Synthetic Metals 160 (2010) 535–539

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Short communication

Synthesis and study of nonlinear optical properties of 4-substituted

benzylidene-2-phenyl oxazol-5-ones by Z-scan technique
Y.L.N. Murthy a,∗ , V. Christopher a , U. Viplava Prasad a , P.B. Bisht b , D.V. Ramanaih b ,
B.S. Kalanoor b , S. Akbar Ali b
a
Department of Organic Chemistry, Andhra University, Visakhapatnam, 530003, India
b
Department of Physics, Indian Institute of Technology, Madras, Chennai 600036, India

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

Article history: 4-substituted benzylidene-2-pheny-5-oxazolones (5 new compounds) were synthesized by both con-
Received 3 February 2009 ventional and microwave assisted synthesis and were characterized by gas chromatography-mass
Received in revised form spectrometry (GCMS), Fourier-transform nuclear magnetic resonance (FT-NMR) spectroscopy, and
29 September 2009
Fourier-transform infrared (FT-IR) spectroscopy. The synthetic methodology of these new compounds is
Accepted 21 November 2009
presented. The results of nonlinear optical study of 4-(4 -N,N-dimethyl benzylidene)-2-phenyl oxazol-
Available online 16 December 2009
5-(4H)-one by using Z-scan techniques are discussed here. The ultrafast fluorescence decay of the
molecule has been explained to be due to the electron transfer from the dimethyl group to the carbonyl
Keywords:
5(4H)-Oxazolone
group.
Nonlinear optics © 2009 Elsevier B.V. All rights reserved.
Picosecond laser

1. Introduction 2. Experimental

Heterocycles containing oxazolone ring are important targets in
synthetic and medicinal chemistry, because of their importance as
potentially active compounds [1–5]. 5(4H)-Oxazolones, represent
a large family of ␲-conjugated materials, having potential appli-
cations in photonics and electronics, have also been studied for
nonlinear optical properties [6]. Their large nonlinearity originates
from extensively delocalized ␲-electron distribution. Studies of
nonlinear optical properties of these dyes with applications in pho-
tonics [7–13] can be carried out by degenerate four wave mixing
(DFWM) and Z-scan techniques [14–17].
The oxazolone derivatives have been found to exhibit NLO
properties in solid state as well as in solutions [18,19]. Their pho-
tophysical properties are important for potential applications in
photonics and electronics [10,11]. In the present work, for the first
time we have synthesized five new 5(4H)-oxazolones. We have
studied the nonlinear optical properties of one of the compounds
(VII), by using Z-scan technique under picosecond and cw pump-
ing. The photophysical parameters of this compound are also given
here.
∗ Corresponding author. Tel.: +91 891 284 4686; fax: +91 891 2525611.
E-mail address: murthyyln@yahoo.co.in (Y.L.N. Murthy).
The melting points were determined on Toshnival hot plate
and are uncorrected. 1 H NMR spectra were recorded on 90 MHz
spectrophotometer (JEOL-JNM EX-90) using deutrated chloroform
(CDCl3 ) as solvent and tetra methyl silane (TMS) as internal
standard. I.R. values were recorded on a I.R spectrophotometer
(Avatar-Thermo Nicolett) in KBr.
2.1. General procedure for the Synthesis of 5(4H)-oxazolones by
both conventional and microwave assisted synthesis
Benzoyl glycine (I) (2.6 mmol), was added to different sub-
stituted aromatic aldehydes (II–VI) (2.3 mmol), in presence of
powdered sodium acetate, (2.4 mmol), high grade acetic anhy-
dride, (7.2 mmol), and refluxed at 110 ◦ C with constant stirring
for 4 h. The crude product (VII–XI) was separated, filtered and
washed with ice cold ethanol and boiling water, recrystallized from
chloroform in good yields [20]. Further we have also confirmed
by microwave assisted synthesis [21,22] of compound (VII). All
the reactants were taken in the same mole ratios as that were
taken in the usual conventional synthesis. It was made sure, before
the reaction, that acetic anhydride was not evaporated from the
mixture. The compound obtained was recrystallized from hot
benzene with a yield of 80% and HPLC purity of 99.5% (retention
time: 2.51 min). The product obtained by this method was iden-
tical with that of the conventional method. Adopting the above
general procedure, five new 5(4H)-Oxazolone derivatives (VII–XI)

