0.0
400 450 500 550 600 400 450 500 550 600

Wavelength, nm Wavelength, nm
1.0 77K
140K
180K
PL intensity, a.u.

0.8 220K
260K
300K
0.6

0.4

0.2 PFBP-2b/nondoped film

0.0
400 450 500 550 600

Wavelength, nm
Figure S11. PL of PFBPs films recorded at different temperatures under nitrogen atmosphere

S19
 1.6x106 PFBP-1a degassed 10000 non-degassed
Id/In-d=2.07 1000 PFBP-1a
non-degassed 100 degassed
8.0x105
10
0.0 1

PL intensity, points
400 450 500 550 600 650 700 750 500 1000 1500 2000
Id/In-d=1.8 10000
8.0x105 PFBP-1b 1000 PFBP-1b
100
4.0x105

Counts
10
0.0 1
400 450 500 550 600 650 700 750 500 1000 1500 2000
10000
4.0x105 Id/In-d=1.36 PFBP-2a 1000 PFBP-2a
100
2.0x105 10
0.0 1
400 450 500 550 600 650 700 750 500 1000 1500 2000
10000 PFBP-2b
8.0x105 Id/In-d=1.37 PFBP-2b 1000
100
4.0x105 10
1
0.0
500 1000 1500 2000
400 450 500 550 600 650 700 750
Wavelength, nm Time, ns
(a) (b)
Figure S12. PL spectra (a) and PL decay curves (b) of the solutions of studied derivatives in non-
deoxygenated and deoxygenated toluene.

non delayed
1.0 PFBP-1a at 300K non delayed 1.0 PFBP-1b at 300K 5s delayed
5s delayed

0.8

Intensity, a.u.
0.8
Intensity, a.u.

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
400 450 500 550 400 450 500 550 600

Wavelength, nm Wavelength, nm

1.0 PFBP-2a at 300K non delayed

1.0 PFBP-2b at 300K
non delayed
5s delayed 5s delayed
non delayed
5s delayed
0.8
Intensity, a.u.

0.8
Intensity, a.u.

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
400 450 500 550 600 400 450 500 550 600

Wavelength, nm Wavelength, nm
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)
D‒H∙∙∙A D‒H (Å) H∙∙∙A (Å) D∙∙∙A (Å) D‒H∙∙∙A (°)
PFBP-1a
C3‒H3∙∙∙F19 0.95 2.52 3.371(2) 149
C5‒H5∙∙∙F28 0.95 2.40 3.284(2) 155
PFBP-1b
C5D‒H5D∙∙∙F25A 0.95 2.48 3.163(6) 129
C13D‒H13D∙∙∙F25C 0.95 2.35 3.273(7) 163
C33B‒H33B∙∙∙F22A 0.95 2.34 3.268(6) 165
PFBP-2a_crystalA
S20
 C39B‒H39B∙∙∙F21 0.96 2.60 3.54(3) 166
PFBP-2a_crystaB
C32‒H32B∙∙∙F22 0.98 2.53 3.298(3) 135
C40‒H40∙∙∙F19 0.98 2.35 3.265(4) 155

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.

S21
 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.

S22
Figure S18. Hirshfeld surface of two neighbouring molecules in compound PFBP-1a.

Figure S19. Hirshfeld surface of two neighbouring molecules in compound PFBP-1b.

S23
 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.

S24
 Glass substrate Z, nm

10.0
1

5.0

Y, μm
10.0
0
5.0
0 X, μm
PFBP-1a : TCz1
PFBP-1a
Z, nm Z, nm
10.0
10.0
24 24

18 5.0 18
5.0
12 12
Y, μm 10.0 6
10.0 6
5.0
5.0 X, μm
X, μm 0 0

PFBP-1b PFBP-1b : TCz1

Z, nm Z, nm
10.0 60 10.0
30
48

5.0 36 5.0 20

Y, μm 24
10
10.0 12 10.0
5.0 5.0
X, μm X, μm 0
0

Rougness parameters
Sample
Rq Rsk Rku Zmean
Glass substrate 0.13 -1.33 6.29 0.87
PFBP-1a 4.74 1.11 4.60 11.09
PFBP-1a:TCz1 3.11 0.50 3.62 10.37
PFBP-1b 10.66 1.56 5.48 19.92
PFBP-1b:TCz1 4.92 1.25 5.40 12.52

Figure S22. (top) AFM 3D topographical images of vacuum deposited thin films as well as glass substrate.
(bottom) summary of roughness parameters.

