Synthesis, third-order nonlinear optical properties and theoretical analysis of vinylferrocene derivatives

Article abstract of DOI:10.1016/j.dyepig.2013.01.028

A series of vinylferrocene derivatives were synthesized from the reaction of ferrocenecarboxaldehyde, alcohol, and triphenylphosphonium bromide in a one-pot, solid-state reaction. Their third-order nonlinear optical (NLO) properties were evaluated in N,N-dimethylformamide at 800 nm using femtosecond degenerate four-wave mixing. The third-order NLO susceptibilities of the compounds were 2.55-3.78 × 10^-13 esu. The second-order hyperpolarizabilities of the molecules were 2.42-3.60 × 10^-31 esu. The response times were 51-98 fs. The energy of the Highest Occupied Molecular Orbital (HOMO), the Lowest Unoccupied Molecular Orbital (LUMO), the energy gap of the HOMO and LUMO (E_gap), natural charge, and molecular orbitals are performed by the Density Function Theory (DFT). The DFT study showed that the third-order NLO properties were increased with the increasing electron-withdrawing ability in accordance with the decreasing E_gap and the increasing charge transfer among the donor, π-bridge, and the acceptor. The experiment and theoretical results show that the vinylferrocene derivatives have potential nonlinear optical applications.

Full text of DOI:10.1016/j.dyepig.2013.01.028

Accepted Manuscript
Synthesis, third-order nonlinear optical properties and theoretical analysis of
vinylferrocene derivatives
Jianhong Jia, Yanhong Cui, Yujin Li, Weijian Sheng, Liang Han, Jianrong Gao
PII:
S0143-7208(13)00060-0
10.1016/j.dyepig.2013.01.028
DYPI 3857
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 6 December 2012
Revised Date: 28 January 2013
Accepted Date: 31 January 2013
Please cite this article as: Jia J, Cui Y, Li Y, Sheng W, Han L, Gao J, Synthesis, third-order nonlinear
optical properties and theoretical analysis of vinylferrocene derivatives, Dyes and Pigments (2013), doi:
10.1016/j.dyepig.2013.01.028.
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ACCEPTED MANUSCRIPT
Highlights
A series of vinylferrocene derivatives were synthesized
The third-order nonlinear optical properties were measured using femtosecond degenerate
four-wave mixing.
The energy of the Highest Occupied Molecular Orbital (HOMO), the Lowest Unoccupied
Molecular Orbital (LUMO), the energy gap of the HOMO and LUMO (Egap), natural charge, and
molecular orbitals are performed by the Density Function Theory (DFT)

ACCEPTED MANUSCRIPT
Synthesis, third-order nonlinear optical properties
and theoretical analysis of vinylferrocene derivatives
Jianhong Jia, Yanhong Cui, Yujin Li, Weijian Sheng, Liang Han and Jianrong Gao*
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou
310014, P R China
Abstract: A series of vinylferrocene derivatives were synthesized from the reaction of
ferrocenecarboxaldehyde, alcohol, and triphenylphosphonium bromide in a one-pot,
solid-state reaction. Their third-order nonlinear optical (NLO) properties were
evaluated in N,N-dimethylformamide at 800 nm using femtosecond degenerate
four-wave mixing. The third-order NLO susceptibilities of the compounds were
2.55~3.78×10−13 esu. The second-order hyperpolarizabilities of the molecules were
2.42~3.60×10−31 esu. The response times were 51~98 fs. The energy of the Highest
Occupied Molecular Orbital (HOMO), the Lowest Unoccupied Molecular Orbital
(LUMO), the energy gap of the HOMO and LUMO (Egap), natural charge, and
molecular orbitals are performed by the Density Function Theory (DFT). The DFT
study showed that the third-order NLO properties were increased with the increasing
electron-withdrawing ability in accordance with the decreasing Egap and the increasing
charge transfer among the donor, π-bridge, and the acceptor. The experiment and
theoretical results show that the vinylferrocene derivatives have potential nonlinear
optical applications.
Keywords: vinylferrocene derivatives; nonlinear optics; DFWM technique; the
third-order NLO; functional dyes; density funtion theory
1

