Probing the Strong Near-IR Two-Photon Transition in

Supramolecular Triphenylamine-Based Polymers by

Nonlinear Absorption Spectroscopy

JessicaDipold1,Marcelo G. Vivas2,*, G. Koeckelberghs3, Jonathas P.

Siqueira1,4,Leonardo De Boni1, Cleber R. Mendonca1,*
1
Instituto de Física de São Carlos, Universidade de São Paulo, Caixa Postal 369, 13560-
970 São Carlos, SP, Brazil.
2
Laboratório de Espectroscopia Óptica e Fotônica, Universidade Federal de Alfenas,
Poços de Caldas, Minas Gerais 37715-400, Brazil.
3
Laboratory for Polymer Synthesis, KatholiekeUniversiteit Leuven, Celestijnenlaan 200 F,
B-3001, Belgium
4
Instituto de Física “GlebWataghin”, Universidade Estadual de Campinas, Campinas,
São Paulo 13083-859, Brazil.
*Correspondence authors: mavivas82@gmail.com, crmendon@ifsc.usp.br

1
 ABSTRACT
Due to their capability of film formation and remarkable optical features,
semiconductor polymers with high two-photon absorption (2PA) have been
studied as potential candidates for the development of organic photonic
platforms. Furthermore, there is a high demand for photonic devices operating
in the near-infrared (IR) region. However, the magnitude of the nonlinear optical
response of random coil polymers in the IR region is weak due to the loss of
molecular structure caused by increasing the π-conjugated backbone. Thus,
herein we aim to investigate the molecular structure and 2PA features
relationship for four polymers with supramolecular (helical) rodlike structure.
Such polymers have a rigid core based on triphenylamine groups connected to
the chiral binaphthalene units and a strong electron-withdrawing group (EWG).
This kind of structure allows a very high chromophore density, which was
responsible for generating 2PA cross-section between 305 GM and 565 GM in
the near-IR (900-1300 nm), depending on the EWG strength. In the light of the
two-level model within the sum-over-states approach, we estimated the degree
of intramolecular charge transfer induced by 2PA in the IR region, and values
as high as 50-70 % were found.Such a critical outcome allows that the 2PA
cross-section in the IR region remains high even though the ratio between the
visible/IR-band 2PA cross-section increases as a function of EWG strength.

2
I - INTRODUCTION

Two-photon absorption (2PA) spectroscopy of organic compounds has

been intensively studied in the past few years due to the wide range of
applications for nonlinearoptical materials. 1-12 Nowadays, semiconductor
polymers are the foundation of organic optoelectronics. Also, there is a growing
demand for organic materials with high nonlinear polarizabilitiesin the near-
infrared (IR) region to application in organic photonic devices such as electro-
optical modulators, biomolecularmarkers, micro-resonators, all-optical
switching, active waveguides, to cite a few.13-17 In this context, the synthesis of
push-pull semiconductor polymers is a molecular strategy very interesting to
achieve a largethird-order optical nonlinearity because it fulfills a series of
requirements. For instance, (i) semiconductor polymers are materials with high
capability for thin film formation in industrial-scale; (ii) they are rich in π-electron
that increases the transition dipole moments; (iii) they are easily modified to
produce push-pull structure by introducing electron-donating and acceptor
groups in the π-conjugated backbone.The last two requirements are closely
related to the high two-photon absorption in the near-IR region. On the other
hand, the dispersion of conjugation length in random coil polymers tends to
cause a structure loss in the lowest-energy 2PA band located in the near-IR
region of the 2PA spectrum, which in general is related to intramolecular charge
transfer (ICT) transition, as compared to the molecules and oligomers. 18 The
polydispersion generates a higher density of 2PA allowed states, which tends to
increase the magnitude of the higher-energy 2PA band (1Ag-like → mAg-like
transition) located at the visible region on the 2PA spectrum. 19-24
Within this context, G. Koeckelberghs et al. 25 proposed a new kind of
chiral triphenylamine-based polymers for nonlinear optical studies. They are
designed from chiral binaphthalene units, connected to the triphenylamine core,
which generates a rigid, supramolecular (helical) rodlike structure. Flexible
chromophores with high hyperpolarizabilities are added to this rigid rodlike
backbone, creating a push-pull molecular architecture. This kind of structure
allows a very high chromophore density because it diminishes and almost
excludes any dipolar interaction between the chromophores, allowing a higher

