22758 | Phys. Chem. Chem. Phys., 2015, 17, 22758--22769 This journal is© the Owner Societies 2015
Cite this:Phys.Chem.Chem.Phys.,
2015, 17, 22758
The optical properties and quantum chemical
calculations of thienyl and furyl derivatives
of pyrene
Krzysztof R. Idzik,*a Piotr J. Cywin´ski,b Wojciech Kuznik,c Jaroslaw Frydel,d
Tobias Lichaa and Tomasz Ratajczyke
A detailed electrochemical, photophysical and theoretical study is presented for various new thienyl and
furyl derivatives of pyrene. Their optical properties are described based on UV-VIS absorption and both
steady-state and time-resolved fluorescence spectroscopy. DFT and TDDFT calculations are also
presented to support experimental data. The calculations results show that HOMO–LUMO orbitals are
delocalized uniformly between aromatic core and aryl substituents. Good electrochemical stability of
thienyl and furyl hybrids of pyrene confirm their potential application for light emitting electrochemical
cells or spintronics mainly due to their beneficial optical and charge transport properties in electrochromic
devices. In order to demonstrate this potential, an OLED device is presented. Synthesized compounds
included in this OLED device both facilitate electron transport and act as a light emitting layer.
1. Introduction
Organic materials possessing an extended p-conjugation have
received immense attention in recent years. This is due to their
unique photophysical and charge transport properties, which
make them potential materials for applications in electronic
devices such as organic light emitting diodes (OLEDs),1–8 organic
photovoltaics (OPV),9–15 or organic thin film transistors (OTFT).16–20
Further, they are attractive due to their promising two photon
absorption21–24 and nonlinear optical21–24 characteristics.
Fluorescence probes based on pyrene moieties have attracted
considerable attention over the past decades.25–32 The pyrene
ring is of special interest because its hydrogen atoms can easily
be substituted using a wide range of chemical groups, particularly
aryl groups such as thiophene or furan. The pyrene structure is
well studied and has been intensively examined in the fields of
biology, chemistry and physics. Moreover, due to its electro-
conductive properties, pyrene and its derivatives have been
successfully applied as micro-environmental sensors,33–36
liquid crystals,37,38 and photoactive polypeptides.39 Pyrene is
a flat aromatic molecule and exhibits excellent fluorescence
properties. Its pure blue emission already permits its exploita-
tion for its use in OLEDs.40 The pyrene core is particularly
interesting in this context, since it offers numerous possibilities
for peripheral group modifications with profound consequences
on the condensed-matter structure. For example, unsubstituted
pyrene forms monoclinic crystals, while tetraethynylpyrene deriva-
tives of phenylethynyl form liquid crystalline columnar phases,41
and pyrenes similarly substituted with diethyleneglycolether deri-
vatives display a liquid phase at room temperature.42 Pyrene is an
efficient luminescent material, which has been investigated for
several decades. However, self-quenching can be observed at high
concentrations or pure crystals due to a molecular aggregation via
p-stacking.43–45 However, the luminescence properties of the pyrene
core might be modulated using the proper molecular substitution,
e.g., with heterocyclic units.
Organic p-conjugated structures containing thiophene units
play an important role in the search for new materials and their
novel applications46 such as organic solar cells47,48 or organic
field effect transistors.49 Thiophenes with well-defined chemical
structures have recently attracted great attention not only as an
example of model compounds for conducting materials, but also
as a new class of functional p-electron systems.50–56
Furan-based polymers are among the most widely used
p-conjugated systems in organic electronic devices. For example,
polymers containing furyl groups show an excellent performance
when acting as building materials for a highly efficient OLEDs.57
Another reason for using furan is its lower resonance stabilization
a Geoscience Centre of the University of Go¨ttingen, Dept. Applied Geology,
Goldschmidtstr. 3, 37077 Go¨ttingen, Germany.