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1. Introduction
Third-order NLO materials had received wide attention in material science due to
their possible applications in the fabrication of devices related to telecommunications,
optical computing, optical storage, and optical information processing[1-6]. Organic
materials had been investigated as alternatives to inorganic species due to their low
cost, fast and large nonlinear response over a broad frequency range, inherent
synthetic flexibility, high optical-damage threshold, and intrinsic tailorability[7-10].
The basic structure of NLO materials are based on the π-bond system. The
delocalization of an electronic charge distribution arising from π-orbital overlap leads
to a high mobility of the electron density. Many studies had focused on the
structure-property trends of donor-acceptor strengths and the effectiveness of different
conjugated backbones[11-18]. Incorporation of a metal atom as the center of the
macrocycle results in two types of charge-transfer transitions, namely, metal-to-ligand
and ligand-to-metal. The molecular hyperpolarizability may be enhanced by
metal-ligand bonding through the transfer of the electron density between the metal
atom and the conjugated ligand systems. The vinylferrocene moiety has been used as
a π-electron donor in several compounds because of its highly conjugated
two-dimensional π-electron system, which produces a large nonlinear optical
response[19-27].
In the present work, a new convenient approach for the high-yield synthesis of
vinylferrocene derivatives from the reaction of ferrocenecarboxaldehyde, alcohol, and
triphenylphosphonium bromide in a one-pot, solid-state reaction without the use of
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phosphorus ylides is described (Fig. 1). The third-order NLO properties were
measured using the femtosecond time-resolved degenerate four-wave mixing
(DFWM) technique. And the quantum chemistry study was performed on six
compounds with the DFT. The excellent NLO properties were illustrated from the
energy of the HOMO, the LOMO, energy gap of the Egap, natural charge, and MOs.
This is the first study of the NLO properties for these compounds both in experiment
and quantum chemistry.
Fig. 1
2 Experimental section
2.1Materials
Unless otherwise stated, starting materials were used as purchased without further
purification. The dimethylformamide (DMF) was distilled from CaH2.
2.2 Instruments
Infrared spectra were recorded on a Vector 22 FT-IR spectrometer using KBr
1
pellets. The H nuclear magnetic-resonance (1H MNR) spectra were obtained on a
Varian XL-200 spectrometer. Ultraviolet-visible (UV-vis) spectra were recorded on a
Shimadzu UV-2550 UV-visible spectrophotometer using a quartz cuvette with a 1 cm
path length. Elemental analyses were performed on a Carlo ERBA 1106 elemental
analyzer. The two reaction vessels were milled simultaneously in a Retsch MM301
mixer mill (Retsch GmbH, Haan, Germany) at a frequency of 30 Hz for 0.5 h.
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2.3 Synthesis
2.3.1 Ferrocenecarboxaldehyde (1)
