The synthesis and NLO properties of 1,8-naphthalimide derivatives for both femtosecond and nanosecond laser pulses

Article abstract of DOI:10.1016/j.dyepig.2012.01.001

Four 1,8-naphthalimide derivatives were synthesized for new nonlinear optical(NLO) materials. Hydrazone group as a p-π structure was introduced into the molecule to extend conjugation and produce NLO properties. Their linear and nonlinear optical (NLO) properties were studied in details. The results show that these compounds possess strong excited-state absorption (ESA) properties and optical limiting with nanosecond laser pulses at 532 nm. Moreover, they also preserve the luminescence originated from naphthalimide and two-photon absorption (TPA) behaviour which can be observed under femtosecond laser pulses ranged from 750 to 870 nm. The broad-band optcial limiting properties of these compounds indicate that they can be potentially applicated in optical limiting materials.

Full text of DOI:10.1016/j.dyepig.2012.01.001

Dyes and Pigments 94 (2012) 271e277
Contents lists available at SciVerse ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
The synthesis and NLO properties of 1,8-naphthalimide derivatives for both
femtosecond and nanosecond laser pulses
Gao-Jie Ye a, Ting-Ting Zhao b, Zheng-Neng Jin a, Pei-Yang Gu a, Jia-Yuan Mao a, Qing-Hua Xu b,
,
a
,
a
c
Qing-Feng Xu a , Jian-Mei Lu , Na-Jun Li , Yin-Ling Song
*
*
a Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University(Dushuhu Campus),
Suzhou, Jiangsu 215123, PR China
b Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
c Key Laboratory of Optics of Jiangsu Province, College of Physics and Technology, Soochow University(Central Campus), Suzhou, Jiangsu 215006, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Four 1,8-naphthalimide derivatives were synthesized for new nonlinear optical(NLO) materials. Hydra-
Received 11 October 2011
Received in revised form
30 December 2011
Accepted 3 January 2012
Available online 30 January 2012
zone group as a p-p structure was introduced into the molecule to extend conjugation and produce NLO
properties. Their linear and nonlinear optical (NLO) properties were studied in details. The results show
that these compounds possess strong excited-state absorption (ESA) properties and optical limiting with
nanosecond laser pulses at 532 nm. Moreover, they also preserve the luminescence originated from
naphthalimide and two-photon absorption (TPA) behaviour which can be observed under femtosecond
laser pulses ranged from 750 to 870 nm. The broad-band optcial limiting properties of these compounds
indicate that they can be potentially applicated in optical limiting materials.
Keywords:
1,8-Naphthalimide
Hydrazone group
Ó 2012 Elsevier Ltd. All rights reserved.
Optical limiting
Excited-state absorption (ESA)
Two-photon absorption (TPA)
Pump probe
1. Introduction
absorption (ESA) materials at high energy end of the visible
(400e600 nm). Recently, optical limiting of fluorescent conjugated
The synthesis of new nonlinear optical (NLO) materials is
fundamental in the development of optoelectronic technologies.
Due to the low cost, easy fabrication and large NLO susceptibility,
organic materials with NLO properties are candidates for potential
applications in optical switching, computing, bistable elements,
optical limiting (OL) and logic devices [1e7]. Among these appli-
cations, optical limiting is one crucial important in the protection of
optical sensors or human eyes from laser beams. Optical limiter
requires that transmission of the substance is high at low-intensity
light but low instantly when exposed to intense laser radiation.
Optical limiting of organic materials mainly originats from
nonlinear absorption under laser irradiation, whose mechanism
includes excited-state absorption (ESA) [8e10] and two-photon
absorption (TPA), etc. [11e13]. Fullerenes (C60) and phthalocya-
nine complexes are commonly considered as classical excited-state
molecules caused by two-photon absorption (TPA) at the low
energy end of the visible (600e800 nm) have attracted much
attention. For example, Tavarekere and coworkers [8] found that
core-modified expanded porphyrins with large third-order
nonlinear optical response at low energy area; Xu et al. [10]
investigated the optical limiting property of a new fluorenyl-
based chromophore, whose mechanism is attributed to TPA.
