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Spectrochimica Acta Part A 79 (2011) 17571761

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Structural, thermal and optical characterization of a Schiff base as a new organic

material for nonlinear optical crystals and lms with reversible
Mario Rodrguez a , Gabriel Ramos-Ortz a, , Jos Luis Maldonado a , Vctor M. Herrera-Ambriz a ,
Oscar Domnguez b , Rosa Santillan b , Norberto Farfn c , Keitaro Nakatani d
Centro de Investigaciones en ptica A.P. 1-948, 37000 Len, Gto., Mexico
Departamento de Qumica, Centro de Investigacin y de Estudios Avanzados del IPN, 07000, Apdo. Postal. 14-740, Mxico D.F., Mexico
Facultad de Qumica, Departamento de Qumica Orgnica, Universidad Nacional Autnoma de Mxico, 04510, Mxico, D.F., Mexico
Laboratoire de Photophysique et Photochimie Supramolculaires et Macromolculaires (UMR 8531 du CNRS), Ecole Normale Suprieure de Cachan,
Avenue du Prsident Wilson, 94235, Cachan, France

a r t i c l e i n f o a b s t r a c t

Article history: Macroscopic single crystals of (E)-5-(diethylamino)-2-((3,5-dinitrophenylimino)methyl)phenol (DNP)

Received 15 February 2011 were obtained from slow cooling of chloroform or dichlorometane saturated solutions at controlled
Received in revised form 12 May 2011 temperature. X-ray diffraction analysis showed that this compound crystallizes in a noncentrosymmet-
Accepted 16 May 2011
ric space group (P21 21 21 ). Thermal analysis was performed and indicated that the crystals are stable
until 260 C. Second-order nonlinear optical properties of DNP were experimentally investigated in solu-
tion through EFISH technique and in solid state through the Kurtz-Perry powder technique. Crystals of
Single crystal growth
compound DNP exhibited a second-harmonic signals 39 times larger than of the technologically use-
Organic compound
Nonlinear optical materials
ful potassium dihydrogenphosphate (KDP) under excitation at infrared wavelengths. In addition, the
second-order nonlinear optical properties of DNP were also studied at visible wavelengths through the
photorefractive effect and applied to demonstrate dynamic holographic reconstruction.
2011 Elsevier B.V. All rights reserved.

1. Introduction development is needed before they can be used in commercial

applications such as optical signal processing, high-speed electro-
Organic molecules that possess nonlinear optical (NLO) prop- optic modulators, data storage and optical frequency conversion
erties have emerged as interesting construction blocks for a new [6]. In this context, research about organic NLO molecules in the
generation of photonic applications due to their large second- and solid state, especially crystals, is the bridge to bind fundamental
third-order hyperpolarizabilities, which in many cases are com- research and real applications. The search of efcient second-order
parable or higher than those for inorganic materials [1]. In the NLO crystals is, in fact, the exploration of polar crystals in which
eld of molecular engineering is well established that pushpull the macroscopic properties reect the internal asymmetric molec-
molecules formed by a -conjugated system substituted by an elec- ular arrangement [7]. Thus, the improvement of the second-order
tron donor group in one end of the -backbone, and by an electron NLO response in organic crystals is commonly based on molec-
acceptor group in the other end, comprise signicant second- and ular units possessing high molecular rst hyperpolarizability ()
third-order nonlinear optical responses [2,3]. This is because the (pushpull architecture) that can be packed in a chiral arrange-
-conjugated system provides an effective pathway for the redistri- ment.
bution of electronic charge across the entire length of conjugation Schiff bases are important organic compounds obtained from
when the perturbation from an external electric eld is present. The reversible condensation between amino and carbonyl groups,
intense research in the topic of nonlinear materials during the last which is one of the most fundamental reactions in chemistry
two decades has produced many -conjugated organic molecules [8]. Azomethine or imine also known as Schiff bases, have been
with high NLO responses [25], but despite these advances more applied successfully in several areas, such as biological chem-
istry [9], materials science [10], and organic synthesis [11]. On
the other hand, polar crystals grown from Schiff bases have been
Corresponding author. Tel.: +52 477 441 42 00; fax: +52 477 441 42 09. obtained through the vanishing of their dipole moment [12], inser-
E-mail addresses: garamoso@cio.mx (G. Ramos-Ortz), jlmr@cio.mx tion of chiral fragments [13] or groups that favor the hydrogen
(J.L. Maldonado). bond interactions [14]. In this work we report the synthesis of a

1386-1425/$ see front matter 2011 Elsevier B.V. All rights reserved.
1758 M. Rodrguez et al. / Spectrochimica Acta Part A 79 (2011) 17571761

Fig. 1. Molecular structure of compound DNP.