A mixture of 5.3 g (28 mmol) ferrocene and 60 mL chloroform was placed in a 50
mL three-neck flask and kept at -5 to -10°C. Afterward, 10.5 mL phosphorus
oxychloride dissolved in 15 mL DMF was added for 1.5 h. The resulting reaction
mixture was refluxed for 12 h. After solvent removal, the product was poured into 100
mL ice water and filtered. The filtrate was neutralized to pH 8-9 using NaOH (10%,
w/v) and then extracted with ether. The organic layer was washed with water and
dried over anhydrous MgSO4. After removal of the solvent, the crimson solid was
1
recrystallized from n-hexane. The purified product (1) weighed 2.3 g (79% yield). H
NMR(CDCl3): δ, 9.95 (s, 1H, HC=O), 4.79-4.80 (d, 2H, Cp-rings), 4.60-4.61(d, 2H,
Cp-rings), 4.28(s, 5H, Cp’-rings). MS(ESI), m/z: 215.0 (M+) FT-IR (KBr): υ(cm-1)
1681(C=O).
2.3.2 Ferrocenyl-2-phenylethylene (2a)
A mixture of 0.214 g (1 mmol) ferrocenecarboxaldehyde, 0.108 g (1 mmol)
benzalcohol, 0.343 g (1 mmol) triphenylphosphonium bromide, and 0.04 g (1 mmol)
NaOH was ball milled at room temperature for 0.5 h. The procedure was monitored
by thin-layer chromatography. The mixture was extracted in 20 mL dichloromethane.
After filtration, the solvent was removed under vacuum to obtain the crude product.
The residue was chromatographed on silica gel using petroleum ether with CH2Cl2
(1:1) as the eluent. The product is a red powder with a yield of 75.2%, as identified
using 1H NMR (500 MHz, CDCl3): δ 7.45 (d, J=7.5 Hz, 4H, Ar-H), 7.35 (d, J=7.5 Hz,
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4H, Ar-H), 7.31 (dd, J=14.3, 6.9 Hz, 4H), 7.24 (t, J=6.7 Hz, 3H), 6.89 (dd, J=16.1 Hz,
2H, CH=CH), 6.72 (d, J=16.2 Hz, 2H, CH=CH), 6.45 (d, J=12.0 Hz, 1H, CH=CH),
6.33 (d, J=11.9 Hz, 1H, CH=CH), 4.48 (s, 4H, C5H4), 4.35-4.21 (s, 4H, C5H4),
4.21-4.14 (m, 14H, C5H4 /C5H5), 4.11 (d, J=3.3 Hz, 5H, C5H5). MS (ESI), m/z:288.1
(M+). FT-IR (KBr), υ (cm-1): 2920(=C-H), 1600 (-C=C-), 960, 753; UV-Vis (CH2Cl2)
λ (nm): 263.5, 280.0, 310.0. From this experiment, the other yields are as follows:
2.3.3 Ferrocenyl-2-(4-methoxyphenyl)ethylene (2b)
Red powder; yield 63.0%.1H NMR (500 MHz, CDCl3) δ 7.40 – 7.36 (m, 8H,
Ar-H), 7.29 (s, 2H, Ar-H), 6.93-6.85 (m, 8H, Ar-H), 6.85-6.81 (m, 2H, Ar-H), 6.72
(dd, 4H,CH=CH), 6.68 (dd, 4H, CH=CH), 6.37 (dd, 1H, CH=CH), 6.27 (dd, 1H,
CH=CH), 4.45 (t, J=1.8 Hz, 8H, C5H4), 4.30-4.24 (m, 8H,C5H4), 4.19 (t, J=1.8 Hz, 2H,
C5H4), 4.16 (d, J=1.9 Hz, 2H, C5H4), 4.14 (s, 20H, C5H5), 4.11 (s, 5H, C5H5), 3.84 (s,
12H, OCH3), 3.83 (s, 3H, OCH3). MS (ESI), m/z: 318.0 (M+). FT-IR (KBr), υ (cm-1):
3091 (C-H), 1636 (-C=C-) λ (nm): 290.0.
2.3.4 Ferrocenyl-2-(3-nitro-phenyl) ethylene (2c)
1
Red powder; yield 81.4%. H NMR (500 MHz, CDCl3) δ 8.30 (t, J=1.9 Hz, 2H,
Ar-H), 8.24 (s, 1H, Ar-H), 8.13 – 8.01 (m, 3H, Ar-H), 7.71 (d, J=7.8 Hz, 2H, Ar-H),
7.67 (d, J=7.7 Hz, 1H, Ar-H), 7.49 (t, J=8.0 Hz, 2H, Ar-H), 7.44 (t, J=8.0 Hz, 1H,
Ar-H), 7.05 (dd, J=16.1 Hz, 2H, CH=CH), 6.74 (dd, J=16.1 Hz, 2H, CH=CH), 6.50
(dd, J=11.9 Hz, 1H, CH=CH), 6.43 (dd, J=11.9 Hz, 1H, CH=CH), 4.52 (s, 4H, C5H4),
4.39-4.34 (s, 4H, C5H4), 4.24 (d, J=20.0, 18.2 Hz, 4H, C5H4), 4.18 (d, J=2.8 Hz, 10H,
5