However, most of the studies are focused on the OL properties at
a certain band of laser, the broad-band OL of organic materials
properties are studied relatively few. It’s probably due to the lack of
suitable NLO materials. To obtain a broadeband optical limiter
covering the whole visible region, Spangler [14] first suggested to
design OL chromophores in a bimechanistic fashion: (1) ESA
behaviour at high energy of the visible (400e600 nm) and (2) TPA
behaviour at the low energy of the visible (600e800 nm) [15,16].
Till now, few pure organic dyes with such properties have been
reported.
Inspired by this idea, we select some usual fluorescent dyes as
original chromophores. As a result, the 1,8-naphthalimide deriva-
tives have been extensively used in the dye industry as strongly
* Corresponding authors. Tel.: þ86 512 65880367; fax: þ86 512 65882875.
E-mail addresses: xuqingfeng@suda.edu.cn (Q.-F. Xu), lujm@suda.edu.cn,
jianmeilu_group@hotmail.com (J.-M. Lu).
0143-7208/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2012.01.001

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G.-J. Ye et al. / Dyes and Pigments 94 (2012) 271e277
Scheme 1. Preparation of NAxPHs.
absorbing dyes [17,18], novel therapeutics [19,20], as well as the
backbone of chemical probes [21,22]. Meanwhile hydrazone group
of the eCH]NeNHe functionality own good hole transport
property for technical applications in organic semiconductor
designing [23,24]. Its simple synthesis and low cost are the
advantages against other classes of charge transport materials.
In this paper, Four 1,8-naphthalimide derivatives containing
hydrazone group with different alky chains have been synthesized.
reduced (98%), 4-bromo-1,8-naphthalene anhydride (90%), Hydra-
zine hydrate (85%), Potassium carbonate (99%), Sodium hydroxide
(96%), anhydrous magnesium sulphate (98%) were purchased from
Shanghai Sinopharm. All reagents used as received without further
purification.
2.2. Instruments
1H NMR spectra were collected on an INVOA 400 Hz NMR
spectrometer. Tetramethylsilane was used as the internal reference
for the NMR analyses and CDCl3 as solvent. Elementary analyses
were conducted on a Carlo Erba-MOD1106 elementary analysis
The new derivatives based on hydrazone group with a p-
p struc-
ture exhibit good NLO absorption and optical limiting properties.
However, the unmodified 1,8-naphthalimide molecule has no NLO
absorption effect using nanosecond laser pulses at 532 nm.
Furthermore, due to the fluorescence of these compounds
preserved at about 550 nm, their TPA properties were also observed
by using femtosecond laser pulses ranged from 750 to 870 nm.
apparatus. UVevis spectra were recorded on a PerkineElmer l-17
spectrometer using a 1 cm square quartz cell. The fluorescence
spectra were measured on Edinburgh-920 fluorescence spectra
photometer (Edinburgh Co. UK) with a slit of 1 nm.
2. Sample preparation and experiments
2.3. Preparation of NAxPHs
2.1. Materials
The intermediate products were synthesized according to the
literature methods [25e27] as shown in Scheme 1. 10 mmol of
4-Vinyl benzyl chloride (90%), P-hydroxybenzaldehyde (99.9%),
P-nitrophenol (99.5%), Brominated alkanes (99%), iron powder
Fig. 1. UVevis spectra of NAxPHs in DMF.
Fig. 2. Fluorescent spectra of NAxPHs in DMF.

G.-J. Ye et al. / Dyes and Pigments 94 (2012) 271e277
273
Table 1
7.46 (m, 4H), 7.21 (d, 2H), 7.03 (m, 4H), 6.74 (m, 1H), 5.80 (d, 1H),
5.30 (d, 1H), 5.14 (s, 2H), 3.97 (t, 2H), 1.81 (t, 2H), 1.48 (m, 2H), 1.31
(m,10H), 0.92 (t, 3H). Elem. Anal. Calcd. For C43H43N3O4: C, 77.57; H,
6.51; N, 6.31; Found: C, 77.55; H, 6.52; N, 6.29. Mp: 262e264 ꢀC.
Photophysical properties of NA3PH, NA6PH, NA9PH and NA12PH.
