Accepted Manuscript

A series of stilbazolium salts with A-π-A model and their third-

order nonlinear optical response in the near-IR region

Yiwen Tang, Hui Liu, Hui Zhang, Dandan Li, Jian Su, Shengyi
Zhang, Hongping Zhou, Shengli Li, Jieying Wu, Yupeng Tian

PII: S1386-1425(16)30732-6
DOI: doi: 10.1016/j.saa.2016.12.017
Reference: SAA 14830
Spectrochimica Acta Part A: Molecular and Biomolecular
To appear in:
Spectroscopy
Received date: 18 September 2016
Revised date: 6 December 2016
Accepted date: 13 December 2016

Please cite this article as: Yiwen Tang, Hui Liu, Hui Zhang, Dandan Li, Jian Su, Shengyi
Zhang, Hongping Zhou, Shengli Li, Jieying Wu, Yupeng Tian , A series of stilbazolium
salts with A-π-A model and their third-order nonlinear optical response in the near-IR
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Please check if appropriate. Saa(2016), doi: 10.1016/j.saa.2016.12.017

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 ACCEPTED MANUSCRIPT

Review article

A series of stilbazolium salts with A-π-A model and their third-order nonlinear
optical response in the near-IR region

Yiwen Tanga, Hui Liua, Hui Zhanga, Dandan Lia, Jian Sua, Shengyi Zhanga, Hongping
Zhoua, Shengli Li a, Jieying Wu* a, Yupeng Tian*a

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a
Department of Chemistry, Key Laboratory of Functional Inorganic Material

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Chemistry of Anhui Province, Anhui University, Hefei 230039, P. R. China
*
Corresponding author: jywu1957@163.com; yptian@ahu.edu.cn

Abstract
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A series of water-soluble stilbazolium salts with A-π-A (A： Acceptor) model have
been synthesized and fully characterized. The results obtained from absorption spectra
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and TD-DFT computational studies show that there is a relative strong intramolecular
charge transfer (ICT) transition from pyridine unit to pyridine cation of the
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stilbazolium salts. Further more, it is found that the three stilbazolium salts (T1, T2,
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T3) show the strong two-photon absorption (2PA) response in the near-infrared (IR)
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region by Z-scan technique using femtosecond laser. And the stilbazolium salt T3
shows the largest two-photon absorption cross-section and third-order nonlinear
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optical (NLO) coefficient (3) at 730 nm, indicating the different terminal substituent
group of the pyridinium plays a vital role in third-order NLO behavior.
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Key words: A-π-A model; Water-soluble stilbazolium salts; Third-order NLO

properties; Near infrared.

1. Introduction
Nonlinear optical (NLO) materials have been highly focused for their potential
applications in optical switching [1], 3D optical data storage [2], biological imaging
[3] and optical power limiting [4] in the modern information science. The organic
NLO materials exhibit many dramatic features, such as flexible tailored [5-8],
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super-speed optical responses [9-11], high optical damage thresholds [12,13], and
facile process ability [14]. It is significantly that the materials with remarkable NLO
properties in the near-infrared (NIR) region (approximately 700-1300 nm) have been
used in optical telecommunications, optical power limiting, upconverted lasing
[15-21].
Generally, the organic NLO materials were constructed with D (D: Donor) and A(A：
Acceptor) peripheral groups at the ends of the π-conjugation system forming the types

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of D-π-A molecules [22]. The length, planarity of the π-conjugate system and the

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electron intensity of D and A groups have been designed to achieve large NLO effects
due to its convenient adjustment of the intense intramolecular charge-transfer from

