Synthesis and photophysical properties of new perylene bisimide derivatives for application as emitting materials in OLEDs

Article abstract of DOI:10.1016/j.dyepig.2018.07.006

Three novel perylene diimide derivatives with bulky aromatic moieties (fluorene, carbazolyl-fluorene, and anthracyl-fluorene) connected via triple bonds with perylene core were successfully designed and synthesized. The chemical structure of prepared compounds was confirmed by ¹H and ¹³C NMR and mass spectrometry. Their optimized ground-state geometry and frontier molecular orbitals were theoretically estimated based on density functional theory. The compounds undergo the reversible electrochemical reduction process and exhibit very low energy band gaps (1.56–1.98 eV) being promising for electronic applications. They also display excellent solubility, high thermal stability and luminescence in solution and in the solid state as a film in the red spectral region. The highest photoluminescence quantum yield (79% in solution and 28% in the film) was found for perylene diimide bearing fluorene unit. All molecules showed the ability for light emission under an applied voltage. The fabricated diodes with structure ITO/PEDOT:PSS/compound/Al exhibited electroluminescence with maximum emission band located between 685 and 732 nm. The most intense electroluminescence, which was additionally plasmonically enhanced by incorporating silver nanowires, was observed for the device based on molecules with anthracene structure.

Full text of DOI:10.1016/j.dyepig.2018.07.006

Accepted Manuscript
Synthesis and photophysical properties of new perylene bisimide derivatives for
application as emitting materials in OLEDs
Marek Matussek, Michał Filapek, Paweł Gancarz, Stanisław Krompiec, Jan Grzegorz
Małecki, Sonia Kotowicz, Mariola Siwy, Sebastian Maćkowski, Anna Chrobok, Ewa
Schab-Balcerzak, Aneta Słodek
PII:
S0143-7208(18)31275-0
10.1016/j.dyepig.2018.07.006
DYPI 6860
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 7 June 2018
Revised Date: 2 July 2018
Accepted Date: 2 July 2018
Please cite this article as: Matussek M, Filapek Michał, Gancarz Paweł, Krompiec Stanisł, Grzegorz
Małecki J, Kotowicz S, Siwy M, Maćkowski S, Chrobok A, Schab-Balcerzak E, Słodek A, Synthesis and
photophysical properties of new perylene bisimide derivatives for application as emitting materials in
OLEDs, Dyes and Pigments (2018), doi: 10.1016/j.dyepig.2018.07.006.
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ACCEPTED MANUSCRIPT
Synthesis and photophysical properties of new perylene bisimide derivatives for
application as emitting materials in OLEDs
1
1
1
1
Marek Matussek , Michał Filapek , Paweł Gancarz , Stanisław Krompiec , Jan Grzegorz
1
1
2
3
4
Małecki , Sonia Kotowicz , Mariola Siwy , Sebastian Maćkowski , Anna Chrobok , Ewa
1
,2*
1*
Schab-Balcerzak , Aneta Słodek
1
Institute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice, Poland
2
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819
Zabrze, Poland
3
Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, 5
Grudziadzka Str., 87-100 Torun, Poland
4
Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, Gliwice,
Krzywoustego 4, 44-100, Poland
*
corresponding authors, E-mail address: ebalcerzak@cmpw-pan.edu.pl (E. Schab-Balcerzak), a.slodek@wp.pl
A. Slodek)
(
Abstract
Three novel perylene diimide derivatives with bulky aromatic moieties (fluorene, carbazolyl-
fluorene, and anthracyl-fluorene) connected via triple bonds with perylene core were
successfully designed and synthesized. The chemical structure of prepared compounds was
1
13
confirmed by H and C NMR and mass spectrometry. Their optimized ground-state
geometry and frontier molecular orbitals were theoretically estimated based on density
functional theory. The compounds undergo the reversible electrochemical reduction process
and exhibit very low energy band gaps (1.56-1.98 eV) being promising for electronic
applications. They also display excellent solubility, high thermal stability and luminescence in
solution and in the solid state as a film in the red spectral region. The highest
photoluminescence quantum yield (79 % in solution and 28 % in the film) was found for
perylene diimide bearing fluorene unit. All molecules showed the ability for light emission
under
an
applied
voltage.
The
fabricated
diodes
with
structure
ITO/PEDOT:PSS/compound/Al exhibited electroluminescence with maximum emission band
located between 685 and 732 nm. The most intense electroluminescence, which was
additionally plasmonically enhanced by incorporating silver nanowires, was observed for the
device based on molecules with anthracene structure.
1

ACCEPTED MANUSCRIPT
Keywords: perylene bisimide, fluorene, carbazole, anthracene, fluorescence, organic
electronics
Graphical abstract
1
. Introduction
Perylene-3,4,9,10-tetracarboxylic acid diimides (Perylene bisimides, PDIs) is a class
of aromatic compounds consisting of perylene core scaffold substituted by imide groups at
peri-3,4 and 9,10 positions. The imide groups with well-defined electron-accepting properties
attached to π-rich perylene core create a donor-acceptor system (D-A). The rigid structure of
highly π-conjugated PDI molecule exhibit appealing electrochemical and spectral properties
being used as stable organic semiconductors of n-type [1-4]. They are characterized by high
-3
electronic affinity (E ≈ -4.0 eV) and good mobility of negative charges in the solid state (10
ea
1
2
-
10 cm /Vs) [5,6], being thus favorably predestined for applications in the area of organic
electronics. Moreover, perylene bisimides exhibit strong absorption in the visible region,
intense luminescence, and external high thermal and chemical (oxidative) stability [7-9].
However, the PDIs due to their flat structure tend to aggregate in the solid state as a result of
π-π interactions [10-12]. Modification of PDIs structure allows to obtain materials with the
desired physicochemical properties and to eliminate unfavorable intramolecular interactions,
which cause fluorescence quenching. The substitution of the nitrogen atom in PDIs by
aliphatic [13,14] and aryl [15,16] motifs allows - in a relatively easy and effective way - to
increase their solubility, and strongly inhibited the aggregation in the concentrated solution
[
17]. The PDI with bulky terminal 2,4-dimethylpent-3-yl substituents showed strong
fluorescence not only in the concentrated solution but also in the solid state with the
2