E-mail: krzysztof.idzik@pwr.wroc.pl
b Functional Materials and Devices, Fraunhofer Institute for Applied Polymer Research,
Geiselbergstr. 69, 14476 Potsdam-Golm, Germany
c Czestochowa University of Technology, Faculty of Electrical Engineering, Armii
Krajowej 17, 42-201 Czestochowa, Poland
d VENITUR Sp. z o.o., Wawozowa 34 B, 31-752 Krakow, Poland
e Polish Academy of Sciences, Institute of Physical Chemistry, Kasprzaka 44/52,
01-224 Warsaw, Poland
Received 26th May 2015,
Accepted 21st July 2015
DOI: 10.1039/c5cp03013g
www.rsc.org/pccp
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PAPER
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energy compared to benzene. Thus, chromophores with furan
moieties display a molecular hyperpolarizability, which is higher
than those of their their benzene analogues.58 Oligofurans with
well-defined structures have also received great attention, not only
exemplarily as model compounds for conducting polyfurans, but
also as a new class of functional p-electron systems.
Considering the current literature, one can conclude that, when
compared to other heteroaromatics such as thiophene or pyrrole,
furan has great potential for further studies.59–66 This may partially
be attributed to the chemical lability of furan and its derivatives. For
example, furan serves as a diene in the [4+2] Diels–Alder reactions
undermilder conditions than those for thiophene and pyrrole.67 On
the other hand, the relatively low aromaticity of furan compared to
those of thiophene and pyrrole may give rise to different electronic
properties in the resulting furan-based materials.68
Over the last decade, highly efficient blue OLEDs have
attracted considerable attention due to their potential applica-
tions in full color ultra-thin flat panel displays.69–75 Organic
light sources are currently made from either low molecular
weight organic materials or polymers. For the former, the layer
structure of the OLED is usually deposited on a rigid base made
from glass or metal.76–79
Suzuki, Stille, Kumada, and Negishi coupling reactions are
well-described synthetic methods that are often used to prepare
electroactive compounds. In this paper, we also present a series
of symmetric molecules in which a pyrene core is connected to
thiophene and furan units. All compounds were obtained using
the Stille cross-coupling reaction. Furthermore, we describe DFT
Fig. 1 OLED structure with the details of the organic materials and their
functions used in each layer.
Scheme 1 Synthesis of thienyl and furyl derivatives of pyrene.
Fig. 2 Electronic absorption spectra for all pyrene thiophene derivatives
in chloroform (in ex. coefficient units).
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22760 | Phys. Chem. Chem. Phys., 2015, 17, 22758--22769 This journal is© the Owner Societies 2015
calculations and TDDFT simulations of molecular materials
based on a pyrene core which is connected to thiophene and
furan units. We also report the results of UV-VIS and fluores-
cence spectroscopy measurements for the obtained compounds.
Additionally, we present a fully functioning OLED device using a
synthesized low molecular weight material to act as an electron
transporting and light emitting layer (Fig. 1).
2. Methods and materials
2.1. Synthesis
All chemicals, reagents, and solvents were used as received
from commercial sources without further purification. Melting
points of the synthesized dyes were determined using a Stuart
smp 20 melting point apparatus.
2.2. Optical measurements
Electronic absorption spectra were collected on a UV-VIS absorp-
tion spectrometer Lambda 35 (Perkin Elmer, Rodgau, Germany).
The spectra were corrected with solvent absorption spectra to
obtain final absorption spectra for the studied compounds.
Steady-state fluorescence emission spectra were collected on an
FLS920-stm spectrometer (Edinburgh Instruments, Livingstone,
United Kingdom). The spectra were detector response corrected.
Fluorescence decays were also acquired on the FLS920-stm
spectrometer using the Time Correlated Single Photon Counting
(TCSPC) technique with a sub-nanosecond pulsed LED (EPLED
320) as an excitation source. Fluorescence decay times were
determined from the decays using the least squares fit method.
The fitting was assumed to be correct when the goodness-of-fit
value w2 was lower than 1.2. Fluorescence quantum yields were
measured on a C9920-02G absolute quantum yield (F) measurement
system from Hamamatsu (Hamamatsu Photonics Deutschland
GmbH, Herrsching am Ammersee, Germany). All measurements
were performed using a 3 ml quartz cuvette (Hellma GmbH,
Germany) with 1 cm light path. All measurements were obtained
for samples with optical densities below 0.15.
2.3. Quantum-chemical calculations
All quantum mechanical calculations were made at the DFT level
using the GAUSSIAN09 package80 and GABEDIT 2.4.6 Graphical
User Interface.81 The 6-31G* basis set and the B3LYP functional
were used. The polarizable continuummodel (PCM) was used in all
calculations to account for the solvent influence (chloroform).82
The absorption and emission spectra and excited state geometries
were obtained from time dependent DFT (TDDFT) singlet calcula-
tions. The reported lowest unoccupied molecular orbitals (LUMO)
energy values are read as DFT highest occupied molecular orbital
(HOMO) level reduced by the TDDFT energy gap.