0379-6779/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2009.11.029
536 Y.L.N. Murthy et al. / Synthetic Metals 160 (2010) 535–539
Scheme 1. Synthesis of oxazolone derivatives (VII-XI).
were synthesized by both conventional and microwave meth-
ods, and were characterized employing advanced spectroscopic
data. (Scheme 1). The spectral and analytical data of synthesized
compounds (VII–XI) are given below.
4-(4 -N,N-dimethyl benzylidene)-2-phenyl oxazol-5-(4H)-one
(VII): mp: 215 ◦ C, yield: 90%, IR (KBr) cm−1 : 1646 (Ar, C C str),
1762 (C O str), 1446 (C–N str). 1 H NMR (90 MHz, CDCl3 ) % (ppm):
3.1 (s, 6H), 6.7 (m, 2H), 7.4 (s, 1H), 7.5–7.7 (m, 2H), 8.0–8.1 (m,
5H). GC-MS m/z 292. Anal. Calcd. For C18 H16 N2 O2 : C (73.97%), H
(5.47%), N (9.58%). Found: C (73.89%), H (5.51%), N (9.52%).
4-(4 -Chloro benzylidene)-2-phenyl oxazol-5-(4H)-one (VIII): mp:
173 ◦ C, yield: 85%, IR (KBr) cm−1 : 1654 (Ar, C C str), 1766 (C O
str), 1450 (C–N str). 1 H NMR (90 MHz, CDCl3 ) % (ppm): 7.3 (s, 1H),
7.1–7.7 (m, 6H), 8.0–8.2 (m, 3H). GC-MS m/z 283. Anal. Calcd. For
C16 H10 NO2 Cl: C (67.72%), H (3.52%), N (4.93%). Found: C (67.69%),
H (3.55%), N (4.88%).
4-(4 -methoxy benzylidene)-2-phenyl oxazol-5-(4H)-one (IX):
mp: 159 ◦ C, yield: 87%, IR (KBr) cm−1 : 1652 (Ar, C C str), 1768 (C O
str), 1448 (C–N str). 1 H NMR (90 MHz, CDCl3 ) % (ppm): 3.9 (s, 3H),
7.2 (s, 1H), 7.1–7.7 (m, 4H), 7.8–8.2 (m, 5H). GC-MS m/z 279. Anal.
Calcd. For C17 H13 NO3 : C (73.11%), H (4.65%), N (5.01%). Found: C
(73.07%), H (4.66%), N (5.05%).
4-(3 -methoxy-4 -hydroxy benzylidene)-2-phenyl oxazol-5-(4H)-
one (X): mp: 210 ◦ C, yield: 82%, IR (KBr) cm−1 : 1650 (Ar, C C
str), 1755 (C O str), 1452(C–N str). 1 HNMR (90 MHz, CDCl3 )
% (ppm): 4.0 (s, 3H), 7.2 (s, 1H), 7.0–7.5 (m, 4H), 7.7–8.0 (m,
4H). 8.2 (s, 1H). GC-MS m/z 295. Anal. Calcd. For C17 H13 NO4 l:
C (67.72%), H (3.52%), N (4.93%). Found: C (67.46%), H (3.53%),
N (4.64%).
4-(3 -nitro benzylidene)-2-phenyl oxazol-5-(4H)-one (XI): mp:
192 ◦ C, yield: 75%,IR (KBr) cm−1 : 1657 (Ar,C C str), 17681 (C O
str), 1530 (N–O str). 1 H NMR (90 MHz, CDCl3 ) % (ppm): 7.5 (s, 1H),
7.4–7.9 (m, 5H), 8.1–8.5 (m, 3H). GC-MS m/z 295. Anal. Calcd. For
C16 H10 N2 O4 : C (67.72%), H (3.52%), N (4.93%). Found: C (67.46%), H
(3.53%), N (4.64%).
2.2. Steady state and time resolved fluorescence measurements
The absorption spectra were recorded using a UV–visible
spectrometer (JASCO, V-570) in quartz cell of 1 mm thickness.
Absorption scan of solvent alone was taken to ensure the absence
of impurities in the pump wavelength region. Fluorescence spectra
were recorded using a fluorescence spectrometer (JASCO, FL-6600)
in a quartz cell of thickness 10 mm.
The second harmonic of a picosecond Nd: YAG laser (Quanta
systems, Himalaya series, 10 Hz, 30 mJ at 1064 nm) and a cw Ar+
laser (Coherent, model Innova 70) were used for the Z-scan experi-
ments. The transmitted energy as a function of the sample position
was measured by a PMT (Hamamatsu, IP28) for the cw laser, and by
a photodiode (Becker and Hickle, PDI-400) for the pulsed laser. The
experiment includes the transmittance measurement as a function
of the sample position at the far field by using a double convex lens
of focal length 200 mm. In the closed aperture Z-scan experiment,
a circular aperture of 3 mm diameter was used before the detector.
Whereas for the open aperture Z-scan experiments a large diameter
double convex lens of focal length 200 mm was used in place of the
circular aperture. The beam was nearly Gaussian and we have con-
sidered the 86% beam criterion [23]. The radius of the beam waist
(wo ) was 24 ␮m with corresponding Rayleigh range (zo ) of 3.5 mm.
The sample thickness (1 mm) was less than the Rayleigh range to
fulfill the thin sample approximation condition. Decay time mea-
surements were carried out with the technique of time-correlated
single photon counting technique (TCSPC) [24]. The analysis of
decay profiles was done by using software (FAST, Edinburgh Instru-
ments). The fitting of the decay curves was judged by the value of
reduced chi square (2 ) and weighed residuals.
3. Results and discussion
3.1. Absorption and fluorescence spectra
Fig. 1 shows the absorption and fluorescence spectra of one of
the compounds (VII) in benzene. The value of extinction coefficient
of 3.4 × 104 M−1 cm−1 is obtained at the absorption maximum. The
compound VII has the emission maximum at 522 nm.
The molecule (VII) is having extended conjugation throughout
its structure with oxazolone ring as the chromophore. The lone
pair of electrons on nitrogen of N,N-dimethyl group exerts posi-
tive mesomeric effect. Thus positive charge is acquired by nitrogen
of N,N-dimethyl group and the negative charge by the oxygen of
carbonyl group, respectively (Fig. 2).
The synthons for this molecule, both benzoyl glycine or hippuric
acid (I) as well as p – N,N-di-methyl benzaldehyde (II) are colourless
crystalline compounds. However, after condensation the molecule
 Y.L.N. Murthy et al. / Synthetic Metals 160 (2010) 535–539 537