ACCEPTED MANUSCRIPT
fluorescence quantum yield nearly 100% [18]. Moreover, modification of the PDI core by
substitution at 1,6,7 and 12- positions (bay-region) increases the steric strain between
naphthalene motifs and, as a consequence, leads to a twist of the perylene core and
disturbance of flat structure, which reduces the intermolecular interactions [19-21]. The PDI
compounds substituted in the bay region by naphthalene and acenaphthalene moieties were
successfully applied as emissive layers in OLED devices. OLED device based on PDI with
acenaphthalene units exhibited the best efficiency in the red spectral region (emission at 693
nm, CIE x = 0.69, y = 0.29) described up to now in the literature [20]. The introduction of
azaborine into bay position of PDI allowed to obtain the fluorescence quantum yield of 81%
notwithstanding the constructed OLED devices with increase of doping ratio of azaborazine-
annulated perylene diimide have shown a decrease of the external quantum efficiency (EQE)
even to 0.05% assigned to the aggregation induced quenching (AIQ) process [21]. The simple
OLED devices composed of layer of dendronized perylene derivatives with the external
quantum efficiency above 0.1% and red emission at 650 nm were reported [22]. The
appealing physicochemical properties of perylene bisimides, including unique electrical
properties and relatively easy and effective PDI structure modification routes, make the
described compounds and their derivatives highly attractive for potential use on the organic
electronics substrate, including in particular organic light-emitting diodes (OLEDs) [20-22],
organic field-effect transistors (OFETs) [23,24], organic photovoltaic cells (OPVs) [25-27],
dye lasers [28], sensors [29], and optical power limiters [30].
Here, we report on the synthesis and photophysical characterization of three perylene diimides
(PDIs) connected via triple bonds (C≡C) with bulky aromatic rings (fluorene (PDI1),
carbazolyl-fluorene (PDI2), and anthracyl-fluorene (PDI3)) in the bay position, and
substituted at N positions by 2-ethylhexyl group. The presence of bulky substituents in PDIs
molecules significantly enhances their solubility and inhibits the intermolecular interaction
and aggregation. We demonstrate that the novel PDI derivatives are promising candidates for
deep red emissive OLEDs.
3

ACCEPTED MANUSCRIPT
2
. Experimental
2
.1 Materials
All reagents were of analytical reagent grade, and were used without further purification.
Solvents were distilled by using standard methods and purged with argon before use.
Column chromatography was carried out on Merck silica gel. Thin-layer chromatography
(TLC) was performed on silica gel (Merck TLC Silica Gel 60). The key intermediates 1-13
and ethynyl derivatives (Et-1 – Et-3) were synthesized according to the well-known
1
13
procedures with minor modifications, and characterized by H NMR and C NMR
spectroscopic analysis (see Supplementary Information for details). Poly[3,4-
(ethylenedioxy)thiophene]:poly-(styrenesulfonate) (PEDOT:PSS) (0.1–1.0 S/cm) and
substrates with pixilated ITO anodes were supplied by Ossila.
2
.2 Synthesis and characterization
General Sonogashira cross-coupling procedure for perylene bisimide derivatives (PDI1–
PDI3)
A solution of 13 (100 mg, 0.138 mmol) in 50 mL degassed TEA was stirred and bubbled with
argon for 20 min. After this time, Pd(PPh ) (16 mg, 10%-mol), and CuI (3 mg, 10%-mol)
3
4
were added, and the resulting mixture was bubbled with argon for another 10 min. Et-1 (69
mg, 0.166 mmol, 1.2 eq), Et-2 (96 mg, 0.166 mmol, 1.2 eq) or Et-3 (102 mg, 0.166 mmol,
1
.2 eq) in 10 mL TEA was then injected through the septum, and the mixture was stirred at 80
°
C for 24h. The resulting mixture was filtered and filtration was evaporated under reduced
pressure. After removal of the solvent, the residue was purified by column chromatography
giving target compounds (PDI1–PDI3).
1
-(9,9-dioctylfluoren-2-ylethynyl)-N,N’-bis(2-ethylhexyl)-3,4,9,10-perylene diimide (PDI1).
The crude product was purified by column chromatography (silica gel, chloroform). The
1
product was obtained as a dark red solid (109 mg, 74% yield). H NMR (400 MHz, CDCl ): δ
3
1
0.22 (d, J = 8.3 Hz, 1H), 8.72 (s, 1H), 8.62 (d, J = 8.3 Hz, 1H), 8.58 (d, J = 8.0 Hz, 1H), 8.51
(
d, J = 8.0 Hz, 1H), 8.44 (d, J = 8.2 Hz, 2H), 7.82-7.76 (m, 2H), 7.71 (s, 1H), 7.65 (dd, J =
1
7
.8 Hz, J = 1.2 Hz, 1H), 7.46-7.37 (m, 3H), 4.29-4.03 (m, 4H), 2.23-2.04 (m, 4H), 2.03-1.86
2
(
m, 2H), 1.51-1.27 (m, 16H), 1.23-1.06 (m, 20H), 0.97 (td, J = 7.2 Hz, J = 1.3 Hz, 6H), 0.91
1 2
4