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C5H5), 4.15 (s, 5H, C5H4). MS (ESI), m/z: 333.0 (M+). FT-IR (KBr), υ (cm-1): 3091
(C-H), 1633(-C=C-). λ (nm): 290.0.
2.3.5 Ferrocenyl-2-(2,4-dichloro-phenyl)ethylene (2d)
1
Red powder; yield 74.3 %. H NMR (500 MHz, CDCl3) δ 7.56 (d, J=8.5 Hz, 3H,
Ar-H), 7.46 (t, J=3.3 Hz, 2H, Ar-H), 7.40 (d, J=2.1 Hz, 3H, Ar-H), 7.31 (d, J=13.2,
6.4 Hz, 2H, Ar-H), 7.23 (d, J=8.5, 2.1 Hz, 3H, Ar-H), 7.16 (d, J=2.0 Hz, 2H, Ar-H),
7.01 (dd, 3H,CH=CH), 6.89 (dd, 3H, CH=CH), 6.46 (dd, J=11.8 Hz, 2H, CH=CH),
6.37 (dd, J=11.8 Hz, 2H, CH=CH), 4.52 (t, J=1.7 Hz, 6H, C5H4), 4.35 (t, J=1.7 Hz,
6H, C5H4), 4.18 (s, 19H, C5H4, C5H5), 4.07 (s, 19H, C5H4, C5H5). MS (ESI), m/z:
356.0 (M+). FT-IR (KBr), υ (cm-1): 3093 (C-H), 1625(-C=C-) λ (nm): 280.0, 328.5.
2.3.6 Ferrocenyl-2-furanoethylene (2e)
1
Red powder; yield 85.5%. H NMR (500 MHz, CDCl3) δ 7.35 (d, J=5.9 Hz, 12H,
C4H3O), 6.77 (d, J=16.1 Hz, 6H, CH=CH), 6.49 (dd, J=16.1 Hz, 6H, CH=CH), 6.37
(m, J=10.2, 3.9 Hz, 24H, C4H3O), 6.19 (d, J=3.2 Hz, 6H, C4H3O), 6.15 (s, 16H,
CH=CH), 4.55 (s, 16H, C5H4), 4.40 (s, 12H, C5H4), 4.25 (d, J=1.7 Hz, 28H, C5H4),
4.11 (d, J=4.7 Hz, 70H, C5H5). MS (ESI), m/z: 279.1 (M+). FT-IR (KBr), υ (cm-1):
3095 (C-H), 1636(-C=C-). λ (nm):295.5.
2.3.7 Ferrocenyl-2-thiophenethylene (2f)
1
Red powder; yield 70.1%. H NMR (500 MHz, CDCl3) δ 7.14 (d, J=13.9 Hz, 2H,
C4H3S), 7.04 (s, 1H, C4H3S), 6.95 (d, J=8.4 Hz, 3H, C4H3S), 6.82 (dd, J=15.9 Hz, 1H,
CH=CH), 6.68 (dd, J=15.6 Hz, 1H, CH=CH), 6.47 (dd, J=12.1 Hz, 1H, CH=CH),
6.31 (dd, J=11.7 Hz, 1H, CH=CH), 4.42 (s, 2H), 4.37 (s, 2H, C5H4), 4.27 (s, 2H,
6