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donor to acceptor [23-26]. In recent reports, various structural models, such as D-π-A
[27-30], D-π-A-π-D [31], A–π–D–π–A [32], have been investigated. However,
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according to our knowledge, there is limited report for third-order nonlinear optical
materials with A-π-A structural model, especially in the range of near-IR region.
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In previous works, Marder’s group reported a series of stilbazolium salts [33]. And
then the kind of the compounds were systematically investigated by Prasad’s [34] and
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Nakatani’s groups [35]. However, most reported stilbazolium salts with NLO
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response were not water soluble, a major obstacle for biological research. Therefore,
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to extend the investigation range and obtain large third-order NLO materials with
highly water solubility in the near-IR region, a series of novel organic molecules with
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A-π-A model were rationally designed and concisely synthesized. The design strategy
is based on the following considerations. Firstly, N-Arylation of the pyridinium unit
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as acceptor in stilbazolium derivatives possesses high active to react with aldehyde

resulting in olefin condensation to extend the -electron delocalization in the
constructed molecule [24,36-42]. Secondly, optical and soluble properties can be
tunable by the terminal anions and different substituent groups of the pyridinium
unit[43,44]. Finally, T1 and T2 were designed as singlet biradical pyridinium
molecules with discrete cations and anion components. However, T3 designed as a
zwitterionic pyridinium molecule contains the cation covalently linked to the
propanesulfonic acid anion.
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2. Experimental
2.1. Materials and apparatus
As shown in Scheme 1, all the compounds under discussion were successfully
obtained through simple routes. They were exactly characterized by 1H NMR, 13
C
NMR, IR, MALDI-TOF-MS and ESI-MS. The 1H-NMR and 13
C-NMR spectra
recorded on at 25 C using Bruker 400 Ultrashield spectrometer were reported as
parts per million (ppm) from TMS (δ). IR spectra were recorded on NEXUS 870

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(Nicolet) spectrophotometer in the 400-4000 cm-1 region using a powder sample on a

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KBr plate. Melting point is measured on FP62 instruments. Elemental analyses were
carried out on a Perkin-Elmer 240 analyzer. ESI Mass Spectrometer were recorded

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using LCQ Fleet. NU
2.2. Synthesis and characterizations of the stilbazolium salts
2.2.1. Synthesis of T1
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1,4-dimethyl pyridinium iodide (2.35 g, 10 mmol) and 2-pyridinecarboxaldehyde

(1.10 g, 10 mmol) were dissolved in 30 ml ethanol. Piperidine was added dropwise,
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with vigorous stirring for 48 h at 78 C, then the mixture was cooled to room
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temperature, filtered, washed with ethanol and water, red solid T1 (2.75 g) was
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obtained with a yield of 85%. 1H NMR (400 MHz, d6- H2O) δ = 8.58 (d, J = 6.7 Hz,
2H), 8.51 (d, J = 4.3 Hz, 1H), 8.05 (d, J = 6.7 Hz, 2H), 7.87 (td, J = 7.7, 1.6 Hz, 1H),
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7.67 (dd, J = 12.0, 4.1 Hz, 2H), 7.53 (s, 1H), 7.40 (dd, J = 6.9, 5.1 Hz, 1H), 4.25 (s,
13
3H). C NMR (101 MHz, d6- H2O) δ =152.80, 151.69, 150.09, 145.29, 139.37,
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137.40, 126.45, 124.87, 124.57, 124.28, 47.12.Anal. Calcd. for C20H26N2O4S: C,

61.52; H, 6.71; N, 7.17 %. Found: C, 60.73; H, 6.746; N, 7.121 %. IR (KBr, cm-1):
3375 (m), 3040 (m), 2915 (m), 2877 (m), 1642 (m), 1590 (s), 1523 (s), 1385 (s), 1164
(s), 1043 (w), 969 (w), 832 (m). M. p. = 202 C. ESI: m/z, cal: 197.11, found: 197.17
[M+].

2.2.2. Synthesis of T2

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1,4-dimethyl pyridinium iodide (2.35 g，10 mmol) was dissolved in 20 ml acetonitrile,

(2.53 g, 10 mmol) silver hexafluorophosphate which dissolved in 10 ml acetonitrile
was added successively with vigorous stirring for 2 h at 50 C. The solution was
filtered in hot and the acetonitrile was evaporated, white solid 1,
4-dimethylpyridin-1-ium hexafluorophosphate(V) (2) (2.52 g) was obtained with a
yield of 92%. 2 (2.53 g, 10 mmol) and 2-pyridinecarboxal dehyde (1.10 g, 10 mmol)

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were dissolved in 30 ml ethanol, piperidine was added dropwise, with vigorous
stirring for 48 h at 78 C, then the mixture was cooled to room temperature and