ACCEPTED MANUSCRIPT
1
3
(
t, J = 7.0 Hz, 6H), 0.82-0.65 (m, 10H). C NMR (126 MHz, CDCl ): δ 163.70, 163.50,
3
1
1
1
1
2
63.47, 163.08, 151.50, 151.42, 143.20, 140.04, 138.45, 134.23, 134.05, 133.65, 133.13,
30.96, 130.89, 130.75, 130.64, 128.77, 128.18, 127.95, 127.10, 126.93, 126.60, 126.39,
26.33, 123.33, 123.21, 123.15, 123.09, 122.83, 122.76, 121.93, 120.49, 120.44, 120.23,
20.13, 102.30, 91.48, 55.42, 44.30, 40.33, 37.99, 31.79, 30.82, 30.07, 29.33, 29.29, 28.76,
4.11, 23.94, 23.14, 23.12, 22.61, 14.17, 14.08, 10.66, 10.64. HRMS (ESI) calcd. for
+
C H N O [M+H] 1027.6353; found 1027.6350.
71
82
2
4
1
-((7-(carbazol-9-yl)-9,9-dioctylfluoren-2-ylethynyl)-N,N’-bis(2-ethylhexyl)-3,4,9,10-
perylene diimide (PDI2). The crude product was purified by column chromatography (silica
1
gel, chloroform). The product was obtained as a black solid (172 mg, 70% yield). H NMR
(
400 MHz, CDCl ): δ 10.05 (d, J = 8.3 Hz, 1H), 8.56 (s, 1H), 8.46 (dd, J = 13.5 Hz, J = 8.1
3
1
2
Hz, 2H), 8.33 (d, J = 8.0 Hz, 1H), 8.22 (dd, J = 8.1 Hz, J = 6.7 Hz, 2H), 8.15 (d, J = 7.8 Hz,
1
2
2
H), 8.04 (d, J = 7.9 Hz, 1H), 7.91 (d, J = 7.8 Hz, 1H), 7.83 (s, 1H), 7.71 (dd, J = 7.7 Hz, J2
1
=
1.1 Hz, 1H), 7.68-7.63 (m, 2H), 7.50 (d, J = 8.2 Hz, 2H), 7.46-7.40 (m, 2H), 7.34-7.27 (m,
2
H), 4.27-4.02 (m, 4H), 2.35-2.10 (m, 4H), 2.08-1.89 (m, 2H), 1.54-1.33 (m, 16H), 1.32-1.14
1
3
(
m, 20H), 1.05-0.98 (m, 6H), 0.97-0.91 (m, 6H), 0.83-0.76 (m, 10H). C NMR (126 MHz,
CDCl ): δ 163.54, 163.37, 163.29, 162.93, 153.37, 151.88, 142.31, 140.89, 139.22, 138.29,
3
1
37.45, 133.96, 133.83, 133.39, 132.97, 131.23, 130.68, 130.59, 130.50, 128.64, 127.86,
26.72, 126.56, 126.45, 126.10, 126.00, 123.49, 123.20, 123.14, 122.76, 122.67, 121.91,
21.89, 121.69, 120.58, 120.46, 120.43, 120.17, 120.06, 109.77, 102.20, 91.77, 55.82, 44.35,
4.32, 40.26, 38.02, 31.81, 30.86, 30.09, 29.43, 29.32, 28.78, 24.23, 24.14, 23.16, 23.14,
1
1
4
+
2
2.62, 14.19, 14.07, 10.66, 10.64. HRMS (ESI) calcd. for C H N O [M+H] 1192.6931;
8
3
89
3
4
found 1192.6929.
1
3
-(7-(anthracen-9-ylethynyl)-9,9-dioctylfluoren-2-ylethynyl)-N,N’-bis(2-ethylhexyl)-
,4,9,10-perylene diimide (PDI3). The crude product was purified by column
chromatography (silica gel, chloroform). The product was obtained as a black solid (136 mg,
1
7
7% yield). H NMR (400 MHz, CDCl ): δ 10.18 (d, J = 8.3 Hz, 1H), 8.70 (s, 1H), 8.61 (t, J
3
=
=
9.7 Hz, 3H), 8.52 (d, J = 8.0 Hz, 1H), 8.47 (d, J = 8.0 Hz, 1H), 8.40-8.31 (m, 3H), 7.94 (d, J
8.4 Hz, 2H), 7.83 (s, 2H), 7.81-7.76 (m, 3H), 7.68 (d, J = 7.7 Hz, 1H), 7.60-7.53 (m, 2H),
7
1
4
.50-7.43 (m, 2H), 4.27-4.06 (m, 4H), 2.32-2.18 (m, 4H), 2.10-1.90 (m, 2H), 1.53-1.31 (m,
6H), 1.30-1.11 (m, 20H), 1.00 (t, J = 7.3 Hz, 6H), 0.94 (t, J = 6.8 Hz, 6H), 0.90-0.81 (m,
1
3
H), 0.76 (t, J = 6.5 Hz, 6H). C NMR (126 MHz, CDCl ): δ 206.97, 163.63, 163.45, 163.43,
3
5