1.0 1.0
PFBP-1a:mCP PFBP-1a:TCz1
PFBP-1b:mCP PFBP-1b:TCz1
PFBP-2a:mCP PFBP-2a:TCz1
PL intensity, a.u.

PL intensity, a.u.

0.8 0.8
PFBP-2b:mCP PFBP-2b:TCz1

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
400 450 500 550 600 650 700
400 450 500 550 600 650 700

Wavelength, nm Wavelength, nm
(a)

S25
 Ex: 374 nm PFBP-1a:mCP(15x85%) Ex: 374 nm PFBP-1a:TCz1(15x85%)
PFBP-1b:mCP(15x85%) PFBP-1b:TCz1(15x85%)
1000 1000 PFBP-2a:TCz1(15x85%)
PFBP-2a:mCP(15x85%)
PFBP-2b:mCP(15x85%) PFBP-2b:TCz1(15x85%)

Counts
Counts
100 100

10 10

1 1
2000 4000 2000 4000
Time, ns Time, ns
(b)
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).

S26
 101 101

Current density, mA/cm2

150V -150V

Current density, mA/cm2

130V -130V
110V -110V
90V -90V
100 70V 100 -70V
50V -50V
30V -30V
10-1 10-1

10-2 10-2
PFBP 1b PFBP 1b
10-3 holes 10-3 electrons
d=2.8 m d=2.8 m

10-5 10-4 10-3 10-5 10-4 10-3

Time, s Time, s
Current density, mA/cm2

150V -150V
101

Current density, mA/cm2

130V -130V
110V 101 -70V
90V -90V
100

100
10-1

10-2
PFBP 2a 10-1 PFBP 2a
-3
holes electrons
10 d=2.65 m d=2.65 m

10-6 10-5 10-4 10-6 10-5

Time, s Time, s

102 -80V
2
Current density, mA/cm

-70V
Current density, mA/cm2

-60V 80V
-50V 70V
60V
101 50V
101

100
100
PFBP 2b PFBP 2b
electrons holes
-1
d=1.15 m 10 d=1.15 m
10-1
10-6 10-5 10-4 10-6 10-5 10-4
Time, s Time, s
Figure S24. Electron and hole time-of-flight current transients for the studied samples PFBP-1b, PFBP-2a,
and PFBP-2b.

S27
 10-3
PFBP 2b:holes

Mobility (cm2/Vs)
10-4

10-5
400 600 800 1000
1/2 1/2 1/2
E (V /cm )
Figure S25. Hole mobility versus electric fields for the PFBP-2b.

DeviceA Device B
1.0 1.0
5V 5V

Normalized intensity, a.u.

Normalized intensity, a.u.

6V 6V
7V 7V
0.8 0.8
8V 8V
9V 9V
10V 10V
0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
400 450 500 550 600 650 400 450 500 550 600 650
Wavelength, nm Wavelength, nm

Device C Device D
1.0 1.0
9V 4V
Normalized intensity, a.u.
Normalized intensity, a.u.

11V 5V
13V 6V
0.8 0.8
15V 7V
8V
9V
0.6 0.6
10V

0.4 0.4

0.2 0.2

0.0 0.0
400 450 500 550 600 650 400 450 500 550 600 650

Wavelength, nm Wavelength, nm

Figure S26. EL spectra of the studied devices at different voltages.

S28
 Device A Device A
Device B Device B
Device C

Power efficiency, lm/W

Device C

Current efficiency, cd/A

Device D 10 Device D
10

1
1

0.1

0.1
10 100 10 100
Current density, mA cm2 Current density, mA cm2

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

S29
Crystal data
Chemical formula C27H14F9N
Mr 523.39
Crystal system, space Monoclinic, P21/c
group
Temperature (K) 100
a, b, c (Å) 8.834 (3), 23.095 (6), 11.074 (4)
β (°) 109.65 (3)
V (Å3) 2127.8 (12)
Z 4
Radiation type Mo Kα
µ (mm−1) 0.15
Crystal size (mm) 0.26 × 0.24 × 0.06

Data collection
Diffractometer Xcalibur, Atlas
Absorption correction Multi-scan
CrysAlis PRO 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
Tmin, Tmax 0.991, 1.000
No. of measured, 37368, 5527, 4407
independent and
observed [I > 2σ(I)]
reflections
Rint 0.027
(sin θ/λ)max (Å−1) 0.694

Refinement
R[F2 > 2σ(F2)], 0.037, 0.093, 1.02
wR(F2), S
No. of reflections 5527
No. of parameters 336
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.34, −0.25

Computer programs: CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015), ShelXT (Sheldrick, 2015),
SHELXL (Sheldrick, 2015), Olex2 (Dolomanov et al., 2009).