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filtered, washed 3 times with ethanol and water, brownness solid 2.97 g was obtained
with a yield of 87%. 1H NMR (400 MHz, d6-H2O)  = 8.60 (d, J = 6.6 Hz, 2H), 8.55

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(s, 1H), 8.08 (d, J = 6.7 Hz, 2H), 7.89 (t, J = 6.9 Hz, 1H), 7.73 (d, J = 13.8 Hz, 1H),
7.68 (m, 1H), 7.56 (d, J = 16.5 Hz, 1H), 7.42 (s, 1H), 4.72 (d, J = 1.2 Hz, 1H), 4.26 (s,
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13
3H). C NMR (101 MHz, d6- H2O) δ =152.83, 151.64, 150.02, 145.23, 139.31,
137.35, 126.39, 124.84, 124.51, 124.28, 47.19. IR (KBr, cm-1): 3375 (m), 3040 (m),
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2915 (m), 2877 (m), 1642 (m), 1590 (s), 1521 (s), 1387 (s), 1168 (s), 1038 (w), 965
(w), 840 (m). Anal. Calcd. for C20H26N2O5S: C, 59.09; H, 6.45; N, 6.89 %. Found: C,
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56.69; H, 6.613; N, 6.580 %. M. p. = 202 C. ESI: m/z, cal: 197.11, found: 197.17
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[M+].
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2.2.3. Synthesis of T3
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A mixture of 1,3-propanesultone (3.66 g, 30 mmol) and 4-pyridinecarboxaldehyde

(2.80 g, 30 mmol) 4-methylpyridine in 50ml acetone was heated to reflux for 4h. The
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mixture was cooled to room temperature and filtered, then washed by ether obtained
3-(4-methylpyridin-1-ium-1-yl)propane-1-sulfonate (3). 3 (2.15 g, 10 mmol) and
2-pyridinecarboxa ldehyde (1.10g, 10 mmol) were dissolved in 30 ml ethanol,
piperidine was added dropwise, with vigorous stirring for 48 h at 78 C, then the
mixture was cooled to room temperature, filtered, washed with ethanol and water, red
solid 2.37 g was obtained with a yield of 78%. 1H NMR (400 MHz, d6-DMSO) δ =
8.68 (d, J = 6.7 Hz, 2H), 8.51 (d, J = 4.4 Hz, 1H), 8.08 (d, J = 6.7 Hz, 2H), 7.86 (td, J

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= 7.8, 1.6 Hz, 1H), 7.69 (d, J = 11.5 Hz, 1H)， 7.65 (d, J = 3.0 Hz, 1H), 7.52 (s, 1H),
7.39 (dd, J = 7.2, 5.1 Hz, 1H), 4.63 (m, 3H), 2.94 (d, J = 7.4 Hz, 2H), 2.40 (s, 2H). 13C
NMR (101 MHz, d6- H2O) δ =152.74, 151.59, 150.06, 145.20, 139.21, 137.34, 126.35,
124.89, 124.53, 124.22, 47.17, 26.83. IR (KBr, cm-1): 3375 (m), 3040 (m), 2915 (m),
2877 (m), 1642 (m), 1590 (s), 1521 (s), 1387 (s), 1168 (s), 1038 (w), 965 (w), 840 (m).
Anal. Calcd. for C20H26N2O5S: C, 59.09; H, 6.45; N, 6.89 %. Found: C, 56.69; H,
6.613; N, 6.580 %. M. p. = 260 C. ESI: m/z, cal: 304.09, found: 305.09[M+].

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2.2.4. X-ray crystallography
The X-ray diffraction measurements were performed on a Bruker SMART CCD area

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detector diffractometer. The determination of unit cell parameters and data collections
were performed with Mo-Kα (λ=0.71073 Å). Unit cell dimensions were obtained with
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least squares refinements, and all structures were solved by direct methods with
SHELXS–97 and refined with SHEXLX-97. The hydrogen atoms were added
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theoretically and riding on the concerned atoms. The other non-hydrogen atoms were
located in successive difference Fourier syntheses. The final refinement was
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performed by full-matrix least-squares methods with anisotropic thermal parameters

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for non-hydrogen atoms on F2.