ACCEPTED MANUSCRIPT
1
1
1
1
3
1
1
63.05, 151.89, 151.78, 142.38, 140.49, 138.37, 134.06, 133.96, 133.47, 133.13, 132.48,
31.19, 131.14, 131.11, 130.77, 130.60, 128.66, 127.92, 127.72, 126.80, 126.68, 126.57,
26.52, 126.47, 126.15, 125.96, 125.65, 123.20, 123.18, 123.08, 123.04, 122.75, 122.66,
21.87, 120.78, 120.63, 120.18, 117.22, 102.07, 101.81, 91.95, 87.12, 55.71, 44.32, 40.38,
8.04, 31.82, 30.95, 30.87, 30.12, 29.42, 29.35, 28.80, 24.15, 24.10, 23.17, 23.14, 22.63,
+
4.19, 14.07, 10.68, 10.67. HRMS (ESI) calcd. for C H N O [M+H] 1227.6979; found
8
7
90
2
4
227.7015.
2
.3 Measurements
1
13
The NMR spectra were recorded in CDCl on a Bruker Advance 400 MHz (for H and C
3
1
3
NMR) or Bruker Advance 500 MHz (for C NMR – target compounds) instruments.
Thermogravimetric analysis (TGA) was carried out on a Mettler Toledo TGA STARe system
-1
-1
with a heating rate of 10 °C·min in a constant stream of nitrogen (20 ml·min ). Differential
Scanning Calorimetry (DSC) was performed with a Du Pont 1090B apparatus using a
-1
heating/cooling rate of 20 ºC·min under nitrogen and aluminum sample pans. UV-Vis
absorption spectra of solutions were recorded using an Evolution 220 UV-Visible
-5
Spectrophotometer at the concentration of 10 mol/L and 1 cm quartz cell and Jasco V-550
Spectrophotometer for films. Photoluminescence spectra of solutions were measured using
Varian Carry Eclipse Spectrometer. Photoluminescence spectra in the solid state were
monitored with Hitachi F-2500 Spectrometer. The quantum yield (Φ ) measurements were
f
performed by using the integrating sphere Avantes AvaSphere-80 (Edinburgh Instruments)
and absolute method. The measurements were performed at room temperature with solvent
(for liquid samples) or Spectralon® reflectance standard (for powdered samples) as blanks.
Electrochemical measurements were carried out using Eco ChemieAutolab PGSTAT128n
potentiostat, glassy carbon electrode (diam. 2 mm), platinum coil and silver wire as working,
auxiliary and a reference electrode, respectively. Potentials are referenced with respect to
ferrocene (Fc), which was used as the internal standard. Cyclic voltammetry experiments
were conducted in a standard one-compartment cell, in CH Cl (Carlo Erba, HPLC grade),
2
2
under argon. 0.2 M Bu NPF (Aldrich, 99%) was used as the supporting electrolyte. The
4
6
-6
3
concentration of compounds was equal 1.0·10 mol/dm . Deaeration of the solution was
achieved by argon bubbling through the solution for about 10 min before measurement. All
electrochemical experiments were carried out under ambient conditions. Electroluminescence
6

ACCEPTED MANUSCRIPT
(
EL) spectra were measured with the voltage applied using a precise voltage supply
GwInstek PSP-405) and the sample was fixed to an XYZ stage. Light from the OLED device
(
was collected through a 30 mm lens, focused on the entrance slit (50 µm) of a monochromator
Shamrock SR-303i) and detected using a CCD detector (Andor iDus 12305). Typical
acquisition times were equal to 10 seconds. The pre-alignment of the setup was done using a
05 nm laser. The layers' thickness were measured using an AFM Park XE-100 instrument
Park System, Korea) operating in tapping mode in the air with standard 125 µm single-
crystal silicon cantilevers. The piezoelectric scanner had a scan range of approximately
(
4
(
1
00 µm x 100 µm.
2
.4 Film preparation
Films on glass substrates were prepared from a homogeneous chloroform solution (10
mg/ml) by spin-coating method (1000 rpm, 60 s). Films were dried for 24h in a vacuum oven
at 50 °C.
2
.5 Device preparation
Devices with sandwich configuration ITO/PEDOT:PSS/PDI/Al were prepared on
OSSILA substrates with pixilated ITO anodes, cleaned with detergent, deionized water, 10%
NaOH solution, water, and isopropyl alcohol in an ultrasonic bath. Substrates were covered
with PEDOT:PSS film by spin-coating at 5000 rpm for 60 s and annealed for 5 min at 120 °C.
The active layer was spin-coated on top of the PEDOT:PSS layer from a chloroform solution
(10 mg/mL) at 1000 rpm for 60 s and annealed for 5 min at 100 °C. Finally, Al was vacuum-
-5
deposited at a pressure of 5·10 Torr.
2
.6 DFT calculation
The calculations were carried out using Gaussian09 [31] program. Molecular geometries of
the singlet ground state of the compounds were optimized in the gas phase at the B3LYP/6-
+
+
3
1g level of theory. For each compound a frequency calculation was carried out, verifying
that the obtained optimized molecular structure corresponds to an energy minimum, thus only
positive frequencies were expected. The contribution of a group (anthracene and carbazole) to
a molecular orbital was calculated using Mülliken population analysis. GaussSum 3.0
7