3
nonlinear response than random coil polymers have. 26 All produced polymers
had the same stable trans-chromophore symmetry, making them homo-
polymers with better stability. A previous study 27 has shown that this class of
polymers is, in fact, interesting for nonlinear optical applications, as they have
no dipole interaction between its chromophores. The conformation adopted by
the polymers can be visualized in Ref. 25.
Thus, we have investigated the molecular structure/2PA properties
relationship with special attention for the near-IR region. For that, we employed
the wavelength-tunable femtosecond Z-scan technique with a low repetition rate
(1kHz). Our results have shown that these push-pull polymers have a large 2PA
cross-section in the near-IR region ranged from 305 up to 565 GM (900-1300
nm), revealing the potential of these samples as an active medium in an organic
photonic platform.

2 – MATERIALS AND METHODS

The structures of the conjugated polymers studied in this work are shown
in Figure 1. As illustrated, the polymers have a core based on triphenylamine
groups connected to the chiral binaphthalene units,and different electron-
withdrawing groups were added in another branch represented by the letters
EWG, generating four distinct push-pull polymers named Polymer 1, 2, 3, and 4.

O
S
O N
EWG= NO 2 N
Ohex O
hexO Neff = 8 Neff = 8.95
Polymer 1 Polymer 3
n
N
S S

N O
O
CN CN
O
Neff = 8.25 Neff = 10 CN
EWG Polymer 4
Polymer 2

Figure 1–Supramolecular polymer main backbone structure (left) and the EWG (right) added to
it. Neff represents the effective number of π-electrons evaluated according to Ref. 28.

4
 Polymer 1 has the simplest chromophore added to it, which is
nitrobenzene-based. The synthesis of this polymer is described in Ref. 25.
Polymers 2 and 3 have approximately the same complexity, as well as
conjugation lengths, which are expected to have similar absorption spectra.
Polymer 4 has the most complex structure, as well as the longest conjugation
length between the four studied chromophores. The synthesis of polymers 2, 3,
and 4 are described in Ref.27.
The samples were dissolved in tetrahydrofuran (THF) in concentrations
of 10-5 M for the linear absorption spectra measurements, which were carried
out using a UV-1800 Shimadzu spectrometer. For the nonlinear optical
measurements (two-photon absorption), the samples were dissolved in
concentrations ranging from 10-4 to 10-3 M, also in THF. To calculate the
concentration of the polymers, we take into account the molecular weight of the
monomers.
Two-photon absorption spectra with linear polarization were obtained
through the open-aperture Z-Scan technique. A Ti:sapphire laser amplifier (775
nm, CPA-2001 system from Clark-MXR Inc.) emitting 150-fs pulses at a 1 kHz
repetition rate is used to pump an Optical Parametric Amplifier (OPA), which
delivers 160-fs pulses in the wavelength range of 470-2200 nm. Before the Z-
Scan setup, a spatial filter is added to assure a Gaussian beam profile to the
laser beam, as required to the technique.
In the Z-Scan measurement, the sample is translated around the focal
plane of a Gaussian beam while its transmittance is measured in the far-field.
When the sample presents nonlinear absorption, its absorbance becomes
dependent on the beam intensity according to α =α 0 + βI , where α 0 is the linear
absorption coefficient, β is the two-photon absorption coefficient, and I is the
beam intensity. From the fitting of the experimental transmittance using Eq. 1, it
is possible to obtain the two-photon absorption coefficient, β, usually expressed
in units of cm2/GW. With β determined, the two-photon absorption cross-section

ℏωβ
(σ2PA) can be calculated through σ 2 PA = , in which is the angular frequency
N
of the light, and N is the concentration of molecules in the solution (cm -3). It is
usually expressed in Göppert-Mayer (GM) units, with 1 GM = 10 -50 cm4s/photon.