Compounds lamax=nm lmb ax=nm
3
c/molꢁ1 Lꢁ1 cmꢁ1 fd
demax=GM sf/ns
NA3PH
NA6PH
NA9PH
NA12PH
464
464
464
464
554
554
554
554
2.20ꢂ104
2.41ꢂ104
2.24ꢂ104
2.28ꢂ104
0.16 90
1.68
1.69
1.66
1.71
NA12PH: yield: 61%. 1H NMR (CDCl3, 400 MHz)
d (ppm): 8.75 (s,
0.19 65
0.17 77
0.19 64
1H), 8.62 (m, 2H), 8.22 (s, 1H), 8.02 (s, 1H), 7.80 (d, 1H), 7.71 (t, 3H),
7.40 (m, 4H), 7.19 (d, 2H), 7.01 (m, 4H), 6.72 (m, 1H), 5.80 (d, 1H),
5.26 (d, 1H), 5.11 (s, 2H), 3.96 (t, 2H), 1.79 (t, 2H), 1.45 (m, 2H), 1.27
(m, 16H), 0.89 (t, 3H). Elem. Anal. Calcd. For C46H49N3O4: C, 78.05;
H, 6.98; N, 5.94; Found: C, 78.01; H, 6.96; N, 5.98. Mp: 249e251 ꢀC.
a, b: liner absorption and one-photon fluorescence maxima peak, respectively. c:
molar absorption coefficient. d: fluorescence quantum yield. e: the maximum two-
photon cross section. f: fluorescence lifetime.
4-hydrazino-N-(4-alkoxy) -phenyl-1,8-naphthalimide and 12 mmol
of 4-(4-benzyloxy-vinyl) benzaldehyde were refluxed for 4 h and
then cooled to room temperature. The product was obtained by
column chromatography with chloroform and ethylacetate.
2.4. Nonlinear optical instruments
2.4.1. Z-Scan measurements
NA3PH: yield: 46%. 1H NMR (CDCl3, 400 MHz)
d (ppm) : 8.86 (s,
The third-order optical nonlinear properties were measured via
the Z-Scan method. The Z-Scan method chooses Nd: YAG nano-
second laser as the light source, which owns a wavelength of
532 nm, a pulse width of 4 ns and a repetition rate of 10 Hz. The
pulse energy on the sample is 10e20 mJ, the thickness of the sample
cell is 2 mm. The measurement can be performed through closed
aperture and open aperture configurations.
1H), 8.63 (m, 2H), 8.27 (s, 1H), 8.01 (s, 1H), 7,85 (d, 1H), 7.70 (t, 3H),
7.46 (m, 4H), 7.21 (d, 2H), 7.01 (m, 4H), 6.76 (m, 1H), 5.81 (d, 1H),
5.31 (d, 1H), 5.14 (s, 1H), 3.92 (t, 2H), 1.83 (m, 2H), 1.06 (t, 3H). Elem.
Anal. Calcd. for C37H31N3O4: C, 76.40; H, 5.37; N, 7.22; Found: C,
76.43; H, 5.41; N, 7.26. Mp: 265e267 ꢀC.
NA6PH: yield: 51%. 1H NMR (CDCl3, 400 MHz)
d (ppm): 8.83 (s,
1H), 8.63 (m, 2H), 8.27 (s, 1H), 8.01 (s, 1H), 7.83 (d, 1H), 7.70 (t, 3H),
7.46 (m, 4H), 7.21 (d, 2H), 7.07 (m, 4H), 6.74 (m, 1H), 5.80 (d, 1H),
5.30 (d, 1H), 5.13 (s, 2H), 3.97 (t, 2H), 1.80 (t, 2H), 1.48 (m, 2H), 1.36
(m, 4H), 0.94 (t, 3H). Elem. Anal. Calcd. For C40H37N3O4: C, 77.02; H,
5.98; N, 6.74; Found: C, 77.04; H, 5.97; N, 6.78. Mp: 268e269 ꢀC.