ACCEPTED MANUSCRIPT
program [32] was used to calculate group contributions to the molecular orbitals and to
prepare the partial density of states (DOS) spectra.
3
. Result and discussion
3
.1 Synthesis
The synthetic routes of intermediates and target compounds are shown in Schemes 1 and 2.
The key intermediates 1-13 and ethynyl derivatives (Et-1 – Et-3) were synthesized according
to the well-known procedures with minor modifications [33-41]. Briefly, the iodination of
fluorene gave 2-iodofluorene 1 and 2,7-diiodofluorene 4 which reacted with n-octyl bromide
in the presence of tetra-n-butyl ammonium bromide (TBAB) as phase transfer catalysis (PTC)
formed 2-iodo-9,9-dioctylfluorene 2 and 2,7-diiodo-9,9-dioctylfluorene 5 with high yield. The
Ullmann condensation of carbazole with 5 in the presence of CuI/1,10-phenanthroline as
catalysts produced 6 in 59% yield. Next, a Sonogashira cross-coupling reaction of
trimethylsilylacetylene (TMSA) with 2 and 6 in the presence of [Pd(PPh ) ]/CuI as catalysts
3
4
afforded 3 and 7. Treatment with NaOH converted compounds 3 and 7 into 2-ethynyl-9,9-
dioctylfluorene (Et-1) and 2-ethynyl-7-(carbazol-9-yl)-9,9-dioctylfluorene (Et-2).
Compound Et-3 was obtained in a four-step reaction. First, the bromination of fluorene gave
8
with 86% yield. Then, N-alkylation of 8 provided 2,7-dibromo-9,9-dioctylfluorene (9).
Sonogashira cross-coupling reaction of deficiency of TMSA with 9 afforded 10 which was
converted to 1-(7-ethynyl-9,9-dioctylfluoren-2-yl)ethynylanthracene (Et-3) (73% yield) by
treatment with NaOH. A brominated derivative of perylene bisimide 13 was obtained by
imidization reaction between 3,4,9,10-perylenetetracarboxylic dianhydride and 2-
ethylhexylamine to give perylene bisimide 12 in 83% yield, then 12 was converted to key
intermediate 13 by a selective bromination reaction using bromine. The desired perylene
bisimide derivatives (PDI1–PDI3) were prepared by Pd-catalyzed Sonogashira cross-
coupling reaction of the respective ethynyl derivatives Et-1, Et-2 or Et-3 with 13 (Scheme 2).
The obtained compounds PDI1–PDI3 were fully characterized by standard spectroscopic
1
13
methods ( H and C NMR, mass spectrometry). The final compounds PDI1–PDI3 exhibit
excellent solubility in common organic solvents, such as hexane, dichloromethane,
chloroform, toluene, and tetrahydrofuran.
8

ACCEPTED MANUSCRIPT
Scheme 1. Synthesis of compounds 1-13. Reagents and conditions:(a) I , H IO ,
2
5
6
AcOH/H O/H SO , 70 °C, 6h; (b) 50% NaOH, TBAB, n-C H Br, DMSO, room temp., 12h;
2
2
4
8
17
(
c) TMSA, Pd(PPh ) , CuI, TEA, room temp., 24h; (d) NaOH, MeOH/THF, room temp., 6h;
3 4
(
e) carbazole, CuI, K CO , 1,10-phenanthroline, DMF, reflux, 30h; (f) Br , Fe, CHCl , 0 °C,
2 3 2 3
4
h; (g) TMSA, Pd(PPh ) , CuI, TEA/PhMe, 35 °C, 20h; (h) 9-ethynylanthracene, Pd(PPh ) ,
3 4 3 4
CuI, TEA, 80 °C, 30h; (i) 2-ethylhexylamine, DMF, reflux, 8h; (j) Br , DCM, room temp.,
2
7
2h.
9

ACCEPTED MANUSCRIPT
Scheme 2. The synthetic route for the preparation of compounds PDI1–PDI3.
3
.2 DSC and TGA studies
The thermal properties of luminescent materials are important for achieving high performance
and long-lifetime optoelectronic devices [42] Thermal properties of the synthesized
unsymmetrical bay substituted acetylene perylene diimides PDI1−PDI3 were evaluated by
differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) carried out
under a nitrogen atmosphere. The obtained data are summarized in Table 1.
Table 1. The thermal properties of synthesized perylene diimide derivatives PDI1–PDI3.
DSC
TGA
Code
Residue at 800°C
%]
Tg [°C]
T5 [°C]
T10 [°C]
[
PDI1
PDI2
PDI3
135
130
98
369
419
425
419
440
443
33
10
21
All compounds gave similar DSC profiles with glass transition temperature (T ) registered at
g
1
35, 130 and 98 °C for PDI1, PDI2, and PDI3, respectively (Fig. S1). It was observed that
the presence of second acetylene unit in PDI3 lowered the T value. The measurements
g
confirmed that the derivatives are amorphous materials and no peaks due to crystallization
and melting appeared in DSC thermograms. TGA thermograms showed that for the obtained
compounds, thermal decomposition started when detected as 5% weight loss (T ) above 369
5
°
C. Based on T and the temperature of 10% weight loss (T ) it can be concluded that the
5 10
1
0