5
3 – RESULTS AND DISCUSSIONS

The linear absorption spectra of the four samples are displayed in Fig. 2
(solid lines). All polymers present two one-photon absorption (1PA) bands at the
UV-VIS region; the higher-energy (HE) one, common for all polymers,is located
at around 350 nm, which is related to the binaphthalene backbone, 25 while the
lowest-energy (LE) band is related to thetriphenylamine core connected to
adistinct EWG. For Polymer 1, which has the smallest EWG strength, the LE
band is located around 440 nm, with a maximum molar absorptivity of about 4
x104 M-1cm-1. Polymers 2 and 3 have chromophores of similar EWG strength
and, therefore, their LE absorption bands are almost in the same region: 550
nm for Polymer 2 and 560 nm for Polymer 3. Also, Polymer 2 presents a molar
absorptivity around 4.5 x104 M-1cm-1, and Polymer 3 around 5.5 x104 M-1cm-1.
Polymer 4 has the strongest EWG strength and, therefore, has the higher
redshift for its LE-band, around 600 nm with a maximum molar absorptivity of
about 5.0 x104 M-1cm-1. It is important to mention that none of these polymers
presented fluorescence emission.
Based on the useful insights provided by the ground-state linear

01
absorption spectroscopy, we calculated the transition dipole moments ( ) for
the electronic state responsible for the lowest energy band. Thus: 29

3103 ln  10  hc n (1)
01 
 2  3 N A01 L2      d

 01
in which h is the Planck’s constant, c is the speed of light, is the transition

frequency,  is the molar absorptivity at excitation frequency, and

N A is

Avogadro’s number.

L  3n 2 / 2n2  1  is the Onsager local field factor introduced
in order to take into account the medium effect, 30 with the refractive index
n=1.407 for THF at 20oC. The transition dipole moments for the lowest-energy
transitions calculated using Eq. (1) are gathered in Table 1, as well as other

6
photophysical parameters. As can be noted, the transition dipole moment
increases as a function of the effective number of π-electron in the polymers.
Such a parameter is calculated by geometrically weighting the number of

N eff   Ni2
electrons in each conjugated path of the molecule, i.e., i , where Ni
is the number of π-electron of the molecule within and outside the conjugation
38
length. More details can be found in Ref. . Figure 1 shows the Neff for each
EWG. Moreover, the molar absorptivity can be evaluated as ε =1.035 x 102(
μ2 E01 /Γ ¿ ,where μ (Debye), E01 (eV) and Γ (eV) are the transition dipole
moment, transition energy and full-width half-maximum (FWHM) linewidth,
respectively. We have estimated the last parameter by fitting the lowest energy
1PA band for all polymer by using the Gaussian line-shaped function. The

 FWHM data showed in Table 1 are for the FWHM linewidth.

Table 1.Photophysical Data of polymers1-4in THF.

Polymers 1 2 3 4
LE
1PA  abs
(nm) 433 545 561 598
HE
1PA  abs
(nm) 340 427 428 460
 LE
max
-1 -1 3.68 x 104 4.55 x 104 5.59 x 104 5.13 x 104
max (M cm )
 HE (M-1cm-1) 6.05 x 104 2.92 x 104 2.92 x 104 2.48 x 104
 FWHM (eV) 0.52 0.43 0.40 0.50
max
01 8.0 ± 0.2 8.9± 0.2 10.0 ± 0.2 10.9± 0.2
max (D)
01 20.0 ± 1.6 15.2± 1.3 21.0 ± 2.0 17.5± 1.5
 LE 2PA (D)
346 305 565 362
 HE 2PA (GM)
340 190 617 536
 2 PA / (GM)
 HE  2 PA
LE 0.98 0.63 1.10 1.48

LE
1PA abs
 1PA abs are the wavelengths corresponding to the first and second band present in the linear
and HE
 2PA

2PA 

absorption spectra; LB and HB are the 2PA cross section related with the first (lowest energy) and
second (higher energy) 2PA band observed along the nonlinear optical spectra.The dipole moments are
given in Debye (D).

Figure (open circles) displays the 2PA spectra for all polymers. Both
1PA and 2PA spectra were plotted together to a better understanding of the
EWG effect on the nonlinear optical response. The first aspect to highlight is
that the spectral shape of the 2PA spectra for the polymers is similar. In other
words, all polymers present a lowest-energy 2PA band (LE-2PA) in the near-
7
infrared region, and a higher-energy 2PA band (HE-2PA) located the visible
region, characteristic of semiconductor polymers.