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2.2.5. Computational details

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Density functional theory (DFT) calculations on all the compounds were carried out
in vacuo for a better understanding of the charge transfer state. Optimizations were
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carried out with B3LYP [LANL2DZ] without any symmetry restraints, and the
TD-DFT {B3LYP[LANL2DZ]} calculations were performed on the optimized
structure. All calculations, including optimizations and TD-DFT, were performed
using the G03 software. Geometry optimization of the singlet ground state and the
TD-DFT calculation of the lowest 25 singlet–singlet excitation energies were
calculated with a basis set composed of 6-31 G* for C, H, N, O and S atoms were
downloaded from the EMSL basis set library.
2.2.6 Third-order NLO properties
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Through the open- and close-aperture Z-scan method, third-order nonlinear optical
(NLO) properties of T1-T3 were measured, including the nonlinear refractive index
(), nonlinear absorption coefficient (), 2PA cross section () and third-order
nonlinear optical susceptibility (3). For the experiments, the pulse length was 140 fs,
the thermal heating of the sample with high repetition rate laser pulse was removed by
the use of a mechanical chopper running at 10 Hz, and the average laser power was 36
mW [45]. A 1 mm cell of the sample in polar solvents at 1.0 ×10-3 mol/L was put in

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the light path, and all measurements were carried out at room temperature.

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Results and discussion

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3.1. Structural description
The optimized structures of T1 and T2 were calculated by TD-DFT calculations (Fig.
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S1). The crystals of T3 were cultured in dichloromethane at room temperature. The
crystal data collection and refinement parameters are listed in Table 1. The selected
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bond distances and angles of T1-T3 are provided in Table S1. As shown in Fig. 1, T3
crystallizes in monoclinic system with P21/c space. The angle of the stilbazolium
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group taking nitrogen atom as core is 120.11(17) ° and the bond length of N(1)-C(4)
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is 1.340(3) Å, N(1)-C(3) is 1.484(2) Å. All the bond lengths are located in

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intermediate range of C-C and C=C bonds (normal bond length of C-C and C=C were
1.53 Å and 1.32 Å, respectively) [46]. The dihedral angle between the pyridine ring
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and pyridinium salt ring is 8.086(22) °, indicating that the main framework structure
of T3 is nearly coplanar. It is interesting that H2O molecules play a vital role in
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constructing the 2D structure by the classical O-H···O hydrogen bond interaction. As

shown in Fig. 2, it can be seen that the adjacent H2O molecules are stacked through
O4-H4B···O6 (H···O is 2.187 Å ) and O6-H6B···O4 (H···O is 2.174 Å ) hydrogen
bond interactions forming one dimensional (1D) chain structure in direction a. Along
c-axis, the 2D structure is formed by another kind of O-H···O hydrogen bonds
O2-H5B···O5 and O3-H5C···O2 with distances of 2.038 Å and 2.262 Å, respectively,
which connecting the 1D chain with oxygen atom from T3 molecules.

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3.2. Linear Photophysical properties

The linear absorption properties of T1-T3 in different solvents are shown in Fig. 3
and Table 2. As shown in Fig. 3, we can see that the absorption spectra of the three
stilbazolium salts exhibit one intense absorption band between 280 and 350 nm,
which result from the -* transition or intramolecular charge transfer (ICT) transition
(from the weak acceptor pyridine unit to the strong acceptor pyridine cation). The

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absorption spectra of T1, T2 and T3 in different solvents display a weak
solvatochromism, which is attributed to a fairly similar polarity between excited state

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and ground state. The maximum absorption wavelengths of T1, T2 and T3 almost
have no shifted in DMF solution, revealing that different anions and terminal

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substituent groups have little influence on the energy gap between the ground state
and the excited state (Fig. 3d). The series stilbazolium salts of T1, T2 and T3 exhibit
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weak fluorescence intensity in different solvents (Fig. S1). Meanwhile, it can be
found that all the compounds possess low quantum yield (< 2 %) (Table 2). The
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behaviors are due to certain nonradiative decay mechanisms that may arise as a result
of “twisted intramolecular charge geometry” (TICT) [47].
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To facilitate investigate the water solubility of T1, T2 and T3, the linear relationship
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between the absorbance and the concentration have been verified. As shown in Fig S3,
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T1-T3 are soluble in pure H2O, and the absorbance are linear to the concentration in
the region of 1-50 M, which is a significant advantage for biological research.
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3.3. Quantum Chemical Calculations