ACCEPTED MANUSCRIPT
introduction of carbazole (PDI2) and anthracene unit (PDI3) improves the thermal stability of
perylene diimide derivatives.
3
.3 UV-Vis absorption and emission investigations
Absorption and emission properties of the prepared perylene diimides PDI1–PDI3 were
studied by means of UV-Vis and photoluminescence (PL) spectroscopy in chloroform
solution and in the solid state as thin film on glass substrates. Electroluminescence ability of
the obtained molecular glasses was studied for diodes of the following configuration:
ITO/PEDOT:PSS/compound/Al. UV-Vis absorption spectra of investigated compounds both
in chloroform solution and as thin film were depicted in Fig. 1, whereas the spectroscopic data
are summarized in Table 2.
(a)
1
.0
PDI-1
PDI-2
PDI-3
1.0
0.8
0.6
0.4
0.2
PDI-1
PDI-2
PDI-3
0.8
CHCl3
Film
-5
c = 10 mol/L
0.6
0.4
0.2
0.0
0.0
250 300 350 400 450 500 550 600 650 700
300 350 400 450 500 550 600 650 700 750 800
Wavelength [nm]
Wavelength [nm]
(b)
5
0
λ ex= 340nm
λex = 380nm
λ ex= 560nm
40
CHCl3
-
5
c = 10 mol/L
30
PDI-1
20
10
0
500
550
600
650
700
750
800
Wavelength [nm]
(c)
1
1

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3
.0
.5
70
60
50
40
PDI-1
PDI-2
PDI-3
PDI-3
PDI-1
PDI-2
1.0
2
0
.8 CHCl
3
Film
λ ex= 520nm
-
5
2.0
c = 10 mol/L
λ ex= 560nm
0.6
1
.5
.0
30
20
10
0
0
.4
1
0.2
0.5
0.0
0.0
5
00
550
600
650
700
750
800
550
600
650
700
750
800
Wavelength [nm]
Wavelength [nm]
Fig. 1. (a) Normalized absorption spectra of PDI1–PDI3 in chloroform solution and films; (b)
photoluminescence spectra of PDI1 in solution under various λ and (c) PL spectra of PDI1–
ex
PDI3 in chloroform solution and films.
Table 2. UV-Vis, photoluminescence and electroluminescence data of bay substituted
perylene diimides PDI1–PDI3.
UV-Vis
PL λ [nm] (Stokes
em
4
a
-1
(ΦPL) [%]
EL
λ [nm]
EL
λmax [nm] (ε·10 )
shift [cm ])
Code
PDI1
b
b
b
CHCl3
Film
CHCl3
Film
CHCl3 Film
2
78(1.3); 338 (1.8);
3
24; 400;
3
4
77 (0.9); 448 (1.3);
79 (1.4); 529 (2.1);
621
(1658)
691
(4540)
488; 526;
79
15
17
28
20
19
706
685
732
sh
583
5
63 (1.8)
2
91 (2.5); 344 (3.0);
3
58;388; 661(2633);
668
(4792)
PDI2
PDI3
376 (2.4); 497 (1.8);
32 (1.9); 563 (2.0)
sh
5
06; 591
711(3697)
5
2
4
4
61 (2.9); 347 (1.8);
10 (2.1); 436 (2.0);
95 (0.9); 526 (0.9);
3
49;406;
444;
613
(1512)
720
(5269)
sh
5
22;580
5
61 (0.9)
a
3
-1
-1
b
-5
molecular absorption coefficient [dm ·mol ·cm ]; c=10 mol/L
Typically PDI-based molecules exhibited strong absorption in the range of 400-550 nm with
two sharp maxima (λmax) at about 480 and 520 nm corresponding to 0-0 and 0-1 vibrational
transition of perylene diimide unit [43,44]. In the case of investigated compounds except
absorption characteristic for perylene diimide structure also band at higher energy in the range
of 300-400 nm due to the presence of fluorene derivative was seen. Compound bearing
anthracene moiety (PDI3) exhibited additionally absorption band with a pronounced
vibrational structure with λmax at 410 and 436 nm. The absorption band at a higher energy
1
2

ACCEPTED MANUSCRIPT
range of the compounds in films is slightly bathochromic shifted compared to its in solution,
indicating the weak aggregation in the solid state (Fig. S2).
The effect of the excitation wavelength (λ ) on maximum emission band (λ ) and its
ex
em
intensity was evaluated and representative PL spectra of PDI1 obtained under various λ are
ex
shown in Fig. 1b. The utilization of λ = 560 nm resulted in the highest PL intensity. All
ex
studied perylene diimides were photoluminescent both in solution and in the solid state and
emitted red radiation with PL quantum yield in the range of 15-79 % in solution and 19-28 %
in film, respectively. Compounds PDI1–PDI3 in the solid state exhibited large Stokes shifts
-1
ranging above 4540 cm . Organic emitting compounds with large Stokes' shift are desired for
various application including lighting and photovoltaic technologies [45]. The presence of an
additional substituent at the fluorene unit (PDI2 and PDI3) influences on the emission
spectra. It was found that substitution of fluorene with N-carbazole moiety (PDI2)
significantly reduced emission intensity and shifted λem to lower energy in solution. On the
other hand, PDI2 in film emitted light with the highest intensity. The presence of second
acetylene bond together with anthracene unit (PDI3) in film lowered PL intensity. However,
the relationship between structure and PL intensity does not correspond to EL intensity.
Considering the EL spectra depicted in Fig. 2 compound without substituted fluorene unit
(PDI1) showed the lowest intensity of emitted light under external voltage, which was the
most intense in the case of molecule bearing anthracene structure (PDI3).
1
3