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C5H4), 4.23 (s, 2H, C5H4), 4.11 (d, J=25.1 Hz, 10H, C5H5). MS (ESI), m/z: 294.0
(M+). FT-IR (KBr), υ (cm-1): 3101 (C-H), 1626(-C=C-) λ (nm): 278.5, 314.2.
2.4 Nonlinear optical measurements
The third-order NLO properties were measured by the femtosecond DFWM
technique using a Ti: sapphire laser. The pulse width was 80 fs, as measured on an
SSA25 autocorrelator. The operating wavelength was centered at 800 nm. The
repetition rate of the pulses was 1 kHz. During the measurement, the laser was very
stable (rms < 0.1%). The input beam was split into two beams (k1 and k2) of nearly
equal energies using a beam splitter, which were focused on the sample plot. The k2
beam passed through a delay line driven by a stepping motor so that the optical path
length difference between the k2 and k1 beams could be adjusted during the
measurement. The angle between the beams was about 5°. When the beams were
overlapped spatially in the sample, the generated signal beam passed through an
aperture, which was recorded by a photodiode, and then analyzed by a lock-in
amplifier and computer (Fig. 2).
The experiments were performed at 22 °C in DMF solutions using a 1 mm-thick
quartz cell. As a reference, the optical nonlinearity of the standard sample (CS2) was
also observed.
Fig. 2
2.5 Calculated method
The ground-state geometry optimizations of all isomers were performed by using
DFT method with B3LYP[28]. The basis set used was 6-31G (d). The vibrational
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frequencies were calculated with the same basis set. All the predicated vibrational
spectra had no imaginary frequency, which implied that the optimized geometries
were locating at the local lowest point on the potential energy
surface[29]_ENREF_27_ENREF_27. Upon the optimized structures predicted by
B3LYP/6-31g (d) level, the MOs and natural charge analyses at the same level of
theory were carried out for isomers. Time-dependent-DFT calculations of the single
excitation energies were performed at the optimized geometries of the ground states,
and the basis set used was 6-31G (d). All the calculations were performed within the
Gaussian 09 quantum chemical package[30]_ENREF_28_ENREF_27.
3. Results and discussion
Among the six vinylferrocene derivatives, 2d is a new compound[31-34]. The
compounds were synthesized by the Vilsmeier reaction and the solid-state Wittig
reaction, as illustrated in Fig. 1.
The linear UV-vis absorption spectra of the six vinylferrocene derivatives in DMF
solutions are shown in Fig. 3. These compounds exhibited absorption peaks between
260 and 330 nm. The laser wavelength (800 nm) used in the DFWM experiment was
far from their resonant bands. Thus, the third-order NLO susceptibilities χ(3) of the
compounds were off-resonant nonlinear responses.
Fig. 3
The third-order NLO susceptibility, χ(3), is calculated by comparing the measured
signal for the sample with that for CS2 under the same experimental condition. The χ(3)
is obtained according to the following formula[35]_ENREF_27:
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
1/ 2

