Synthesis, ellipsometry and non-linear optical features of substituted 1,3,5-triphenylpyrazolines

Article abstract of DOI:10.1016/j.dyepig.2018.11.004

Ellipsometric and nonlinear optical properties of new, differently substituted, 1,3,5-triphenylpyrazolines dyes, were studied. Results of theoretical calculation within a framework of density functional theory (DFT) technique were verified by spectroscopic ellipsometry and optical second harmonic generation (SHG) experiment at fundamental laser wavelength 1064 nm. Absorption bands and complex refractive indices were determined. Principal role of 2-thienyl substituent for first order nonlinear optical properties was demonstrated.

Full text of DOI:10.1016/j.dyepig.2018.11.004

Accepted Manuscript
Synthesis, ellipsometry and non-linear optical features of substituted 1,3,5-
triphenylpyrazolines
Ewa Gondek, Jacek Nizioł, Andrzej Danel, Mateusz Kucharek, Jarosław Jedryka,
Paweł Karasiński, Natalia Nosidlak, Andrij A. Fedorchuk
PII:
S0143-7208(18)31772-8
https://doi.org/10.1016/j.dyepig.2018.11.004
DYPI 7148
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 9 August 2018
Revised Date: 16 October 2018
Accepted Date: 2 November 2018
Please cite this article as: Gondek E, Nizioł J, Danel A, Kucharek M, Jedryka Jarosł, Karasiński Paweł,
Nosidlak N, Fedorchuk AA, Synthesis, ellipsometry and non-linear optical features of substituted 1,3,5-
triphenylpyrazolines, Dyes and Pigments (2018), doi: https://doi.org/10.1016/j.dyepig.2018.11.004.
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ACCEPTED MANUSCRIPT
Synthesis, ellipsometry and non-linear optical features of substituted 1,3,5-
triphenylpyrazolines
1
,*
2
3
3
4
Ewa Gondek , Jacek Nizioł , Andrzej Danel , Mateusz Kucharek , Jarosław Jedryka , Paweł
5
1
6
Karasiński , Natalia Nosidlak , Andrij A.Fedorchuk
1
2
3
4
5
6
Institute of Physics, Cracow University of Technology, ul. Podchorążych 1, 30-084
Kraków, Poland
AGH University of Science and Technology, Faculty of Physics and Applied Computer
Science, al. Mickiewicza 30, 30-059 Krakow, Poland
Institute of Chemistry, Department of Food Technology, University of Agriculture,
ul. Balicka 122, Krakow, Poland
Institute of Optoelectronics and Measuring Systems, Faculty of Electrical Engineering,
Czestochowa University Technology, ul. Armii Krajowej 17, Czestochowa, Poland
Department of Optoelectronics, Silesian University of Technology, ul. B. Krzywoustego 2,
4
4-100 Gliwice, Poland
Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla i
Mefodiya Str., 6, 79005, Lviv, Ukraine
(*) corresponding author: egondek@pk.edu.pl
Keywords: Nonlinear optics, pyrazolines, DFT method, spectroscopic ellipsometry
Abstract: Ellipsometric and nonlinear optical properties of new, differently substituted, 1,3,5-
triphenylpyrazolines dyes, were studied. Results of theoretical calculation within a framework
of density functional theory (DFT) technique were verified by spectroscopic ellipsometry and
optical second harmonic generation (SHG) experiment at fundamental laser wavelength 1064
nm. Absorption bands and complex refractive indices were determined. Principal role of 2-
thienyl substituent for first order nonlinear optical properties was demonstrated.
1
.
Introduction
Compounds containing azole groups represent an important part of organic materials
applied in modern organic electronics. For example thiazole derivatives have been
successfully applied in organic field-effect transistors [1], phosphorescent OLEDs [2] and in
organic solar cells [3]. Similarly, pyrazole derivatives have been incorporated in
electroluminescent devices [4, 5] and studied because of their nonlinear optical (NLO)
properties [6]. A particular case present 1,3,5-triarylpyrazolines. At the early stage of
investigations they were exploited as photo- and radio-luminophores [7, 8] or as optical
brighteners [9]. Recently they have been used also for fabrication of plastic scintillators [10].
Because of excellent photoemissive properties, an array of 1,3,5 triarylpyrazolines have been
2
+
2+
also applied as sensitive material for detection of various ions, for example Cd , Zn [11] or
2
+
Hg [12] and in OLEDs of strong bright blue-green emission [13].
Unfortunately triarylpyrazolines have a tendency to crystallization, but this
inconvenience disappears if they are chemically bounded to a polymer. The DFT (density
functional theory) calculations for pyrazoline derivatives revealed large ground state dipole
moment magnitude. Such a feature is an important asset to fabricate bulk materials with NLO
1