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3
3
2
2
1
1
500
000
500
000
500
000
4
0000
ITO/PEDOT:PSS/PDI-1/Al
16 V
18 V
ITO/PEDOT:PSS/PDI-2/Al
1
2 V
1
9 V
20 V
1 V
22 V
13 V
4 V
30000
1
2
2
0000
0000
0
1
5
00
0
400
500
600
700
800
900
400
500
600
700
800
900
Wavelength [nm]
Wavelength [nm]
ITO/PEDOT:PSS/PDI-3/Al
70000 ITO/PEDOT:PSS+AgNWs/PDI-2/Al
60000
50000
40000
30000
20000
10000
0
8
9
V
V
7
8
9
V
V
V
60000
50000
40000
30000
20000
10000
0
10 V
1 V
2 V
1
10 V
11 V
12 V
1
400
500
600
700
800
900
400
500
600
700
800
900
Wavelength [nm]
Wavelength [nm]
Fig. 2. Electroluminescence spectra of fabricated diodes as a function of the applied voltage.
All the devices based on the PDI derivatives showed electroluminescence and emitted light
with a maximum of EL band ranging from 685 to 732 nm (Table 2). In the case of devices
based on PDI1 and PDI2 together with the increase of applied voltage the increase of
intensity of emitted light was observed contrary to the diode with PDI3 (Fig. S3). For diode
contains PDI3 the intense of electroluminescence rapidly decreases above external voltage
above 11 V. Device based on PDI3 exhibited the best performance considering the EL
intensity. Additionally, in order to test the possibility of the EL intensity enhancing in OLED
devices a layer of silver nanowires (AgNWs) was incorporated during the preparation of the
diode based on PDI2. Device with structure ITO/PEDOT:PSS/AgNWs(1:1)/PDI2/Al was
prepared. Considering the EL spectra of such diode depicted in Fig. 2, when PDI2 mixed with
plasmonically active silver nanowires, the compounds exhibited significantly stronger
electroluminescence signal, associated presumably with plasmonics enhancement [46,47].
1
4

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3
.4 Quantum calculations
To gain further insight into the electronic structure of the compounds the quantum theoretical
calculations at the density functional theory level were performed. Based on the optimized
geometries the energy and electronic distribution of molecular frontier orbitals were
calculated in dichloromethane for a comparison with experimental (electrochemical)
potentials. Three-dimensional plots of the electron density for the highest occupied molecular
orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of PDI1–PDI3 are
shown in Fig. 3, whereas the orbital energies and compositions are summarized in Table S1 in
SI.
LUMO
HOMO
PDI1
PDI2
1
5

ACCEPTED MANUSCRIPT
PDI3
Fig. 3. Contours of HOMOs and LUMOs of PDI1–PDI3 compounds.
Moreover, Fig. S4 in Supplementary Materials shows the partial density of states diagrams.
The molecule of each compound was divided into two fragments such as perylene diimide, 2-
etynylfluorene (R) with appropriate alkyl chains and the substituent (R ֹ’ ) in fluorene moiety,
respectively and their contribution to each molecular orbital was calculated. The electronic
structures of the compounds of PDI2–PDI3 are similar and HOMOs are localized on the
substituent (R and R’) in the perylene moiety (Fig. 3, Fig. S4, and Table S1). In the case of
PDI1 both molecule aromatic fragments i.e. perylene diimide and 2-etynylfluorene participate
in HOMO. LUMOs in each case are localized on the antibonding orbitals of perylene diimide
moiety. The calculated energies of LUMO are the same for each molecule which is
understandable considering the electronic structures of these compounds. HOMO energies
increase in the range of PDI1 to PDI3. The increase of the HOMO energy is related to the
molecular structure of the R and R’ substituents and thus its effect on the electronic structure
of the molecule. So, in the PDI2 and PDI3 molecules the LUMO is mainly localized on the
R’ substituent in the fluorene part i.e. carbazole and ethynyl anthracene moieties, respectively
(Table S1).
3
.5 Electrochemical properties
The electrochemical properties of PDI1–PDI3 were investigated in CH Cl solution by means
2
2
of cyclic voltammetry (CV). The electrochemical oxidation and reduction onset potentials
1
6