orbitals are formed, the lower energy molecular orbital for the com-
pound (VII) is occupied in the ground state. The transition from this
molecular orbital to the new upper molecular orbital is responsi-
ble for the new lower energy absorption band observed in this case
(Fig. 3).

3.2. Optical nonlinear study by Z-scan

3.2.1. Under picosecond pumping

Fig. 1. Absorption (solid line) and fluorescent spectrum (o) of the molecule (VII) in
benzene (5 × 10−5 M).
acquires reddish–orange colour. This is probably because during
the condensation, the bond formation between the molecular pairs
is brought about when filled ␲-orbitals of donor (II) overlap with
the depleted orbitals of the acceptor (I). The two new molecular
The observed open aperture (OA) profile (Fig. 4, Panel A) of
compound VII under picosecond pulse pumping, did not exhibit
any nonlinear absorption under low values of irradiance i.e., upto
Io = (5.19 ± 0.78) × 1010 W/cm2 . However, a 10-fold increase in the
irradiance results in the nonlinear absorption. The Z-scan profile
has a symmetric valley around the focal point, which indicates
the effect of reverse saturable absorption (RSA). The compound
VII has a small absorption coefficient of 8 × 102 M−1 cm−1 at
532 nm (Fig. 1). Since working wavelength is far from the peak
of the absorption i.e., in the low absorbance region, the nonlin-
ear absorption is due to either excited state absorption (ESA) or the
two-photon absorption (TPA). These effects suppress the peak and
relatively enhance the valley in the measured profile. The closed
aperture (CA) profile was also recorded. Although the signal to
noise ratio was not very high, it showed a peak-valley structure

Fig. 2. Charge transfer mechanism in compound VII.

Fig. 3. Modifications to the orbital on synthesis of compound VII.

Fig. 4. (A) Closed aperture Z-scan, (B) Open aperture Z-scan profiles of VII (5 × 10−3 M) pumped. with picosecond laser (Io = 5.19 ± 0.78 × 1011 W/cm2 ).
538 Y.L.N. Murthy et al. / Synthetic Metals 160 (2010) 535–539

Table 1
Photophysical parameters of compound VII in benzene [5 × 10−3 M].

␭abs a (nm) ␭em b (nm) Picosecond pumping (532 nm) Io = (5.2 ± 0.8) × 1011 W/cm2 cw pumping (514.5 nm) Io = (2.50 ± 0.3) × 103 W/cm2
−11 −9
ˇ (cm/W) (×10 ) im (3)
(esu) (×10 ) ˇ (cm/W) (×10−2 ) im (3) (esu)

466 522 2.97 ± 0.28 7.17 ± 0.30 3.5 ± 0.4 8.1 ± 0.1
a
Wavelength of absorption maximum.
b
Wavelength of emission maximum.

(Fig. 4 panel B) which indicates the negative sign for the refractive
nonlinearity and the positive sign for the absorptive nonlinearity
[25].
In case of the open aperture Z-scan experiments the following
expression is used to analyze the obtained transmission (T(z)) as a
function of the scanning distance z [26].