2
IS
Ir
Lr ns
α
Lexp(
αL / 2)
(3)
(3)







(1)
χ s
=
χ r

Ls nr

1− exp(−
α
L)



Where I is the intensity of the phase-conjugated beam, L is the sample path length,
n is the linear refractive index, and α is the linear absorption coefficient. The
subscripts ‘s’ and ‘r’ refer to the sample and CS2, respectively. The fraction
αL exp(αL
1 − exp( −αL
/ 2) comes from the sample absorption and equals to 1 approximately while
)
the sample has little absorption around the employed laser wavelength (800 nm). The
Lr
Ls
fraction
equals to 1 approximately while the sample and CS2 were detected with
the same pool in our experiment. Thus, the equation (1) might be modified as follows:


1 / 2 2
I
I
ns
( 3)
( 3)
S
r








(2)
χ s
=
χ r
nr




The values of χr(3) and nr for CS2 are 6.7× 10-14 esu and 1.632, respectively[36-38].
The values of ns for the sample were measured by 2WAJ Abbe refractometer.
The second hyperpolarizability γ of a molecule in isotropic media is related to the
solution χ(3) by:
χ (3)
γ
=
(3)
4
Nf
Where f4 is the local field correction factor which is [(n2 +2)/3]4 (n is the linear
refractive index of the solution), N=NAꢀC/M is number of solution molecules per unit
volume and NA is Avogadro number.
The nonlinear refractive index n2 in isotropic media is estimated through the follow
equation (4).
12πχ( 3)
=
(4)
n2
2
nr
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The temporal response of the phase conjugate signal as a function of the delay time
of the input beam is shown in Fig. 4. The response times (τ) of the samples is
half-peak width, and the intensity of the optical conjugate wave (I) is peak height.
The values of χ(3), n2, γ and response times for the samples deduced and calculated
from the experimental results are listed in Table 1.
Fig. 4
Table 1.
The vinylferrocene derivatives 2a–2f possess a highly delocalized π-conjugated
electron system. The γ values of the vinylferrocene derivatives are higher than that of
the other third-order NLO materials, such as organobimetallic Ru(II)-Re(I)
4-ethynylpyridyl complexes[39]_ENREF_30, which is about 6×10-34 esu, and are also
higher than that of ferrocene, which is 1.6×10-35 esu[40]_ENREF_30.
The fully optimized geometries of the six compounds were shown in Fig. 5. All the
C atoms of one cyclopentadiene in ferrocene, the ethylene, and the benzene ring are
almost in the one plane with the 1.4° largest dihedral angle. This excellent coplanarity
implies these compounds could have good third order NLO properity. The energy of
HOMO, LUMO, and the Egap were listed in Table 2. The electron-withdrawing
substituents aryl (e.g. –NO2 and –2Cl) decrease the energy of LUMO and
HOMO-LUMO Egap as shown in Fig. 6. The lower energy of LUMO illustrates the
electron injection was improved. The lower Egap illustrates these compounds with
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electron-withdrawing substituents aryl would have larger three-order NLO which
accord with the above experiment as well.
Table 2.
Fig. 5
Fig. 6
These derivatives contain electron-withdrawing substituents aryl radical groups
and electron-donating ferrocenyl in the form of a D-π-A structure, resulting in a
stronger intermolecular charge transfer. Then the natural charges of 2a to 2d were
calculated listed in Table 3. Electron-withdrawing substituents such as the -NO2 and
-2Cl have higher natural charge values (-0.07 e) than that of 2a (-0.03 e) and 2b (-0.01
e). The natural charge of the -CH=CH- bridge is increased with the increasing of the
electron-withdrawing ability of the substituents such as the -Cl has 0.06 liarge than
that of -OCH3. The charge transfer among the D, -CH=CH- bridge, and the
substituents are accord with the γ values of these complexes. The stronger is the
electron-withdrawing ability of the substituents of the aryl groups, the higher are the γ
values.
Table 3.
On the basis of the optimized ground geometry, the significant exited states are
calculated with TD-DFT. For the majority of the excited states with the largest
oscillator strengths, the electron translates mainly from the HOMO-2 to LUMO when
the substituents are not -NO2 (mainly from the HOMO-2 to LUMO+1). In order to
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illustrate the differences, the frontier molecular orbitals (FMOs) of 2a to 2f