2.4. OLED preparation
Indium tin oxide (ITO)-coated glass with a sheet resistance of
about 8–12 O sq1 (Sigma-Aldrich) was used for preparing the
OLED, while the cathode was made from Al. The hole-conductive
layer (HTL) was PEDOT: PSS poly(3,4-ethylenedioxythiophene):
poly(styrenesulfonate) (Sigma-Aldrich). Synthesized low molecular
materials were used for the preparation of the light-emitting layer
(EML). All measurements were performed using laboratory power
supply EA-PS 2032-025 (Fig. 1).
3. Results and discussion
3.1. Synthesis
The chemical structure and synthetic route to the pyrene deriva-
tives are illustrated in Scheme 1. Bromination of pyrene (1) with
one to four equivalents of bromine gave the mono-, di-, tri-, and
tetrabromopyrenes, respectively. The bromination resulted in
1-bromopyrene (2), 1,6-dibromopyrene (3) or 1,4-dibromopyrene (4),
1,3,6-tribromopyrene (5), and 1,3,6,8-tetrabromopyrene (6),21
respectively. Mono- and dibromopyrene were prepared in DCM,
while in the case of tri- and tetrabromopyrene we used nitro-
toluene as a solvent. The cross-coupling reaction of these bromo-
pyrenes with 2-(tributylstannyl)furan under the conditions of the
Stille reaction gave mono-, bis-, tris-, and tetrakis(furyl) pyrenes
7–11, respectively. For the preparation of di(furyl)pyrenes we used
Fig. 3 Normalized fluorescence emission spectra for all dyes in chloroform.
Fig. 4 Electronic absorption spectra for all dyes in chloroform (in ex.
coefficient units).
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a mixture of 1,6-dibromopyrene (3) and 1,4-dibromopyrene (4).
We successfully isolated 1,6-di(furyl)pyrene (8) from 1,4-di(furyl)-
pyrene (9). Instead of 2-(tributylstannyl)furan we used 2-(tributyl-
stannyl)thiophene to prepare the thienyl derivative of pyrenes 12–15.
The reactions were conducted under easy-to-perform, mild
conditions with moderate to good yields. All compounds studied in
this work were obtained by the Stille cross-coupling methodology
according to the procedure reported in our previous work
(Scheme 1).83–86 Table 7 presents the melting points of the
synthesized dyes.
Table 1 Absorption and emission properties of the studied thienyl derivatives of pyrene
Name/struktur labs (nm) e (M
1 cm1) lem (nm) F (%) Dn (cm
1) t (ns) kf (10
8 s1) knr (10
8 s1)
292 2 4000 435 19.7 3893 0.40 4.9 20.1
372 34 000 461
268 28 000 470 22.0 3354 0.46 4.8 17.0
315 31 000
406 36 000
295 27 000 435 22.2 3893 0.61 3.6 12.8
372 34 000 461
280 25 000 405 15.1 4044 0.95 1.6 8.9
348 26 000
305 27 000 446 18.1 3220 0.43 4.2 19.0
390 40 000 464
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22762 | Phys. Chem. Chem. Phys., 2015, 17, 22758--22769 This journal is© the Owner Societies 2015
3.2. Optical measurements
Electronic absorption spectra collected for thienyl and furyl
derivatives are shown in Fig. 2 and in Fig. 4, respectively. Unlike
for pyrene itself, for which three bands are observed in its
absorption spectrum, most of the studied thienyl and furyl
derivatives have only two absorption bands.