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To further insight into the effect of electron distribution and the influence of different
substituent groups on the spectroscopic properties, TD-DFT calculations and
molecular orbital analyses for the three stilbazolium salts were carried out to
investigate the electron transition processes. The optimized structure of T1 and T2 are
given by theoretical calculation are shown in Fig. S1. The computed bond distances
(Å) and angles ( ° ) for the optimized structure of T1, T2 are shown in Table S1.
The molecular orbital contours show that the densities of HOMO are mainly located
in the pyridine moiety for T1, T2 and T3 (Fig. 4). After excited, the electrons are
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concentrated on the center pyridine cation moiety for T1, T2 and T3. Further more,
compared electron densities with HOMO orbitals, the electron densities of LUMO
orbitals exhibit decreased in propanesulfonic acid anion within T3. The transitions at
cal. 346 nm (f = 0.9523) for T1 originating from H-3→L transitions are assigned as
the ICT transitions. For T2 and T3, the transitions at cal. 363 nm (f = 0.9202) and 343
nm (f = 1.0291) originating from H→L and H-1→L transitions are all assigned as the

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ICT transitions, respectively. Basically, the calculated results for T1-T3 are in
reasonable agreement with the experimental λmaxab in the absorption bands observed

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in the experimental spectra (Table 3). By comparing the charge transfer processes
within these stilbazolium salts, it can be concluded that there is a highly π- electron

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delocalized system in the molecule T3, which is the necessary condition for it bearing
a strong NLO active.
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3.4. Third-order NLO properties
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To examine the nonlinear optical properties of compounds T1-T3, open- and

close-aperture Z-scan techniques were carried out by femtosecond laser pulses. The
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open-aperture data were shown in Fig. 5 and Fig. S4, the obvious minimum
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transmittance unambiguously suggested a biggish nonlinear absorption, which was

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ascribed to the third-order NLO effect in polar solvents. The filled squares represent
the experimental data, and the solid line is the theoretical curve modified from the
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following equations [45]:

[−𝑞 (𝑧)]𝑚 𝛽𝐼0 𝐿𝑒𝑓𝑓
𝑇(𝑧, 𝑠 = 1) = ∑∞ 0
𝑚=0 (𝑚+1)3⁄2 ; 𝑞0 (𝑧) = (1)
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1+𝑥 2

where x = z/z0, in which z0 = πω02/λ is the diffraction length of the beam, ω0 is the
spot size at the focus, λ is the wavelength of the beam, and z is the sample position. I0
is the input intensity at the focus z = 0 and equals the input energy divided by πω 02.
Leff = (1 − e−αL)/α is the effective length, in which α is the linear absorption coefficient
and L is the sample length. The molecular TPA cross-section () could be determined
by using the following relationship:
=h×10-3/NAd (2)

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where h is the Planck’s constant,  is the frequency of input intensity, NA is the

Avogadro constant, and d is the concentration of the sample. We investigated the NLO
properties of T1-T3 in different solvents (Table 4 and Table S2), and detailed
discussions in DMF were given as follows.
As shown in Table 4, the two-photon absorption cross-sections were 2689 GM at 780
nm for T1, 1341 GM at 820 nm for T2, 73965 GM at 730 nm for T3. And the values
of two-photon absorption coefficient β for T1-T3 are calculated as 0.064, 0.033 and

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1.636 cm/GW, respectively. Unlike pyridinium salts T1, T2 linked by discrete cation

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and anion components, T3 was designed as a zwitterionic pyridinium molecule
contains the cation covalently linked to the propanesulfonic acid anion. Importantly,

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the cubic hyperpolarizability γ enhancement strategies have focused on extended
planar linear π-conjugation, where the π-system is charge-neutral, and have significant
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known NLO response [34,48]. Based on the results in TD-DFT calculation, compared
the charge transfer processes with these stilbazolium salts, it can be concluded that
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there is a highly π- electron delocalized system in the molecule T3. Furthermore, it is

obvious that T3 shows larger f in the ICT transition process when compared with T1
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and T2. Therefore, it is reasonable that T3 should exhibit a larger two-photon

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absorption cross-section [49-51].