T (z) = 1 + T (z) + Tϕ (z) (1)

where T˚ (z) and T (z) are the transmittance due to nonlinear
refraction (NLR) and nonlinear absorption (NLA), respectively given
as
4x
T (z) = 
(x2 + 9)(x2 + 1)
2(x2 + 3)
T (z) = − 
(x2 + 9)(x2 + 1)

where x = z/zo in which zo is Rayleigh range, ˚ and  are

parameters determining phase shift near the focal point as a
result of nonlinear refraction and nonlinear absorption respec-
tively, ˚ = kn2 Io Leff and  = ˇIo Leff /2. Here Io is laser radiation Fig. 5. Open aperture Z-scan profiles of VII (5 × 10−3 M) pumped with cw laser.
intensity at the focal point, Leff ( = [1 − exp(−˛0 L)]/˛0 ) is the effec- (Io = 2.50 ± 0.34 × 103 W/cm2 ).
tive length of the sample with L as the sample length,˛0 is the linear
absorption coefficient, n2 is nonlinear refractive index and ˇ is the
aromatic system enables a sort of intramolecular charge transfer
nonlinear absorption coefficient.
in the molecule [29]. The molecule is conjugated throughout its
Generally, in OA profile, mainly the absorptive nonlinearity is
structure, which acts as an electron bridge.
dominant, and the contribution of the refractive nonlinearity can
This suggests that VII resembles twisted intramolecular charge
be neglected. Therefore, the obtained OA profile of Fig. 4(A) was
transfer (TICT) type molecular structure of Nile Red, a laser dye
fitted by keeping the refractive term as zero. Even after includ-
which has exc – 552 nm and em – 636 nm in methanol. Thus
ing the NLR term in the transmission function upto 10% did not
compound VII on electronic excitation initially forms a moder-
improve the fitting. This confirmed that fact that in OA profile, the
ately non polar state with geometry similar to that in the ground
contribution of NLR is negligible even with tenfold increase in the
state. Therefore in the nonpolar excited state the molecule under-
irradiance.

3.2.2. Under cw pumping

The Z-scan study was also carried out under cw laser pumping
(514.5 nm) to verify the thermal contribution to the observed non-
linearity. The observed symmetric valley structure around the focal
point shows the effect of RSA (Fig. 5). Various parameters of com-
pound VII in benzene are given in Table 1. It can be seen that under
pulsed (ps) excitation the optical nonlinearity is of the same order
as that of the other dyes [27]. However, with continuous pumping,
large values of (3) are observed. This is due to the thermal contri-
bution arising out of continuous absorption of the argon ion laser
by the sample [28].

3.3. Time resolved fluorescence and mechanism of intermolecular

charge transfer

The decay profile of the compound in benzene is shown in Fig. 6.

The measurement was done after completely blocking the scattered
light from pump. Even though the fluorescent decay data fall almost
on the data of the instrumental response function, a fit with the
single exponential function gives a decay time of 115 ± 12 ps. This
Fig. 6. Fluorescence decay profile of molecule (VII) [10−4 M] in benzene
indicates an extremely fast deactivation of the excited state in this
(exc = 470 nm) (Panel A). The data points are indicated by circles (o) and the thick
molecule. As described previously, the pushing (donating) effect of line shows the fit with the single exponential function. Panel B gives the residual for
N(CH3 )2 group and pulling effect exerted by carbonyl group and the fit.
 Y.L.N. Murthy et al. / Synthetic Metals 160 (2010) 535–539
goes an intermolecular transfer of an electron from donor N(CH3 )2
to the acceptor (aromatic system and carbonyl group), and this
is accompanied by a twist about the bond joining the donor and
acceptor groups to the molecule. The molecule goes from a nearly
planar [16], nonpolar state to highly polar TICT state in which the
donor and the acceptor moiety are mutually perpendicular. The
rate of TICT state formation is too fast to be observed with the
time resolution employed in the present study. Thus strong polarity
dependence of the TICT process is found to be responsible for the
mimics of the chromophore. Rhodamine dye lasers [30] and Rho-
damine B (in specific) have almost similar melting point (210 ◦ C)
as that of compound VII (215 ◦ C) with emi = 543 nm, although the
fluorescence quantum yields are very high.
4. Conclusions
In conclusion, we have synthesized five new oxazolone deriva-
tives via conventional and microwave assisted synthesis. The
nonlinear optical properties of compound (VII) have been studied
using the Z-scan method. Time-correlated single photon counting
measurements show that the compound (VII) has an extremely
short excited state decay time, indicating the fast electron transfer
within the molecule. The results are explained based on non-
radiative channels in these systems. The ESA and TPA appear to
be the phenomena responsible for the small value of the optical
nonlinearity.
Acknowledgement
We (PBB and BSK) thank CSIR, New Delhi for financial assistance.
We also thank DRDO for financial support.
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