The derivative containing four thiophenes exhibits similar
absorption features to pyrene; however, the spectrum displays a
significant red shift. This feature can be associated with pyrene
or furan electron transitions mixed with the transitions charac-
teristic for thiophene. Depending on the derivative, the higher
energy transitions (presumably p- p*) can be observed in the
Table 2 Absorption and emission properties of the studied furyl derivatives of pyrene
Name/structure labs (nm) e (M
1 cm1) lem (nm) F (%) Dn (cm
1) t (ns) kf (10
8 s1) knr (10
8 s1)
297 31 000 433 67.1 2546 1.6 4.2 2.1
390 42 000 463
330 32 000 479 65.8 2379 1.8 3.7 1.9
430 32 000
299 30 000 433 68.7 2679 1.9 3.6 1.6
388 33 000 463
289 29 000 403 38.2 2810 3.3 1.2 1.9
362 29 000 423
315 35 000 460 63.2 2651 1.7 3.7 2.3
410 39 000 480
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range of 280–315 nm, while the lower energy transitions
(presumably n - p*) can be found in the spectral range
between 350 nm and 405 nm. The n - p* transitions can be
associated with the presence of heteroatoms (O or S) within the
dye structures. A bathochromic shift can also be observed with
an increasing number of electron-donating thiophene or furan
moieties within the chemical dye structure. However, for the
thienyl derivatives the observed shift is lower than the one
for furyl derivatives. For the higher energy band the shift is
approximately 35 nm for thienyl and 50 nm for furyl derivatives,
while for the lower energy band the shift is respectively larger
with 55 nm and 75 nm, respectively. Both, hyperchromic effect
and hypochromic effect are also observed for molecules with
different numbers of thiophene moieties. Both effects can be
associated with the structural symmetry. In non-symmetrical
systems, the absorption increases with the number of thio-
phene moieties, while for symmetrical molecules it decreases.
Depending on the derivative and the investigated absorption
band, molar extinction coefficients (e) determined on the basis
of the Beer–Lambert law were found in the range of 24 000–
40 000 M1 cm1 for thienyl derivatives and in the range of
29 000–42 000 M1 cm1 for furyl derivatives. Noticeably, the
e values are basically in the same order of magnitude as the
corresponding values for pyrene itself. The summary of para-
meters determined for thienyl and furyl derivatives based on
absorption measurements are presented in Table 1 and Table 2,
respectively.
The steady-state fluorescence emission spectra collected for
thienyl and furyl derivatives are shown in Fig. 3 and in Fig. 5,
respectively. For both classes of compounds, a bathochromic
Fig. 5 Normalized fluorescence emission spectra for all dyes in
chloroform.
Fig. 6 Experimental (top panel) and TDDFT electronic absorption spectra of the pyrene derivatives K1–K5.
Fig. 7 Experimental (top panel) and TDDFT fluorescence spectra of the
pyrene derivatives K1–K5.
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shift is observed with an increasing number of electron-donating
(thiophene or furan) groups and the relative ratios between
corresponding peaks are different for different derivatives.
Noticeably, when two substituents are present within the
chemical structure either in cis or trans form, the fluorescence
emission spectra are identical, which shows that the position of
substituent has no effect on the emission frequencies. This
effect has been observed both for thienyl and furyl derivatives.
Importantly, pyrene emission is still dominating in the emis-
sion observed for derivatives with only one side group, but for
the derivative with four substituents the spectrum is almost
completely merged into one bold spectrum, even though the
separate peaks can still be recognized. The spectra collected for
derivatives with 2 and 3 substitutes are more structured. The
merging effect can be associated with decreasing energies due
to radiationless deactivation. In all cases, the third band on the
Table 3 Molecular parameters derived from (TD)DFT calculations
HOMO
[eV]
LUMO
(=Eg  HOMO) [eV]
Eg (absorption)
[eV nm1]
Eg (emission)
[eV nm1]
Average dihedral angle between the
central moiety and the substituents
in ground/excited state [deg]
K1 5.23 2.25 2.97/417 2.39/518 133/153
K2 5.15 2.47 2.68/463 2.16/573 130/144
K3 5.23 2.25 2.98/416 2.39/518 131/152
K4 5.30 2.08 3.22/384 2.65/467 134/159
K5 5.18 2.37 2.81/440 2.28/544 131/148
Table 4 Graphical representation of HOMO and LUMO orbitals in the studied molecules in the ground and excited states
Compound HOMO LUMO HOMO – excited state LUMO – excited state
K1
K2
K3
K4
K5
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spectra stays virtually unaffected and only a red shift is
observed for it. Independent from the spectral features similar
for both classes of compounds, significant differences in
photophysical properties can be noticed when quantum yields
(F) and decay times (t) are considered. The thienyl derivatives
exhibit significantly lower F (70% vs. 20%) and much shorter
fluorescence lifetimes (from 0.4 to 0.95 ns compared toB2 ns)
when compared to their furan-substituted counterparts. Notice-
ably, the fluorescence quantum yield is virtually independent of
the number of substituents and their orientation (cis or trans).