ACCEPTED MANUSCRIPT
properties using electrical poling process [14]. For several pyrazoline derivatives substituted
with –CN and nitro groups the phenomenon of amplified spontaneous emission and two-
photon absorption [14] also was observed. An efficient light second harmonic generation
(SHG) was found to be typical for push-pull systems of 1-phenyl-2-pyrazolines substituted
with nitro-styryl groups [15]. Nevertheless, despite their promising potential,
triarylpyrazolines have not yet been sufficiently well studied in domain of nonlinear optics.
The last factor has motivated us to pursue studies of 1,3,5-triphenylpyrazolines and the impact
of different substituents on optical properties.
Here we report on chemical synthesis, theoretical calculations related to electronic
structure, experimental measurements involving ellipsometry and SHG. The obtained results
suggest that 1,3,5-triphenylpyrazolines may be an interesting alternative to already known
molecules in domain of nonlinear optics.
2
. Materials
2
.1 Synthesis
The synthesis reaction is depicted in Fig. 1. The starting aldehydes 1 or 4 were prepared by
reaction of appropriate pyrazolines with DMF/POCl . Aroylacetonitriles
3
2
a or 2b were synthesized from acetonitrile and methyl thiophene-2-carboxylate or methyl 4-
methoxybenzoate and sodium hydride. In the final step the aldehydes have been condensed
with carbonyl compounds in the presence of catalytic amount of piperidine.
Fig. 1. Principal scheme of the studied pyrazoline derivatives synthesis. “Process” means ethanol/piperidine
(
cat)/8 hours/boiling.
Synthesis-general procedure.
2

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A round-bottomed flask (25 mL) equipped with a magnetic stirring bar and reflux condenser
was filled with 96% ethanol (10 mL), aldehyde 1 or 4 (1 mmol), aroylacetonitrile 2 (1.2
mmol) and three drops of piperidine as catalyst. Such prepared contents were boiled under
reflux condenser for 8 hours. After this the reaction mixture was cooled and the precipitate
was filtered off and crystallized from appropriate solvent. The final purification was
accomplished with column chromatography filled with silica gel 60 (70-230 mesh) using
toluene/ethyl acetate (4:1) as eluent (compound PR1 and PR2) or with preparative TLC
1
(
compound PR3). The product’s contents were confirmed with H NMR spectra and
elemental analysis
Compound PR1:
1
Red crystals, 200 mg, 90%, mp. 246-8 °C (toluene). H NMR(600 Hz, DMSO, δppm): 8.17(s,
1H, Hvinyl), 8.11-8.08(m, 2H), 8.01(d, J = 9Hz, 2H), 7.87-7.84(m, 2H),7.51-7.45(m, 3H), 7.39-
7.35(m, 2H), 7.31-7.23(m, 5H), 7.18-7.14(m, 3H), 5.81-5.77(m, 1Hpyrazoline ring), 4.09-4.01(m,
1Hpyrazoline ring). The peaks from the third proton of pyrazoline ring (ca. 3.20 ppm) were
covered with d -DMSO signals. Anal. cald for. C H N OS: C 75.81; H 4.61; N 9.14. Found
6
29 21
3
C 75.96; H 4.73; N 8.97.
Compound PR2:
1
Yellow crystals, 200 mg, 88%, mp. 178-180 °C (toluene). H NMR(600 Hz, CDCl , δppm):
3
7
7
7
1
.96(s, 1Hvinyl); 7.93(d, J = 9.2Hz, 2H), 7.82-7.81(m, 2H), 7.77-7.76(m, 2H), 7.56(t, J =
.45Hz, 1H), 7.47(t, J = 7.69 Hz, 2H), 7.43-7.40(m, 3H), 7.35(t, J = 7.41Hz, 2H), 7.29(t, J =
.37Hz, 1H), 7.26-7.24(m, 2H), 7.12(d, J = 8.2Hz, 2H), 5.44(dd, J = 12.07Hz, 5.35Hz,
Hpyrazoline ring), 3.93(dd, J = 12.1Hz, 17.34Hz, 1Hpyrazoline ring), 3.25(dd, J = 5.4Hz, 17.3Hz,
Hpyrazoline ring). Anal. cald for. C H N O: C 82.10; H 5.11; N 9.26. Found: C 81.76; H 4.97;
1
31
23
3
N 9.05.
Compound PR3:
1
Red crystals, 220 mg, 94%, mp. H NMR(600 Hz, CDCl , δppm): 8.26(dd, J = 3.9Hz,
3
1.02Hz, 1Hthiophene), 8.19(s, 1H, Hvinyl), 7.96(d, J = 9.15Hz, 2H), 7.96(d, J = 9.1Hz, 2H),
7.70(dd, J = 4.97Hz, 1.01Hz, 1Hthiophene), 7.49(d, J = 7.2Hz, 2H), 7.39(t, J = 7.21Hz, 4H),
7.32(t, J = 7.27Hz, 2H), 7.26-7.22(m, 3H), 7.17-7.19(m, 1Hthiophene), 7.09(d, J = 8.81Hz, 2H),
6.7(d, J = 16.4 Hz, 1Hstilbene), 5.42(dd, J = 12.00Hz, 5.21Hz, 1Hpyrazoline ring), 3.81(dd, J =
17.1Hz, 12.1Hz, 1Hpyrazoline ring), 3.14(dd, J = 17.2Hz, 5.13Hz, 1Hpyrazoline ring). Anal. cald for.
C H N OS: C 76.74; H 4.77; N 8.63. Found: C 76.83; H 4.75; N 8.56.
31
23
3
Pyrazole derivatives are difficult to be deposited in form of a thin layer, because they may be
crystallized or form other aggregates. A common remedy to this constraint is to disperse
molecules inside an optically inert, polymeric matrix, typically in polymethyl metacrylate
(PMMA). The synthesized dyes were co-dissolved together with PMMA for each dye in
identical molar ratio. Next, thin blend films were deposited on soda-lime microscope slides by
spin-coating.
2
.2 Quantum chemical theoretical studies
Quantum chemical calculations of dipole moments, first order (β) (at a wavelength of 1064
nm) and second order (γ) molecular nonlinear hyperpolarizabilities as well as determination of
HOMO and LUMO, were done using Gaussian W09 computer program package [17] within a
3