The optical limiting test was based on the above described Z-
scan platform. An attenuator (Newport Co., USA) was fixed at the
luminous point of the laser light. The sample was placed at the lens
focus. By adjusting the attenuator, the incident energy increases
from low to high at a constant rate. During the energy increasing,
the incident energy and the outgoing energy were received and
recorded by detector D1 and D2, respectively. By a program
NA9PH: yield: 61%. 1H NMR (CDCl3, 400 MHz)
d
(ppm): 8.79 (s,
1H), 8.64 (m, 2H), 8.27 (s, 1H), 8.02 (s, 1H), 7.85 (d, 1H), 7.71 (t, 3H),
Fig. 3. Electron density distribution of frontier molecular orbital of NaxPHs.

274
G.-J. Ye et al. / Dyes and Pigments 94 (2012) 271e277
Table 2
manipulation, the change curves of outgoing energy and trans-
mittance with the change of the incident energy can be obtained.
Nonlinear optical value of NA3PH, NA6PH, NA9PH, and NA12PH in DMF solution.
Sample
T0a(%)
Eb(
m
J)
b
c(MKS)
8.76 ꢂ 10ꢁ9
8.00 ꢂ 10ꢁ9
7.94 ꢂ 10ꢁ9
7.53 ꢂ 10ꢁ9
2.4.2. Two-photon excitation fluorescence
NA3PH
NA6PH
NA9PH
NA12PH
70
70
70
70
3.27
3.18
3.29
3.30
The two-photon excitation fluorescence measurements were
performed by using an Avesta femtosecond Ti: sapphire oscillator
as the excitation source. The output laser pulses have a tunable
center wavelength from 750 to 870 nm with pulse duration of 80 fs
and a repetition rate of 85 MHz. The samples were dissolved in DMF
with the concentration of 2 ꢂ 10ꢁ5 M and the two-photon fluo-
rescence spectra were measured in the range of 760e870 nm using
fluorescein as the reference. The TPA cross section of these four
compounds was calculated using the equation:
a
The linear transmittance.
The energy in measurement.
Nonlinear absorption coefficient.
b
c
enhance the film-forming ability in further fabrication. Moreover,
styrene as an electron donor was introduced for providing an active
site for polymerization.
The UVevis spectra of NAxPHs in DMF solution were shown in
Fig. 1. All of the one-photon absorption spectra exhibit two main
absorption bands. The absorption bands at 330 nm and 460 nm are
ds ¼ ½ðFsFrC Þ ðFrFsCsÞꢃdr
(1)
=
r
In this equation, subscripts s and r represent the sample and
reference, respectively. F is the integral area of the two-photon
fluorescence spectra,
number density of the molecules in solution and
F
is the fluorescence quantum yield, c is the
is the TPA cross
attributed to
pep* transition of aromatic rings and typical inter-
d
molecular charge transfer absorption of 4-substituted naph-
thalimide, respectively [25].
section. The two-photon fluorescence measurements were
measured in the region that fluorescence intensity showed
a quadratic dependence on excitation laser beam power.
All molecules exhibit a strong green fluorescence emission. As
shown in Fig. 2, the emission spectra exhibit a single broad-band,
which indicates that the emission occurs from the lowest excited
state with the largest oscillator strength. The emission bands of
NAxPHs are similar but red shift to 556 nm (lex ¼ 460 nm) in
comparison with naphthalimide group (440 nm). Meanwhile, the
intensity of fluorescence is enhanced obviously. This is assigned to
the significant ICT and larger conjugation by introducing hydrazone
group. The fluorescence quantum yield and fluorescence decay are
also measured and the data are collected in Table 1. These
compounds possess the similar linear optcial properties because of
their similar structure. These results can be inferred from theo-
retical calculations. The electron density distribution of the frontier
molecular orbital were shown in Fig. 3. The band gaps of all
compounds are similar, ranging from 3.182 to 3.184 eV. In the
HOMO of NAxPHs, the electrons were distributed throughout the
whole molecule. While in the LUMO, the electrons were mainly
concentrated on 1,8-naphthalimide. Upon excitation, the electrons
were mainly transferred from hydrazone structure to 1,8-naph-
thalimide, indicating that eNHeN]Ce moiety serves as donor for
charge transfer.