For the thienyl derivatives the non-radiative processes rate
constant knr is on average 5 times larger than the radiative
process rate constant kf, while for the furyl derivatives kf was on
average two times greater than knr. This result is a clear
evidence for the domination of the non-radiation processes in
the deactivation path of thienyl derivatives. In comparison to
furyl derivatives, the thienyl derivatives have larger Stokes shifts
on average of about 1000 cm1. This is another evidence for the
domination of non-radiative processes in the thienyl based
systems. All the photophysical properties determined for thienyl
and furyl pyrene derivatives based on fluorescence measure-
ments are also summarized in Table 1 and Table 2, respectively.
3.3. Quantum-chemical methods
3.3.1. Thienyl derivatives of pyrene. The results of the DFT
calculations are presented in Fig. 6 and 7 as well as in Tables 3
and 4. All of the studied molecules are optically active, they
absorb light in the UV-violet spectral range and emit in the
violet-blue part of the spectrum. Noticeably, the theoretical
TDDFT predictions are in good agreement with experimental
absorption and fluorescence spectra apart from the under-
estimation of the energy gap by 0.35 eV (equivalent to approxi-
mately 70 nm). However, this deviation is often encountered
in DFT calculations. Nonetheless, the trend along the series
K1–K5 is well reproduced in the theoretically derived spectra,
including the very close overlapping of K1 and K3 in both
absorption and emission spectra. The order of the rising energy
gap is K2o K5o K1 = K3o K4. This is clearly connected to the
number of thiophene substituents adding their electrons to the
molecular conjugate system. Interestingly, the overlap of K1
and K3 spectra indicate that in the case of an isomer mixture
the relative position of the substituents does not influence the
energy levels of HOMO and LUMO orbitals as the substituents
contribute to the molecular orbitals in a similar manner (see
also Tables 3 and 4).
HOMO and LUMO orbitals are distributed throughout the
whole molecule for all studied compounds (Table 4), which is
due to the partially planar structures of both ground and
Fig. 8 TDDFT (bottom panel) and experimental (top) absorption spectra of the compounds K6–K10.
Fig. 9 TDDFT (bottom panel) and experimental (top) fluorescence spectra
of the compounds K6–K10. K6 and K8 in bottom panel closely overlap.
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22766 | Phys. Chem. Chem. Phys., 2015, 17, 22758--22769 This journal is© the Owner Societies 2015
excited states (Table 3). The large overlap between HOMO
and LUMO orbitals results in quite efficient absorptions and
emissions.
3.3.2. Furyl derivatives of pyrene. The optical properties of
the studied compounds K6–K10 obtained from TDDFT calcula-
tions confirm the influence of each additional furan substituent
Table 5 Molecular parameters derived from (TD)DFT calculations
HOMO [eV]
LUMO
(=Eg  HOMO) [eV]
Eg (absorption)
[eV nm1]
Eg (emission)
[eV nm1]
Average dihedral angle between the
central moiety and the substituents
in ground/excited state [deg]
K6 5.10 2.32 2.78/446 2.33/531 150/164
K7 4.95 2.53 2.42/512 2.07/599 154/162
K8 5.09 2.29 2.80/443 2.33/531 149/168
K9 5.23 2.14 3.09/402 2.63/471 150/168
K10 5.02 2.43 2.59/478 2.18/568 151/162
Table 6 Graphic representation of HOMO and LUMO orbitals in the studied molecules in the ground and excited states
Compound HOMO LUMO HOMO – excited state LUMO – excited state
K6
K7
K8
K9
K10
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on the absorption and emission properties (Fig. 8 and 9, Table 5).
The TDDFT-predicted UV-VIS absorption spectra presented in
Fig. 8 are in very good agreement with experimental data apart
from the underestimation of the energy gap by approximately
0.4 eV commonly encountered in such calculations. Nevertheless,
the relative spectral positions of the lowest energy absorption
peak, attributed by the TDDFT calculations to the HOMO–LUMO
transition, are reproduced well in the calculation. The order of
the rise in the energy gap is K7o K10o K6 = K8o K9 and this is
also found in the emission spectra, both theoretically derived and
experimentally observed (Fig. 9). It is quite clear that the HOMO–
LUMO energy gap and the related optical properties depend
on the number of furene substituents attached to the pyrene
molecule. Interestingly, the spectra measured for the K6 and K8
compounds with two furyl units in trans- and cis- positions
respectively, are nearly overlapping. Apparently, the contribution
of the furyl substituents to the crucial HOMO and LUMO orbitals
is independent of their position in the compounds, as can be
seen in Table 6.