ACCEPTED MANUSCRIPT
framework of DFT and B3LYP functional supplement with the standard 6-31G(d) basis set.
An example of calculated HOMO and LUMO orbitals are depicted for PR1 in Fig.2.
Following the DFT calculations it was established that the studied molecules have partial
charge transfer, namely - a part of the electron density from a HOMO could be transferred on
the 2-thienyl (PR1 and PR3) or on corresponding benzene ring (PR2) at the LUMO, although
it is distributed throughout the π-conjugated chain.
(
a)
(b)
Fig. 2 Visualization of modelled theoretically HOMO (a) and LUMO (b) orbitals for PR1.
Numerical results of quantum chemical calculations are compared to experimental data in
Table 2, further in the text, in the disscussion of experimental data.
3
. Equipment and Methods
Measurements of absorbance, refractive indices n, extinction coefficients
κ
and film
thicknesses d were carried out with application of spectroscopic ellipsometer Woollam
M2000 (J.A. Woollam Co. Inc.). Measurements of absorbance were carried out in
transmission mode and the other ones were done in reflection mode. The base of ellipsometry
is effect of the change in polarization of light reflected on thin film. This effect is determined
by the ratio of Fresnel reflection coefficients for both s- and p- polarized light [18]:
rp
i∆
ρ
=
= tan Ψ
e
,
(1)
rs
where
Ψ
(amplitude ratio) and
∆
(phase shift) are determined for ellipsometry experiment.
) requires a model
Determination of optical function from measured ellipsometric angles (
Ψ,∆
that describes an interaction of the incident light with the film or application of B-spline one,
which don’t need any assumptions about physical properties of film.
In our studies the dependences of the ellipsometric angles
Ψ, ∆ on photon energy E
(dispersion characteristics) were measured with light beam conveyed to the sample at angles
6
0°, 65° and 70°. The probing light on the sample surface was formed by a beam a spot about
2
.5 mm.
The data obtained experimentally (Ψ and ∆) were explored as follows. First, samples
thicknesses were deduced using Cauchy approximation to the data from transparent part of the
optical spectrum. To exclude noise from the recorded characteristics of the ellipsometric
angles, their dispersions were approximated with B-spline functions [19,20]. The number of
included free terms was the least possible, necessary to obtain a reasonable mean square error
4