2.4.3. Ultrafast pump-probe measurements
The ultrafast relaxation dynamics of the NAxPHs in DMF were
measured by using ultrafast transient absorption experiments,
which were performed by using a femtosecond Ti: sapphire
amplifier laser system (Spectra Physics). The laser pulses were
generated from a mode-locked Ti: sapphire oscillator seeded
regenerative amplifier with a pulse energy of 2 mJ at 800 nm and
a repetition rate of 1 kHz.
3. Results and discussions
3.1. Experimental section
All NAxPHs molecules were synthesized via a similar six-step
route (Scheme 1) in high yields: 1, 8-naphthalic anhydride was
first reacted with aniline to obtain 1,8-naphthalimide. 1,8-
naphthalimide further reacted with aromatic aldehyde to obtian
the target molecules. Therefore, 1,8-naphthalimide was linked
directly with a hydrazone bond. Alkane chain was introduced to
Fig. 5. Optical responses to laser light of NA3PH, NA6PH, NA9PH, NA12PH in DMF
Fig. 4. Z-scan data of NA3PH in DMF solution nonlinear absorption of NA3PH.
with a linear transmission of 70%.

G.-J. Ye et al. / Dyes and Pigments 94 (2012) 271e277
275
m
N
P
½ꢁq0ðZÞꢃ
TðZ; S ¼ 1Þ ¼
;
for jq0j < 1
m ¼ 0 ðm þ 1Þ1=2
ꢀ
ꢁ
(2)
q0ðZÞ ¼ a2I0ðtÞLeff = 1 þ Z2=Z2
Leff ¼ ½1 ꢁ expðꢁa0LÞ=a0ꢃ 0
Where a2 is the nonlinear absorption coefficient, I0 (t) is the
intensity of laser beam at focus (z ¼ 0), Leff is the effective thickness
with a0 the linear absorption coefficient and L the sample thickness,
z0 is the diffraction length of the beam, and z is the sample position.
The nonlinear absorption coefficient of the NAxPHs can be deter-
mined by fitting the experimental data of open-aperture Z-scan.
The calculation results of the nonlinear optical coefficients are
shown in Table 2. According to Table 2, NAxPHs exhibit large
nonlinear optical coefficient (
b
) ranged from 7.53 ꢂ 10ꢁ9 MKS to
8.76 ꢂ 10ꢁ9 MKS. Meanwhile, the 4-NHNH2 naphthalimide did not
show any nonlinear absorption phenomenon. The results indicate
the nonlinear absorption of these compounds may be attributed to
the introduction of hydrazone group based on excited-state
absorption (ESA) behaviour. By introducing hydrazone group,
highly efficient donoreacceptor pairs were formed, in which
naphthalimide as acceptor and hydrazone group as donor. It was
proved that optimizing donor and acceptor pairs enhance
nonlinear absorbtion [28,29]. In addition, the resonance structure
of hydrazone with naphthalimide group may be also benefit to
nonlinear absorbtion [30]. It’s clearly that alkyl chain does not
significantly affect the push-pull system and the values nonlinear
absorption coefficients are quite close. NLO absorption coefficient
slightly decreases from shorter arkyl chain to longer chains. This
might be attributed that longer arkyl chain makes the arrangement
of chromophore more disordered [31]. Therefore, NA3PH behave
the largest nonlinear optical coefficient value.
Fig. 6. Optical responses to laser light of NA3PH and C60 with a linear transmission of
70%.
3.2. Nonlinear optical properties for nanosecond laser pulse
The Z-Scan patterns of NAxPHs in DMF solution were measured
under a wavelength of 532 nm and a pulse width of 4 ns and the
linear transmittance of NAxPHs were maintained at 70%. Fig. 4
exhibits the nonlinear absorptive pattern of NAxPHs and the
results demonstrate that all compounds have strong nonlinear
absorption. In theory, the normalized transmittance for the open
aperture configuration can be written as:
Fig. 7. Dependence of output fluorescence intensity (Iout) of NA3PH (a), NA6PH (b), NA9PH (c) and NA12PH (d) on the input laser power (Iin) at 800 nm.

276
G.-J. Ye et al. / Dyes and Pigments 94 (2012) 271e277
4000
3500
3000
2500
2000
1500
1000
500
0
400
500
600
700
Wavelength (nm)
Fig. 10. Femtosecond transient absorption spectra of NA3PH, NA6PH, NA9PH and
NA12PH in DMF at 1.0 ps delay time under excitation at 400 nm.