Fig. 2. Photograph of single crystals grown from compound DNP. Each tiny square
is of 1 mm2 .
new pushpull Schiff base with double meta-substitution (3,5-
nitro) that promotes the chiral packing in the solid state; this
vents at 35 C. By slow solvent evaporation at room temperature
property was exploited to grow organic nonlinear crystals show-
only the formation of microcrystals was promoted; to carry out
ing a second-harmonic generation (SHG) efciency 6 times larger
the X-ray diffraction analysis these microcrystals were used. In
than that for urea and 39 times larger than that for potassium
contrast, by preventing the solvent evaporation and from a slow
dihydrogenphosphate (KDP) at the IR wavelength of 1907 nm.
decrease of the temperature (at a rate of 5 C per day, controlled by
Furthermore, the second-order nonlinearities of this Schiff base
using a hotplate), bulk red crystals were obtained after 3 days with
were also demonstrated at a visible wavelength (633 nm) through
typical dimensions of about 2 mm 2 mm 0.5 mm and with good
dynamic holography experiments.
optical quality (Fig. 2).

2. Experiment
3.3. UVvis absorption

For the preparation of DNP the reagents 3,5-dinitroaniline and

To determine the transparency range of the DNP single crystals
4-diethylaminobenzaldehyde were obtained from SigmaAldrich
their UVvis absorption spectra were acquired in the wavelength
(USA) and used without any further treatment. 1 H and 13 C NMR
range from 200 to 1100 nm. Fig. 3 displays a typical absorption
spectra for the title compound were recorded on a JEOL Eclipse
spectrum obtained with these crystals. This gure shows that the
GX 270. Chemical shifts (ppm) were relative to (CH3 )4 Si for
1 H and 13 C. Infrared spectra were measured on a Perkin-Elmer samples were optically transparent in the wavelength range from
650 nm to 1200, a feature that promotes possible optical applica-
Spectrum RX1 spectrophotometer using KBr pellets while UVVis
tions in devices operating at the near infrared wavelength range,
spectra were obtained with a Perkin-Elmer Lambda 900 spec-
i.e., ultrafast modulators and switches [6,7]. Inset of Fig. 3 shows
trophotometer. X-ray diffraction studies of single crystals were
the absorption spectrum of compound DNP in chloroform solution,
performed on an Enraf-Nonius diffractometer with a CCD detector
where the maximum absorption band at 413 nm is assigned to the
(MoK = 0.71073 A, monochromator: graphite). Frames were col-
n * electronic transition.
lected at T = 293 K via / rotation. Direct methods SHELXS-86 [15]
were used for structure solution and SHELXL-97 [16] program pack-
3.4. FT-IR studies
age for renement and data output. Thermal analysis was carried
out using a Thermobalance Mettler Toledo TGASDTA851e thermal
The functional groups present in the structure of compound DNP
were conrmed through Fourier transform infrared (FTIR) spec-
trum analysis. In this case a sample was prepared by processing
3. Results and discussion organic microcrystals with KBr into pellet form. The IR spectrum of
DNP shows the OH stretching peak at 3415 cm1 and for CO at
3.1. Synthesis

Compound DNP (Fig. 1) was prepared using the typical syn-

thetic method for imine derivatives [8]. A ethanol solution of
3,5-dinitroaniline and 4-diethylaminobenzaldehyde was reuxed
by 2 h, and after complete reaction the solution was cooled down
to room temperature and then the product was precipitated and
separated by ltration. The compound was puried by recrystal-
lization processes in chloroform previous to the complete chemical
characterization. 13 C NMR spectra for compound DNP showed a
set of thirteen signals corresponding to the same number of carbon
atoms in its structure. In particular, the signal at 163.7 ppm con-
rmed the iminic moiety and the signal at 164.1 ppm showed the
presence of the phenoxy carbon, which is involved in the NHO
intramolecular hydrogen bond.