S30
Tables S3. Experimental details for compound PFBP-1b

Crystal data
Chemical formula C42H28F8N2
Mr 712.66
Crystal system, space Monoclinic, P21
group
Temperature (K) 100
a, b, c (Å) 8.791 (3), 50.622 (9), 15.001 (4)
β (°) 96.16 (3)
V (Å3) 6637 (3)
Z 8
Radiation type Mo Kα
µ (mm−1) 0.12
Crystal size (mm) 0.53 × 0.29 × 0.05

Data collection
Diffractometer Xcalibur, Atlas
Absorption correction Multi-scan
CrysAlis PRO 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
Tmin, Tmax 0.818, 1.000
No. of measured, 70499, 31163, 23810
independent and
observed [I > 2σ(I)]
reflections
Rint 0.056
(sin θ/λ)max (Å−1) 0.694

Refinement
R[F2 > 2σ(F2)], 0.063, 0.150, 1.06
wR(F2), S
No. of reflections 31163
No. of parameters 1889
No. of restraints 1
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.34, −0.34
Absolute structure Flack x determined using 8244 quotients [(I+)-(I-)]/[(I+)+(I-)]

S31
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Absolute structure 0.3 (3)
parameter

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, Monoclinic, P21/c
space group
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 Analytical
correction 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, 13429, 6480, 2086
independent and
observed [I >
2σ(I)] reflections
Rint 0.133
(sin θ/λ)max (Å−1) 0.625

Refinement

S32
R[F2 > 2σ(F2)], 0.096, 0.336, 0.91
wR(F2), S
No. of reflections 6480
No. of parameters 445
No. of restraints 106
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e 0.31, −0.33
Å−3)

Computer programs: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018), ShelXT (Sheldrick, 2015),
SHELXL (Sheldrick, 2015), Olex2 (Dolomanov et al., 2009).

Tables S5. Experimental details for compound PFBP-2b_crystalB

Crystal data
Chemical formula C35H30F9N
Mr 635.60
Crystal system, space Triclinic, P-1
group
Temperature (K) 100
a, b, c (Å) 10.512 (4), 11.169 (4), 14.712 (4)
α, β, γ (°) 97.80 (3), 108.96 (3), 106.05 (3)
V (Å3) 1520.8 (10)
Z 2
Radiation type Mo Kα
µ (mm−1) 0.12
Crystal size (mm) 0.38 × 0.18 × 0.05

Data collection
Diffractometer Xcalibur, Atlas
Absorption correction Multi-scan
CrysAlis PRO 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
Tmin, Tmax 0.950, 1.000
No. of measured, 27147, 7537, 5361
independent and
observed [I > 2σ(I)]
reflections

S33
Rint 0.027
(sin θ/λ)max (Å−1) 0.694

Refinement
R[F2 > 2σ(F2)], 0.043, 0.112, 1.02
wR(F2), S
No. of reflections 7537
No. of parameters 461
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.33, −0.24

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.

S34
References

(1) J. C. de Mello, H. F. Wittmann, R. H. Friend. Adv. Mater. 1997, 9, 230–232.

(2) N. A. Kukhta, D. Volyniuk, L. Peciulyte, J. Ostrauskaite, G. Juska, J. V. Grazulevicius.

Dyes. Pigm., 2015, 117, 122–132.

(3) D. Gudeika, J. V. Grazulevicius, D. Volyniuk, G. Juska, V. Jankauskas, G. Sini. J. Phys.

Chem. C, 2015, 119, 28335−28346.

(4) G. Grybauskaite-Kaminskiene, D. Volyniuk, V. Mimaite, O. Bezvikonnyi, A. Bucinskas, G.

Bagdziunas, J. V. Grazulevicius. Chem. Eur.J. 2018, 24, 9581 –9591

S35