ACCEPTED MANUSCRIPT
of the fit. The fitting procedure retained only physical solutions, fulfilling Kramers–Kronig
relations. To evaluate dielectric and optical function dispersion (complex permittivity and
complex refractive index) in a more rigorous manner, the experimental data are usually
parameterized using different theoretical models. In the case of the reported samples, the best
matching parameterization of B-spline approximations have been occurred using of Tauc-
Lorentz model [21]. This model describes very well optical functions for different amorphous
materials like semiconductors [22], insulators [23], many organic [24] or even biological
materials [25]. This model simulates the dispersion of imaginary part of the dielectric function
by multiplying the Tauc [26] joint density of states and the
obtained from the Tauc-
Lorentz oscillator model. The
real part) of the dielectric function is derived from using
Kramers–Kronig integration, as shown in Eqs 2 and 3.
2









AE B E − E
0
(
g
)
⋅
2
1



, E > Eg ,
2
(2)
2
2
2
ε
(
)
E =
E
2
(
E − E0
)
+ B E



0
E ≤ Eg.
2
∞
x ⋅ε2
( )
dx.
2
x
(3)
ε1(E) = ε1(∞) + P
∫E
2
π
g
x − E
In the above equations
means optical energy band gap,
- principal peak inter-band
transition, - amplitude and - broadening term,
P stands for the Cauchy principal part of
the integral. The integral in Eq.(3) can be solved in closed form [21].
Measurements of non-linear optical properties for the studied materials were carried out
using measurement system presented in Fig. 3. The studied powder-like chromophore were
electrically poled and oriented in the dc-electric field about 8 kV/cm. The sample orientation
controlled by polarimetry was equal to about 83 % in terms of observed optical polarization
variation.
5

ACCEPTED MANUSCRIPT
Fig. 3 A measuring set-up for determination of the second harmonic generation efficiency versus the varying
fundamental energy power density at wavelength of 1064 nm.
The second harmonic generation (SHG) were observed for
s-p polarization of the incident
light. The samples were illuminated with fundamental 1064 nm pulsed beam from a Nd:YAG
1
1
0 ns nanosecond laser (Spectra-Physics Lasers Inc., USA, Quanta Ray INDI), pulse duration
2 ns, repetition rate 12 Hz and energy 60 mJ. The laser energy density was continuously
2
tuned by Glan polarizers up to 150 J/m . All the measurements were carried out in classical
architecture with rotation stage as outlined in Fig. 3 and already explained in Ref. 16.
4
. Experimental results and discussion
In Fig. 4 are shown absorption spectra for the studied chromophore embedded in PMMA
matrix, measured using transmission. The first absorption maxima occur at ca. 2.5eV
(λ=495.6 nm). However PR2, in contrast to the two remaining chromophore, features two
distinct absorption maxima in the available wavelength range and the first one is apparently
weaker than for the case of PR1 and PR3. The PR2 dye contains a phenyl pendant group
instead of 2-thienyl as PR1 and PR3. This observation may indicate a crucial role of 2-thienyl
group on significant variation of electronic levels.
Fig. 4. Typical absorbance spectra for the studied molecules in PMMA matrix. The spectra are re-scaled
vertically, but relative magnitudes are retained.
In Fig. 5 are plotted as an example, experimentally obtained
Ψ and ∆ dependence versus light
energy. This picture illustrates level of noises occurred during the experiment studies and
accuracy of B-spline approximation (dashed lines). The part of data (energies lower than
2
eV, compare to Fig.4) used to determine thicknesses of the sample were characterized by
particularly low noise.
6

ACCEPTED MANUSCRIPT
(
a)
(b)
(a) and (b) functions dispersions measured for PR2 embedded in PMMA
Fig. 5 Ellipsometric angles
matrix. Solid lines represent experimental data while dashed ones are B-spline fits. Labels on graphs
correspond to the probing light incidence angle.
Although Cauchy parameterization allows to calculate thickness and real part of refractive
index, it does not provides any parameters describing observed electronic molecular
transitions. That is why (as it was explained earlier in this report), the experimental data were
fitted using of Tauc-Lorentz model. An example of experimental data fitted with Tauc-
Lorentz are depicted in Fig. 6. In the case of PR2 dye two spectral peaks had to be included in
the model contrary to the two other dyes. However, it was not possible to parameterize
unambiguously the tail originating from spectral resonances appearing in vacuum UV spectral
ranges. So it was excluded from calculations. However, Tauc-Lorentz fits very well agreed to
the B-spline plot.
Fig. 6 Dispersion relations of refractive index (left), extinction coefficient (right) for PR2 chromophore
dispersed in PMMA matrix,. Solid lines represent data derived from B-spline fits, while dashed lines depict
data obtained from Tauc-Lorentz parameterization.
In this way, values parameters necessary to interpret results of SHG experiment were
obtained. Calculated energies of optical band gap Eg, transition energies E0, absorptions and
real part of refractive indices for the wavelengths of interest are summarized in Table 1.
7