3.2. Crystal growth

Recrystallized powder of DNP was used to prepare saturated Fig. 3. UVvis absorption spectrum from a DNP single crystal (thickness: 1 mm).
solutions with the use of chloroform or dichloromethane as sol- Inset: Absorption spectrum of compound DNP in chloroform solution.
M. Rodrguez et al. / Spectrochimica Acta Part A 79 (2011) 17571761 1759

bond NHO in DNP promotes the planar conformation on the

salicilydene fragment, with AD distance of 2.633(3) and AHD
angle of 146.2(5) . However, for the complete -backbone structure
a non planar conformation is observed, this is because the phenyl
ring of the aniline moiety is deviated 47.4 from the plane of the
salicilydene part. Crystal packing of compound DNP is controlled
by intermolecular non classical hydrogen interactions promoted
by NO2 groups. Crystallographic data for compound DNP have
been deposited in the Cambridge Crystallographic Data Centre
as supplementary publications No. CCDC 808275. Copies of the
data can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, U.K. (fax: +44 1223 336 033;
deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).

3.6. Thermal analysis

Fig. 4. IR spectrum for compound DNP.
In order to know the thermal behavior of the macroscopic crys-
1236 cm1 . C C and C N stretching and annular stretching appear tals, thermogravimetric analysis (TG and DTA) of samples was
at 1637 cm1 and 1585 cm1 , respectively, and a band at 1338 cm1 carried out for the temperature range of 25500 C in a nitrogen
due to CN bond. The nonsymmetric and symmetric stretching atmosphere at the heating rate of 10 C/min. The resulting ther-
bands of N O bonds in NO2 groups appear at 1532, 1512 cm1 and mogram and its differential thermogravimetric curve are shown in
1319, 1303 cm1 , respectively (Fig. 4). Fig. 6. TG graph indicates that the crystals of compound DNP are
thermo stable until 260 C, after this temperature and until 320 C,
3.5. X-ray diffraction analysis a strong loss of weight is shown. The DTA thermogram shows an
endothermic peak at 297 C, which is attributed to the melting point
X-ray diffraction analysis was carried out on monocrystals; this of the crystal and to a complete material decomposition. It is impor-
technique conrmed the structure of the compound DNP. The tant to mention that the solvent used for the crystallization process
CH hydrogen atoms were placed in geometrically calculated posi- was not present in the crystal structure according to the invariant
tions using a riding model. OH hydrogen atoms were localized by behavior of the TG plot between 25 and 260 C.
difference Fourier maps and their bond distances and isotropic tem-
perature factors were rened freely. The crystal packing of the new 3.7. Second-order nonlinear optical characterization
imine derivate is presented in Fig. 5. This compound crystallizes
in the P21 21 21 space group and in an orthorhombic crystal sys- The rst hyperpolarizability () was experimentally determined
tem, with one isolated molecule in the asymmetric unit cell. The by using the electric eld induced second-harmonic (EFISH) tech-

crystallographic data for this crystalline system are a = 6.6367(2) A, nique [17]. Briey, the EFISH experimental apparatus is described
and c = 30.9362(9) A.
b = 8.1942(2) A, The intramolecular hydrogen as follows: a Nd:YAG laser emitting picosecond pulses (1.064 m

Fig. 5. Crystal packing of compound DNP.

Fig. 6. TG and DTA analysis of crystals obtained from compound DNP.

1760 M. Rodrguez et al. / Spectrochimica Acta Part A 79 (2011) 17571761

Fig. 7. (a) Diffraction efciency and (b) refractive index modulation as a function of E for thick solid PR lm with composition DNP:PVK:ECZ:C60 at 25:49:25:1 wt.%. Inset of
(a): (i) photograph of the object, (ii) holographic reconstruction of the object obtained through the diffracted signal at an external applied electric eld E = 45 V m1 .