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were used for estimation of the HOMO and LUMO energies (or rather, ionization potentials
and electron affinities) of the materials (assuming that IP of ferrocene equals -5.1 eV) [48].
The calculated HOMO and LUMO levels together with electrochemical energy band gap (Eg)
are presented in Table 3. All measurements were carried out on glassy carbon electrode (the
working electrode). In comparison to the platinum electrode, it allows to record up to three
separate reduction peaks (for PDI3), which was not possible on platinum wire (diam. 1mm)
electrode.
Table 3. The calculated HOMO and LUMO levels together with electrochemical energy band
gap (Eg).
a
b
c
E1red
E1ox
[V]
E2ox
[V]
HOMO
(CV)
LUMO
(CV)
HOMO
(DFT)
LUMO
(DFT)
Eg(CV)
[eV]
Eg(DFT)
[eV]
Code
E
2red
E
3red
[V]
[V]
[V]
PDI1
PDI2
PDI3
-1.02
-0.99
-0.97
-1.15
-1.10
-1.08
-
-
0.96
0.74
0.59
1.10
1.05
-
-6.06
-5.84
-5.69
-4.08
-4.11
-4.13
-5.66
-5.43
-5.18
-3.54
-3.54
-3.53
1.98
1.73
1.56
2.12
1.89
1.65
-2.01
a
b
c
HOMO= -5.1- Eox; LUMO= -5.1-Ered
g
E = Eox (onset) −Ered(onset)
For each polyimide a fully reversible reduction process towards the formation of an anion
radical according to mechanism put forward by S.-H. Hsiao et al. [49] was recorded (similar
as we reported before [50,51]).
The first reduction peak onset (E1red) is as high as -1.02, -0.99, and -0.97 V for PDI1, PDI2,
and PDI3, respectively (Fig. S5). This process is ascribed to the reduction of the imide core
-
(
i.e. PDI/PDI ). However, the values in each case are significantly lower compared with the
unsubstituted perylene derivatives [52]. This is a direct consequence of π-excessing moieties
incorporation in PDI's position 1, proving a strong influence on physical properties. By
-
2-
further lowering of potential all imides underwent second reduction step (PDI /PDI ), also
fully reversible. It is worth noting that difference of ending group in the molecule chain in
each case affected reduction values, but not change the high stability of PDI anion and
dianion itself. Finally, for PDI3 the third reduction peak at a potential slightly below -2 V was
also recorded. In this potential region, only this molecule underwent the reduction process,
which suggests, that it is the reduction of anthracene moiety (Fig. 4).
1
7

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8
6
4
2
0
2
4
6
8
-
-
-
-
1
2
3
PDI-3
-
10
12
-
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
+
E \ V vs Fc/Fc
Fig. 4. Cyclic voltammograms for PDI3. CV sweep rateν = 100 mV/s, 0.1 M Bu NPF in
4
6
CH Cl with different lower vertex potential.
2
2
On the other hand, for PDI1 and PDI3 oxidation was non-reversible (E C type, which means
r
i
that reversible electrochemical reaction (E ) is followed by an irreversible chemical reaction
r
(
C )), with onsets at 0.96 and 0.52 V, respectively. In the case of PDI2 oxidation is slightly
i
+
different in nature, giving characteristic carbazole/carbazole response. Taking into
consideration this fact, the possibility of anodic polymerization was evaluated. As can be seen
in Fig. 5 after first cycle new peak with onset at 0.46 appears.
2
2
1
1
5
0
5
0
5
0
5
1
st cycle
next cycles
PDI-2
-
-
0.5
0.0
0.5
1.0
1.5
+
E \ V vs Fc/Fc
Fig. 5. Cyclic voltammograms for PDI2. CV sweep rate ν = 100 mV/s, 0.1 M Bu NPF in
4
6
CH Cl . Arrows indicate shifts in peak maxima.
2
2
1
8

ACCEPTED MANUSCRIPT
Nevertheless, electrochemically determined band gaps for the investigated PDIs are as follow
1
.97, 1.73, and 1.57 eV. For PDI1 this value is in agreement with optical band gap (2.02 eV)
while in the case of PDI3 difference is quite high, suggesting that HOMO and LUMO are
separated in space. The electrochemical study shows that introduction into PDI molecule a
moiety with the desired redox properties can modify the electrochemical properties of the
final material. Very good reduction properties of the studied compounds, make them good
candidates for new organic n-type semiconductors, which is extremely important for the
organic electronics field.
4
. Conclusion
The synthesis and characterization of novel perylene diimides with bulky aromatic moieties in
bay positions were reported. The introduction of aromatic substituents to perylene core as
well as N-substitution by 2-ethylhexyl group considerably improves solubility and prevents
aggregation and π-πstacking of PDIs. The presence of substituents in bay positions of PDIs
has an impact on their properties. The prepared perylene diimides were amorphous and
showed T ranging from 98 to 135 ºC. The presence of carbazole structure (PDI2) resulted in
g
an increase of T . They exhibited high thermal stability with the beginning of decomposition
g
above 370 ºC. All examined perylene diimides are photo- and electroluminescent. They
emitted light in the deep red region. The substitution of fluorene in diimide with carbazole
and anthracene units significantly reduced PL intensity in solution, however, had a less
pronounced impact on PL quantum yield in the solid state. The introduction of carbazole
derivative into PDI hypsochromically shifted, compared to the others, the maximum of PL
and EL bands. It was found that compound bearing anthracene unit (PDI3) exhibited the most
intense electroluminescence under the lowest applied voltage. Thus, it seems to be the most
promising for further investigations.
Acknowledgment
This work was supported by the National Science Centre of Poland, Projects OPUS-11 No
2
016/21/B/ST5/00805 and Sonata Bis DEC-2013/10/E/ST3/00034. Calculations were carried
out at the Wroclaw Centre for Networking and Supercomputing (http:// www.wcss.wroc.pl);
grant number No.18. We particularly indebted to Dr. Henryk Janeczek for DSC
measurements.
1
9

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Highlights
•
•
•
•
Three novel perylene diimide (PDI) derivatives with bulky aromatic moieties were
synthesized.
Photophysical properties of the obtained compounds were thoroughly studied and
compared with DTF calculations.
The effect of substituents in bay positions of PDIs derivatives on photophysical
properties was discussed.
The emission enhancement of perylene diimide derivatives was presented by
incorporation of silver nanowires due to plasmonics enhancement.