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Table 1 Samples thickness and parameters in Tauc-Lorentz parameterization deduced from ellipsometry data.
Parameter/Sample
Thickness [nm]
Eg [eV]
PR1
81.2
PR 2
54.5
PR 3
80.3
1.946 ± 0.002
2.477 ± 0.001
1.882 ± 0.001
2.537 ± 0.006
3.185 ± 0.008
0.040
1.819 ± 0.010
2.459 ± 0.001
E0 (1) [eV]
E0 (2) [eV]
abs (λ=532nm)
n (λ=532nm)
n (λ=1064nm)
0.151
1.784
1.551
0.153
1.716
1.548
1.690
1.546
Fig. 7 Dependences of the SHG output versus the fundamental laser energy density for the studied materials.
Fig. 7 presents the results of the SHG signal dependences versus the fundamental energy
density. The observed SHG intensities from the studied samples are significantly lower than
the reference Nd:BiB O crystals [27]. because poling process was not the subject of
3
6
optimization. To eliminate the scattering background the additional interferometer filters at
20 nm and 542 nm have been applied. Additionally to evaluate the parasitic fluorescence
5
background the rare earth doped glasses have been applied [28]. Nevertheless, the dependence
is close to parabolic, as expected theoretically. The least intense signal was observed for PR2,
despite the lowest absorption at wavelength 532 nm. This observation again points out the
role of 2-thienyl substituent.
Table 2 Comparison of experimental and theoretical parameters. The dipole moments D and first order
(2)
molecular hyperpolarizabilities β were theoretically calculated, while values of second order susceptibility χ
were deduced from results of SHG studies obtained for PMMA blends with the studied dyes.
Parameter/sample
PR1
PR2
PR3
Dipole moment (
D) [Debye]
11.82
11.47
11.81
First order hyperpolarizability (β) [esu]
5
.35
4.11
1.69
7.58
2.67
-28
×10
(2)
Second order susceptibility
χ
, [pm/V]
2.12
8

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In Table 2 are summarized results of theoretical calculations concerning molecular electronic
(
2)
properties and values of second order susceptibilities
χ
, deduced from SHG measurements.
, but hyperpolarizibility
As can be seen, all three molecules have a similar dipole moments
D
β
increases in the following order – PR2, PR1 and PR3. It follows then, that 2-thienyl is more
efficient donor. In addition the case of PR3 confirms, that the extension of π-conjugated
length in the opposite end of molecule, converts this side to a more efficient acceptor. The
(2)
similar order was found for susceptibilities
χ . Taking into account similar dipole moments
and molecular volume of all three dyes, poling efficiency can be supposed identical for
(2)
PMMA films blended with these dyes. For this reason susceptibilities
χ
can be directly
related to hyperpolarizibility . In other words, results of DFT calculations were confirmed by
β
SHG experiment. The obtained values are commensurable with other organic dyes [30,31],
however they have more smooth dispersions of the optical functions which do they more
applicable.
5
. Conclusions
Joint theoretical and experimental studies concerning linear and nonlinear optical properties
of new 1,3,5-triphenylpyrazolines have been reported. Since steric architecture may be crucial
for poling efficiency, three similar molecules were synthesized. The sole difference was in
extremities of push-pull system. It was established how this differences may enhance (or
decrease nonlinear optical properties). It was established that the extension of π-conjugated
length in the opposite end of molecule, converts this side to a more efficient acceptor. The
(2)
similar order was found for susceptibilities
demonstrated.
χ . The crucial role of 2-thienyl substituent was
Acknowledgements
This work was partially supported by the National Science Center – Poland on the basis of
decision DEC-2017/25/B/ST7/02232 and by the Faculty of Physics and Applied Computer
Science AGH UST statutory tasks within subsidy of Ministry of Science and Higher
Education.
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Highlights
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New, differently substituted, 1,3,5-triphenylpyrazolines dyes, were synthesised.
DFT calculations for pyrazoline derivatives were made.
Optical properties of the new materials were determined via ellipsometric way.
Nonlinear properties of studied materials were determined.