at 10 Hz repetition rate) was used to pump a hydrogen cell (1 m the concentration of 25:49:25:1 wt.%, respectively. Details of sam-
long, 50 bar). The outcoming Stokes-shifted radiation at 1.907 m ple preparation and holographic experimental characterization can
generated by the Raman effect was used as the fundamental beam be found elsewhere [24,25]. Briey, for sample preparation, a small
to carry out the EFISH experiments. This fundamental beam was piece of the ready PR polymer was melted at 130135 C between
focused into dichloromethane solutions of DNP (at concentrations two ITO-coated transparent glasses. The PR lm thickness (110 m)
of 5 mM and 10 mM) which were contained in a cell with quartz was controlled by using calibrated glass spacers.
windows in a wedge congurations separated by 1 mm. The cen- In the PR experiments an external electric eld (E) is applied
trosymmetry of the solution was broken by dipolar orientation of through the ITO electrodes of the composite lm containing DNP,
the chromophores by applying a high voltage (5 kV) synchronized this breaks the centrosymmetry of the lm and induces second-
with the laser pulses. The second-harmonic signal (at 953.5 nm) order nonlinear optical effects. The PR polymer lms were tested
was selected through a suitable interference lter, and detected by means of the widely used holographic technique of Four Waves
by a photomultiplier tube. Therefore the ONL response was pro- Mixing (FWM) [2] with a HeNe laser (633 nm). In this technique
portional to the product of being the dipole moment of the refractive index modulation of the PR sample is estimated from
the chromophore. The EFISH measurements gave a value of plots of light diffraction efciency at different values of E. Fig. 7(a)
3 1046 esu D for compound DNP, which is 2.5 times smaller than shows the diffraction efciency plot with a maximum value of
that shown by a Schiff base reported by Lacroix [18]. The reduc- 15.8% at E = 72 V/m while Fig. 7(b) shows the refractive index
tion of is a consequence of the sustitution of the NO2 groups modulation (n) plot estimated from the diffracted signal. The
in 3,5-positions, situation that decreases in some extent the dipole maximum n value is 0.6 103 which is larger than that of some
moment of the molecule. Thus, althouhg there is a reduction in of the best existing PR inorganic crystals such as lithium niobate
the dipolar moment, such substitution was employed to promote (LiNbO3 ) and lithium tantalate (LiTaO3 ) [3,6]. This diffracted signal
intermolecular links that lead to the formation of chiral crystals is rather small in comparison with highly efcient PR lms [25],
[19]. A more efcient NLO compound would, certainly, contain a however, in terms of photonic applications is possible to have holo-
NO2 group in the para-position to complete the push-pull charac- graphic image reconstruction with just 3% of diffraction efciency
ter, but it is well know that such condition favors the crystallization [26]. As a demonstration of dynamic holographic application, a 2-
in centrosymmetric space group [18]. dimensional image of an object (numeral 4 ) was recorded in a
Additionally, the SHG efciency of DNP in solid state was PR polymer lm doped with compound DNP. Here the eld E was
evaluated by the KurtzPerry powder test [20,21]. Samples were 45 V/m and according to Fig. 7(a) a 2.8% of diffraction efciency
prepared by crushing crystalline powder of compound DNP is achieved. Photographs of the object and the holographic recon-
between two transparent glass plates. Samples were exposed to struction of its image are shown in the inset of Fig. 7(a). In this case
picosecond laser radiation at 1.907 m, and the SHG signal was the holographic process is reversible (dynamic) as the image can
detected by a photomultiplier tube after eliminating the pump light be erased or reconstructed by simply eliminating or applying the
with a color lter. The efciencies were quantied versus a refer- electric eld E.
ence sample of powdered urea. The SHG efciency in average was
six times larger than that of urea. By comparing the SHG capacity of
urea and that of the technologically useful KDP [22], it results that 4. Conclusions
single crystals grown from DNP exhibited a SHG efciency about
39 times higher than KDP. This study illustrates that chromophores A new Schiff base with a moderate pushpull character was
with rather modest value can exhibit sizeable SHG efciencies, synthesized. EFISH experiments conrmed the molecular second-
once an optimized molecular orientation is achieved in the solid order nonlinear optical response in solution with a value for the
state. product of 3 1046 esuD. Although the double meta substitu-
To further assess the nonlinear behavior of DNP we imple- tion of NO2 groups in the molecular structure of DNP presumably
mented photorefractive (PR) characterization of solid state thick diminishes the molecular dipole moment, it generates a packing
lms containing such compound. The PR phenomenon consists in a noncentrosymmetric arrangement capable of producing SHG
in the reversible modulation of the refractive index of a mate- signals 6 and 39 times more efcient than that for urea and KDP,
rial through the Pockels effect [23] and has many technological respectively, under excitation at IR wavelengths. The second-order
applications such as dynamic volume holography and reversible nonlinear optical features of the Schiff base molecule DNP were also
data storage [2,3]. PR lms were prepared using the guest:host studied in amorphous lms in which reversible noncentrosymmet-
approach by mixing the pushpull Schiff base DNP with the ric arrangement was induced through the application of an external
photo-conducting polymeric matrix polyvinylcarbazole (PVK), the electric eld to observe the PR effect; the latter was subsequently
plasticizer ethylcarbazole (ECZ) and the sensitizer fullerene C60 at used for holographic reconstruction at visible wavelengths.
M. Rodrguez et al. / Spectrochimica Acta Part A 79 (2011) 17571761 1761

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