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The nonlinear refraction indexes of the title compounds were determined by the
close-aperture Z-scan technique. The effective third-order NLO susceptibility χ(3) of
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the sample can be calculated by the following equations [52]：

(3) (3) (3)
Re χ =10-4n020c2/； Imχ =10-2n020c2/42； χ =√(R χ(3) )2 + (I χ(3) )2 (3)
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e m

Where 0 is the vacuum permittivity, c is the light velocity in vacuum (in units of mol
L-1) and n0 is the linear refractive index of solvents. The third-order nonlinear
refractive index  can be derived from the equations [53]:
Tp=0。406(1-S)0.25,  =KLeffI0 (4)
Tp is the difference between the peak and the valley of the normalized transmission,
S is the fraction of the transmitted beam through the aperture, and  is the on-axis
phase shift, K = 2/. The resulting data and fitted curve were shown in Fig. 6 and

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Table 4.
It is known that the real part of χ(3) leads to an induced refractive index(n2 value)
change which is described by Δn = n2I, while the imaginary part is responsible for the
two-photon absorption characterized by the value of  [34]. As shown in Table 4, the
Re (χ(3)) of the three compounds are similar, however, the Im (χ(3)) of compound T3
was larger than that of T1 and T2. Considering the high two-photon absorption cross
section and remarkable value of χ(3) due to highly delocalized -electronic

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configuration and large intrinsic polarizability [51]. The terminal propanesulfonic acid

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anion part of T3 can extend the π-electron delocalized system and enhance the
electron communication going forward ICT process, which makes it for third-order

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nonlinear responses [54]. NU
4. Conclusions
Three novel stilbazolium salts with small size with A-π-A configuration have been
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efficiently synthesized. Their photophysical properties including linear absorption

properties and third-order NLO properties were investigated both experimentally and
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theoretically. It was found that the three compounds show few differences in the linear
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absorption properties. However, among the three salts, T3 exhibits much enhanced
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two-photon absorption cross-section and large value of the cubic hyperpolarizability

χ(3) in the near-IR region. The results suggest that zwitterionic pyridinium salts T3
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shows more intense NLO response in near-IR region compared with its iodide (T1)
and hexafluorophosphate ion (T2) analogues (discrete cation and anion components).
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Significantly, compared with other pyridinium salts reported, not only does this work
solve the problem of water solubility, but it also enhanced the NLO response in the
near-IR region. The investigation results offer a powerful confidence to design small
molecule (A-π-A model) organic materials having nonlinear optical (NLO) properties
in the near-IR region for biological and optoelectronics applications.

Acknowledgments
This work was supported by the National Natural Science Foundation of China
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(51372003, 21271004, 51432001, 51672002, 51472002, 21275006), Focus on

returned overseas scholar of Ministry of Education of China, the Higher Education
Revitalization Plan Talent Project (2013).

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Scheme and Figures

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Scheme 1. Synthesis routes for T1, T2 and T3.

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Fig. 1 ORTEP drawing for T3. Thermal ellipsoids are shown at the 50% probability
level.
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Fig. 2 (a) The 1D structure of T3 in direction a. (b) The 2D structures of T3 in

direction c.

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Fig. 3 Absorption spectra of compound T1(a), T2 (b)and T3(c) in different solvents

of different polarities with a concentration of 1×10-5 mol·L-1. (d) Absorption spectra
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of compound T1, T2 and T3 in DMF with a concentration of 1×10-5 mol·L-1. Inset:

The normalized absorption spectra of T1-T3.
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Fig. 4 Frontier molecular orbital diagram for T1, T2 and T3.

