Third-order nonlinear optical properties and optical limiting behavior of
1,1-ferrocenedicarbaldehyde
Cheng-Bao Yao
a,b
, Yun-Dong Zhang
a,
⇑
, Hai-Tao Yin
b
, Qing-Yu Meng
b
, Chang-Qiu Yu
a
, Jin Li
a
, Ping Yuan
a
a
National Key Laboratory of Tunable Laser Technology, Institute of Optoelectronics, Harbin Institute of Technology, Harbin 150080, China
b
Key Laboratory of Photonic and Electric Bandgap Materials, Ministry of Education, School of Physics and Electronic Engineering, Harbin Normal University, Harbin 150025, China
article info
Article history:
Received 3 March 2013
In final form 10 May 2013
Available online 17 May 2013
abstract
We investigated nonlinear optical properties of 1,1-ferrocenedicarbaldehyde (FePz) with a nanosecond
Nd:YAG laser pulse at 532 nm. The nonlinear absorption coefficient and nonlinear refractive index were
measured using standard Z-scan technique. The experimental results show that the values of the nonlin-
ear absorption coefficient and nonlinear refractive index were 43.32 cm/GW and 1.65 10
10
esu,
respectively. Moreover, the transmission measurement technique was used to study the optical limiting
of FePz. These molecules exhibit an interesting optical limiting performance with nanosecond laser
pulses. With good excellent nonlinear optical coefficient, the samples were expected to be the potential
applications in optical devices.
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction
Ferrocene has attracted the attentions of worldwide scientists
because of its numerous applications in chemical sensing, asym-
metric catalysis and material science [1]. To integrate a ferrocene
unit into macrocyclic architectures has been recognized as an
attractive way to endow molecules with secondary functionalities.
On the other hand, it is well known that third-order optical nonlin-
earity is associated with bandgap, the smaller the bandgap of a
P
-conjugated polymer, the higher the third-order optical nonlin-
earity. The above results of the ferrocenophanes have been verified
in various photonics devices, such as all-optical switching (A-OS),
optical limiting (OL), etc. Nalwa [2] investigated the third-order
nonlinear optical susceptibilities
v
(3)
of ferrocene-containing
polyazines by the third harmonic generation. The
v
(3)
values of
2.23 10
11
esu at 1.8
l
m for ferrocene-containing polyazine
were observed. Up to now, experimental result about third-order
nonlinear optical properties and OL behavior of 1,1-ferrocenedi-
carbaldehyde have been seldom reported.
In this Letter, the Z-scan [3–5] and transmission measurement
technique [6,7] are used to study the nonlinear optical properties
and OL of a 1,1-ferrocenedicarbaldehyde (FePz), which shows large
nonlinear absorption coefficient and strong reverse saturated
absorption. This material is especially convenient for nonlinear
investigations because of its high durability, simple process ability,
and low linear absorption. The results reveal that the OL efficiency
is dependent on the one-photon absorption (OPA)-induced ex-
cited-state absorption (ESA) process, and the FePz exhibits strong
OL effect at nanosecond laser pulses. The experimental results pro-
vide reliable reference for the application of ferrocene in all-optical
switching and OL.
2. Synthesis and experiment
All reagents were purified and dried before it could be used
according to standard procedure. FePz was synthesized according
to the literature [8,9]. In 50 mL flask, 0.92 mL (4.64 mmol) triethyl
phosphonoacetate was added in 15 mL anhydrous THF, under
78 °C. Then, 2.5 mL (4.64 mmol) n-BuLi was added by drop wise.
After half an hour, 0.51 g (2.11 mmol) 1,1-ferrocenedicarbaldehyde
in 5 mL tetrahydrofuran (THF) was dropped. The reaction was kept
in 78 °C for 2 h, and then was placed under the room temperature
for 10 h. It was quenched by adding water, and was extracted with
15 mL CH
2
Cl
2
three times. The combined organic layer was dried
with Na
2
SO
4
. The product was separated through column chro-
matograph, eluted with petroleum ether:ethyl acetate = 4:1 (v/v).
Red solid 0.65 g, yield: 73.5%. The absorption spectra of FePz were
recorded by UV–VIS–NIR spectrophotometer, as presented pre-
sented in Figure 1. Clearly, FePz exhibits a strong linear absorption
band with a peak at k
abs
= 340 nm and highly transparent in the
near infrared range; and therefore, one may choose the excitation
wavelength k
exc
of 532 nm for FePz in order to fulfill the require-
ments (k
abs
< k
exc
<2k
abs
) of two-photon absorption (2PA) studies
[10,11]. The molecular structure of FePz is shown in inset (a) of
Figure 1.
The Z-scan technique is used to measure the nonlinear optical
properties, which shows great advantages due to its simplicity
0009-2614/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cplett.2013.05.019
⇑
Corresponding author at: National Key Laboratory of Tunable Laser Technology,
Institute of Optoelectronics, Harbin Institute of Technology, Harbin 150080, China.
E-mail addresses: yaochengbao5@163.com (C.-B. Yao), ydzhang@hit.edu.cn
(Y.-D. Zhang).
Chemical Physics Letters 576 (2013) 35–38
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Chemical Physics Letters
journal homepage: www.elsevier.com/locate/cplett