compounds are listed in Fig. 7. The FMOs (LUMO+2, LUMO+1, LUMO, HOMO,
HOMO-1, and HOMO-2) of the six calculated isomers are similar to each other in
principal character except the substituents of -NO2. The reverse of the LUMO and
LUMO+1 in the complex with the substituents on benzene ring is -NO2 results the
more difficult transition of electron from HOMO-2 to LUMO+1. Therefore, the
complex with -NO2 has smaller coefficient of third-order NLO than the complex with
two -Cl. The HOMO-2 is mainly composed by the p atomic orbital of C in
cyclopentadiene, -CH=CH-, and -Ph. The HOMO-1 mainly located on the ferrocene,
especially the d atomic orbital of Fe atom. The HOMO is mainly contributed by the p
atomic orbital of C in cyclopentadiene and -CH=CH-. The π* is formed between the
cyclopentadiene and -CH=CH- in HOMO-2, and HOMO. However, the
cyclopentadiene and -CH=CH- formed π bond with p atomic orbital of C.
Fig. 7
4. Conclusions
Six vinylferrocene derivatives possessing D-π-A srtuctures were synthesized by a
one-pot solid-state reaction, and characterized by UV, IR, and 1HNMR spectroscopy.
The third-order NLO properties in the femtosecond range were investigated using the
DFWM technique at 800 nm. The γ values increase with the strength of
electron-accepting characteristics. The γ value of heterocyclic radical groups is higher
than that of aryl groups. These compounds possess ultrafast response times of < 98 fs.
The DFT study showed that the third-order NLO properties were increased with the
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increasing electron-withdrawing ability in accordance with the decreasing Egap and the
increasing charge transfer among the donor, π-bridge, and the acceptor.
Acknowledgements
We are very grateful to Dr. Shian Zhang from the Key Laboratory of Optical and
Magnetic Resonance Spectroscopy in East China Normal University, for the DFWM
experiment and the helpful discussion. This research was financially supported by the
National Natural Science Fund of China (Grant no. 20876148).
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Table 1. The values of χ(3), γ, n2, and the respond times for 2a-2f.
χ(3)
(10-13esu)
3.14
n2
γ
Response
sample
I
n
(10-12esu) (10-31 esu) time τ(fs)
2a
2b
2c
2d
2e
2f
2.86776
1.90160
3.11582
4.18241
2.96993
3.06783
1.4297
1.4294
1.4294
1.4286
1.4294
1.4295
5.79
4.01
6.03
6.98
5.89
5.98
2.98
2.42
3.10
3.60
3.03
3.08
57.03
51.34
68.76
51.67
97.57
55.46
2.55
3.27
3.78
3.19
3.24
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Table 2. The energy (in eV) of the Highest Occupied Molecular Orbital (HOMO, EHOMO), the Lowest Unoccupied
Molecular Orbital (LUMO, ELUMO), and the HOMO-LUMO gap (Egap).
Compound EHOMO ELUMO
Egap
2a
2b
2c
2d
2e
2f
−5.111 −1.047 4.064
−4.934 −0.844 4.090
−5.394 −2.320 3.073
−5.306 −1.447 3.860
−4.973 −0.941 4.032
−5.362 −2.146 3.215
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Table 3. The Natural Charge (in e) of the complexes at the B3lYP/6-31G (d) level.
2a
2b
2c
2d
π-brige
0.04
−0.03
0.03
−0.01
0.05
0.06
(-CH=CH-)
Substituents on aryl
−0.07 −0.07
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Captions:
Fig.1 Synthetic routes of vinylferrocene derivatives.
Fig. 2 Optical path of DFWM.
Fig. 3 The UV-vis spectrum of 2a-2f in DMF.
Fig. 4 DFWM signal versus delay time for 2a-2f in DMF solution.
Fig. 5 The geometries optimized by B3LYP/6-31G (d) level.
Fig. 6 The energy of the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO) of the compound
2a to 2f.
Fig. 7 Frontier Molecular Orbitals of the compounds of 2a to 2f.
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Fig.1 Synthetic routes of vinylferrocene derivatives.
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Fig. 2 Optical path of DFWM.
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Fig. 3 The UV-vis spectrum of 2a-2f in DMF.
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Fig. 4 DFWM signal versus delay time for 2a-2f in DMF solution.
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Fig. 5 The geometries optimized by B3LYP/6-31G (d) level.
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Fig. 6 The energy of the highest occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO) of the compound 2a to 2f.
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Fig. 7 Frontier Molecular Orbitals of the compounds of 2a to 2f.
26