Fig. 8. Two-photon fluorescent spectra of NA3PH.
Originated from the 4-substituted naphthalimide, NAXPHS
exhibit strong two-photon emission fluorescence (TPEF). TPEF
spectra of NA3PH was shown in Fig. 8. Compared with SPEF spectra,
one- and two-photon spectra overlap reasonably well and exhibit
well defined vibronic structure. The two-photon cross section of
these compounds with the same concentration in DMF at different
excitation wavelength was shown in Fig. 9 and the data were
collected in Table 1. NAXPHS showed moderate two-photon
Fig. 5 shows the optical limiting properties of NAxPHs at the
same linear transmittance (T ¼ 70%, ¼ 532 nm) in DMF at the
energy range of 1.5 Je140 J. The linear transmittance was
measured under the energy of 1.5 J. As shown in Fig. 5, when the
input fluence further increases, the transmittance starts to
decrease, displaying optical-limiting activity. According to Fig. 5,
the optical limiting performance of NA3PH is slightly prior to the
others, consistent with the results of the nonlinear property
analysis.
l
m
m
m
absorption cross section because of its D-p-A configuration. In
general, each compound displays a gradual increasing trend in two-
photon absorption cross section with the maxima TPA cross-section
value of 90 GM for NA3PH, 65 GM for NA6PH, 77 GM for NA9PH
and 64 GM for NA12PH. NA3PH behave the largest two-photon
absorption cross section, the others are very close. However, due
to the similar values of Fdmax for NAXPHS, the different results of
two-photon absorption cross section are mainly caused by their
The optical limiting properties of NA3PH and C60, a benchmark
optical limiter, have been compared in this investigation. The
results are exhibited in Fig. 6, which show comparable optical
limiting properties between NA3PH and C60
.
3.3. Two-photon absorption properties for femtosecond laser pulse
quantum yields
F of one-photon fluorescence.
Two-photon absorption spectra of NA3PH, NA6PH, NA9PH and
NA12PH were measured using two-photon excited fluorescence
(TPEF) method in which excitation wavelength was adjusted from
750 to 870 nm. During this process, fluorescein solution (pH ¼ 11)
was used as a reference to calibrate the TPEF spectra of these four
samples. As can be seen from Fig. 7, two-photon excitation fluo-
rescence intensity of four samples was found to be linear with the
square of input laser power, indicating a nonlinear two-photon
absorption process.
3.4. Ultrafast pump probe measurements
For a detailed understanding of optical limiting mechanisms in
these strong push-pull systems (NAxPHs, x ¼ 3, 6, 9, 12) in DMF,
femtosecond transient absorption measurements have been per-
formed under excitation at 400 nm using femtosecond laser pulses.
Fig. 10 shows the transient spectra in the range from 450 to 800 nm
at a delay time of 1 ps. It can be seen that the transient features of
four compounds are quite similar in DMF. All four compounds
display a positive transient absorption between 450 and 560 nm
and ground state bleaching in the region of 560e725 nm. The
positive transient absorption is due to excited state absorption
(ESA, S1eSn). The bleaching in the 560e615 nm regions with
a maximum around 590 nm could be ascribing to the stimulated
emission. No change in transient absorption spectra was observed
by increasing alkyl chain length. It suggests that electronic transi-
tion in hydrazone and naphthalene push-pull system is not affected
by elongating alkyl chain. All the compounds display strong excited
state absorption at 532 nm. The results suggest that excited state
absorption contribute significantly to the observed optical limiting
effects at 532 nm.
4. Summary
In conclusion, a series of 1,8-naphthalimide derivatives with
hydrazone group were synthesized. These compounds show strong
excited state absorption at 532 nm using nanosecond laser and
Fig. 9. Two-photon excitation spectra for NA3PH, NA6PH, NA9PH and NA12PH at
a concentration of 10ꢁ5 M in DMF.

G.-J. Ye et al. / Dyes and Pigments 94 (2012) 271e277
277
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Acknowledgements
Authors gratefully thank Chinese Natural Science Foundation
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