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Fig. 5 Z-scan data for T1(a), T2(b) and T3(c) in DMF with the concentration of
1.0×10-3 mol·L-1 in DMF, obtained under an open-aperture Z-scan. The blue dots are
the experimental data and the solid curve in the theoretical fitting. (d) Theoretical
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curves of a representative open-aperture Z-scan data for T1, T2 and T3 in DMF with
the concentration of 1.0×10-3 mol·L-1.
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Fig. 6 Z-scan data for T1, T2 and T3 in DMF with the concentration of 1.0×10-3
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mol·L-1 in DMF, obtained under closed-aperture Z-scan. The blue dots are the
experimental data and the solid curve in the theoretical fitting.

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Graphical abstract
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Tables
Table 1. Crystal data and structure refinement for compound T3.
Compound T3

Empirical formula C15H16N2O3S·3(H2O)

Formula weight 358.41

Temperature 296(2) K

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Wavelength 0.71073 Å
space group P21/c

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Crystal system monoclinic
a/Å 14.031(7)

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b/Å 7.547(4)
c/Å 16.342(8)
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α/(º) 90
β/(º) 93.124(6)
γ/(º) 90
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3
V/Å 1727.9(15)
Z 4
Dc/Mg m-3 1.378
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μ/mm 0.220
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F(000) 760.0
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R1 = 0.0406,
Final R indices [I>2σ(I)]
wR2 = 0.1223
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Goodness-of-fit on F2 1.079
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Table 2. Linear photophysical properties of T1, T2, T3 in different solvents.

Compounds Solvents max a(εmax b) max c △v d τe
EA 332(2.2) 420 88 1.19
EtOH 332(2.4) 403 71 0.27
MeCN 316(2.3) 407 91 0.41
T1
MeOH 329(1.7) 406 77 ---
DMF 336(2.7) 410 74 ---
H2O 329(1.8) 417 88 ---
EA 331(1.6) 430 99 0.46
T2
EtOH 330(0.9) 406 76 0.14
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MeCN 316(1.6) 407 91 0.17

MeOH 332(0.7) 406 74 0.27
DMF 335(1.9) 411 76 0.22
H2O 324(1.4) 417 93 0.10
EA 342(0.47) 419 77 1.77
EtOH 331(0.9) 406 75 0.15
MeCN 329(1.0) 408 79 0.18
T3
MeOH 327(0.6) 406 79 0.46
DMF 337(1.7)2.3 410 73 0.46
H2O 323(0.9) 418 95 0.11

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a
Peak position of the largest absorption band in nm (1.0×10 mol· L-1).
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b
Maximum molar absorbance in 104 mol-1·L·cm-1.
c
Peak position of SPEF, exited at the absorption maximum.

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d
Stokes shift in nm.
e
Quantum yields determined by using quinine sulfate as standard.

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Table 3. Calculated linear absorption properties(nm), excitation energy (eV),
oscillator strengths and major contribution for T1, T2 and T3.
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Compounds λ(nm) E(eV) f Composition Character

T1 346 3.58 0.9523 65→69 (H-3→L) (0.64812) ICT

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T2 363 3.41 0.9202 87→88 (H→L) (0.60913) ICT

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T3 343 3.61 1.0291 79→81 (H-1→L) (0.63471) ICT

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Table 4 Open- and closed-aperture Z-scan measurement data for the third-order
nonlinearity parameters of T1, T2, T3.
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Compounds T1 T2 T3

Wavelength (nm) 780 820 730

γ (cm2/W) 6.44  10-9 6.80  10-9 8.34  10-9

Re (χ(3)) (esu) 3.34 10-11 3.53 10-11 4.33 10-11

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2PA coefficient β
0.064 0.033 1.636
(cm/GW)
two-photon cross section
2689 1341 73965
σ(GM)

Im (χ(3)) (esu) 2.05 10-7 1.13 10-7 4.93 10-6

χ(3) (esu) 3.92 10-7 3.71 10-7 4.95 10-6

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Highlights
• Three stilbazolium salts with A-π-A model have been synthesized and fully
characterized.
• A relative strong intramolecular charge transfer (ICT) transition
• The excellent third-order NLO response in the near-infrared (IR) region by
Z-scan technique using femtosecond laser.
• The different terminal substituent group of the pyridinium plays a vital role in

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third-order NLO behavior.

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