3.4. OLED preparation
Fig. 1 shows the layer structure of the OLED device with details
on the used organic compounds and the function of each layer.
Indium tin oxide (ITO)-coated glass (size 5  5 cm) with a sheet
resistance of about 8–12 O sq1 was used as the backing
material. ITO deposited on the glass was cleaned by sonication
in a detergent solution and then rinsed using de-ionized water.
An aqueous solution of PEDOT/PSS (poly(3,4-ethylenedioxy-
thiophene)/poly(styrenesulfonate)) (HTL) forming a hole con-
ductive layer, was deposited onto ITO. Then water was removed
under low pressure in a nitrogen atmosphere. The light-emitting
layer (EML) (thienyl and furyl derivatives of pyrene) was deposited
on the cathode, which was an aluminum plate of size 0.5 0.5 cm.
Plates were superimposed onto each other. Then, the device was
connected to a DC power source and a 24 V voltage was passed
through it to give a current equal to 0.2 A. A bright light with a
color characteristic for the corresponding pyrene derivatives was
observed under such conditions. Fig. 10 displays the working
diode prepared using 1,3,6,8-tetra(2-furyl)-pyrene as an active
emitting layer.
4. Conclusions
In this work we have presented photophysical properties and
theoretical calculations for two new classes of lowmolecular weight
materials based on a pyrene core substituted either with thiophene
or furan units. All studied molecules can absorb light in the UV or
violet visible range and emit in the blue-violet spectral region. We
observed that the replacement of the thiophene by furan increases
the fluorescence quantum yield, most likely due to the more planar
structure of the former allowing for a efficient contribution of the p
electrons. Furthermore, we described DFT calculations and TDDFT
simulations for the presented materials. These quantum-chemical
calculations fully support obtained experimental data. HOMO and
LUMO orbitals are delocalized uniformly on the pyrene core and
its aryl substituents. Theoretical calculations provided values for
the HOMO–LUMO gaps for the neutral states of the compounds.
Compounds described in this paper fulfill the technological
requirements for materials to be successfully applied in the con-
struction of organic–electronic devices as demonstrated by the
OLED device presented in this paper. In order to verify the practical
usefulness of the synthetized materials we built a prototype diode
(OLED) using thienyl and furyl derivatives of pyrene and also
bithienyl derivatives of triazine. Obtained OLEDs emitted blue light
at a voltage of 12 V and a yellow light at a voltage of 24 V. Following
the physico-chemical measurements and a successful practical
application in OLEDs, the synthesized heterocyclic units can be
used as innovative, efficient, cost-effective and environmentally
friendly (mercury free) materials for light sources. These units
can be flexibly designed and emit a broad spectrum of visible light,
when appropriately tuned. The manufacturing of this type of light
sources is one of the global research priorities, because it is based
on a combination of new organic materials and economic produc-
tion methods, thus enabling a variety of innovative products to be
designed. Considerable progress in nanotechnology that has been
made in recent years has resulted in the launch of the first
electronic products made of organic materials.
Acknowledgements
This work was supported within the research grant no 2011/01/N/
ST4/02251 from National Science Centre, Poland. Calculations have
Table 7 Melting point of thienyl and furyl derivatives of pyrene
Compound K1 K2 K3 K4 K5 K6 K7 K8 K9 K10
Melting point (1C) 238–239 291–292 129–130 85–86 154–155 151–152 229–230 91–92 Oil 124–125
Fig. 10 Effect of the organic light-emitting diodes made from 1,3,6,8-
tetra(2-furyl)-pyrene.
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22768 | Phys. Chem. Chem. Phys., 2015, 17, 22758--22769 This journal is© the Owner Societies 2015
been carried out in Wroclaw Centre for Networking and Super-
computing (http://www.wcss.wroc.pl, grant No.135). The presented
study was partially funded by the German Federal Ministry of
Environment (promotional reference No. 0325417, Reaktherm).
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