2PA wavelength (nm) 2PA wavelength (nm)

600 700 800 900 1000 1100 600 800 1000 1200 1400
8 1000 12 1000
Molar Absorptivity (10 M cm )

Molar absorptivity(10 M cm )
1PA spectrum 1PA spectrum
-1

-1
2PA spectrum 2PA spectrum

2PA cross section (GM)

(a) (c)
2LM fitting 800 2LM fitting 800
-1

2PA Cross section (GM)

-1
6 9
4

4
600 600
4 6
400 400

2 3
200 200

0 0 0 0
300 350 400 450 500 550 300 400 500 600 700
1PA wavelength (nm) 1PA wavelength (nm)

2PA wavelength (nm) 2PA wavelength (nm)

700 900 1100 1300 1500 600 800 1000 1200 1400 1600
9 1000 10 1000
Molar Absorptivity (10 M cm )

1PA spectrum

Molar absorptivity (10 M cm )

1PA spetrum
-1

-1
2PA spectrum
2PA spectrum

(b) (d)
2LM fitting
2LM fitting 800 8 800
-1

-1

2PA cross section (GM)

2PA cross section (GM)
4

6 4

600 6 600

400 4 400
3

200 2 200

0 0 0 0
350 450 550 650 750 300 400 500 600 700 800
1PA wavelength (nm) 1PA wavelength (nm)

Figure 2 - Linear absorption spectrum (solid line) along with two-photon absorption
measurements (circles) and its 2ELM fitting (dashed line) for a) polymer 1; b) polymer 2; c)
polymer 3, and d) polymer 4. The standard deviation for 2PA measurements was estimated at
20 %.

It is worth mentioning that the LE-2PA band for all polymers has a great
magnitude (300-565 GM) and corresponds, in energy, to the same transition
strongly 1PA allowed. Although it is prohibitive in centrosymmetric molecules
that an optical transition is simultaneously 1PA and 2PA allowed, in
noncentrosymmetric molecules like the polymers 1-4, the electric dipole
selection rules are relaxed. 31 According to several works about the 2PA
properties of organic molecules based on the triphenylamine-core, the lowest-
20,32-34
energy 2PA band has an ICT character.
For polymer 1 (Fig. 2a), the LE-2PA allowed band is located at 890 nm
with a magnitude of (3.5 ± 0.7) x 10 2 GM and the HE-2PA at 650 nm with a
magnitude of (3.4 ± 0.7) x 10 2 GM. For polymer 2 (Fig. 2b), the HE band around
850 nm, shows a 2PA cross section of (1.9 ± 0.4) x 10 2 GM, while the other one

8
at 1100 nm (LE) has a maximum 2PA cross-section of (3.0 ± 0.6) x 10 2 GM.
Both bands are red-shifted with respect to Polymer 1, which was expected
because the EWG connected to the core is stronger, similar to the features
observed to the ground-state absorption spectrum.
Figure c shows the 2PA spectrum for Polymer 3, in which the two 2PA
bands can be observed, one at 860 nm with (6.2 ± 1.1) x 10 2 GM(HE-2PA
band), and the other at 1140 nm with (5.6 ± 1.1) x 10 2 GM(LE-2PA band).
The two 2PA bands for Polymer 4 are located at 1020 nm ((5.4 ± 1.0) x
102 GM) and at 1230 nm ((3.6 ± 0.6) x 10 2GM), as seen in Figure d. It is
observed that the polymer 3 present the higher 2PA cross-section for both 2PA
allowed bands. This same behavior was observed for the molar absorptivity,
even though their transition dipole moment is smaller than the one obtained for
polymer 4. Such a result can be explained because the polymer 3 has the
lowest transition linewidth (Table 1). Such an important aspect also contributes
to the higher 2PA cross-section observed for polymer 3. The 2PA cross-section
values found here for all polymers associated with the LE-2PA band located in
the near-IR is higher than for other semiconductor polymers with random coil
18,20-22
structure such as thiophene/phenylene, fluorene, phenanthrene, etc.
To shed more light on the 2PA outcomes obtained in this work, we
quantified the ICT from the EWG to the triphenylamine core. Due to the
absence of fluorescence emission in all polymers investigated, it was not
possible to obtain the induced charge separation using the approach based on
solvatochromic Stokes shift measurements and the Lippert-Mataga
equation.34,35 Nevertheless, in the context of the two-energy level model (2ELM)
for 2PA, the value of the permanent dipole moment change, which reflects the
induced charge separation during the electronic transition assisted by ICT, can
be obtained from the 2PA cross-section correspondent to the peak of the LE-
2PA band. Therefore, we can evaluate the maximum change in the permanent
9,35
dipole moment corresponding to the ICT transition by using:

1/2
 
max  15 N A hc n 01  2 PA max 
01   01  01   ,
  2

 2 2 cos     1  2  3  10 ln  10  L max  01 
2 3 2 

 (2)

9
  2 PAmax 
in which  01 is the 2PA cross-section value at the peak of transition, and θ
max max
01 01
is the angle between the dipole moments. Herein, both and are
reported as maximum values because we considered that only one 2PA
allowed excited state to contribute effectively to the LE-2PA band. To find θ, we
performed 2PA measurements with circular and linear polarization. The ratio
between the circular and linear 2PA cross-section provides the angle of the

max
01
dipole moment for the 2ELM. 36,37 values between 15 Debye (D) and 20
Debye were obtained. Table 1 shows these values for each polymer. Thus, the

  reff / r reff   / e
degree of ICT can be evaluated from the relation , where
defines the effective charge transfer, e is the electron charge, and r is the
distance between the core and the first EWG atom obtained from the theoretical
calculations. As polymers have a great number of atoms, it becomes a hard
task to find r from the ab-initio quantum chemical calculations. Therefore, we
estimated r from previous works based onthe Density Functional Theory
34
framework for organic molecules containing a triphenylamine-core (see Ref )
and fixed the r value at ~ 6.0 x10 -10 m (higher value found for triphenylamine
core). Based on this approach, we obtained a degree of ICT of 69 % for
polymer 1, 53 % for polymer 2, 73 % for polymer 3, and 61 % for polymer 4.
These values are slightly higher than the ones observed for organic molecules
based on the triphenylamine core.24,33,34
Figure 3 illustrates a comparison between the transition dipole moment (
max max
01 01
) and permanent dipole change ( ) as a function of the EWG
strength, showing that while the transition dipole moment increases, the
permanent dipole changes oscillating between 15.2 ± 1.3 D for the polymer 2
and 21.0 ± 2.0 D for polymer 3, which present, respectively, the lowest and
highest 2PA cross-section for the IR transition. Thus, the greatest permanent
dipole change and the lowest linewidth transition are the main factors that are
contributing to the high 2PA cross-section found for polymer 3. Furthermore,
this behavior is accompanied by an increase in the ratio between the HE-2PA

10
  2 PA /   2 PA
 HE
and LE-2PA cross-section ( LE ), as shown in Table 1. For example, for

 2 PA /   2 PA
 HE
polymer 2 the LE rate is about 0.63 while we found 1.48 for polymer
4. These results suggest that stronger EWG tends to enhance the octupolar
character of the branched polymer, which is associated with the rise of the HE-
2PA cross-section. According to the Frenkel exciton model, 38-40 such behavior is
achieved in multi-branched molecular systems when there is a strong electronic
coupling among the branches.
Besides, Makarov et. al.33, have studied the branching, symmetry, and
planarization influence on the 2PA spectra of triphenylamine-core containing
diarylboryl-based molecules. They found that branching causes suppression (3-
11 times) on the 2PA cross-section for the LE 2PA band and a strong
enhancement (4-8 times) of the HE 2PA allowed band depending on the EWG
strength.Therefore, the authors concluded that anelectronic coupling amongthe
branches (octupolarcharacter) redistributes the 2PA cross-section, favoring the
HE-2PA over the LE-2PA band.41,42

12 24.0

11 21.5
(Debye)
(Debye)

10 19.0

9 16.5

8 14.0
7.5 8.0 8.5 9.0 9.5 10.0 10.5
Neff

Figure 3 – Transition dipole moment (circles) and permanent dipole moment change
(squares)as a function effective number of π-electrons. The solid line is only a guide for the
eyes.

Recently, we have observed similar behavior for triphenylamine-based

molecules containing distinct EWG strength. 32 We showed that a cooperative

11
effect among the branches for this class of molecules generates exponential
enhancement of the 2PA cross-section for the HE-2PA band as a function of the
EWG strength in contrast to a linear increase for the LE-2PA band. Thus, a
significant breakthrough obtained in the present work was that such molecular
architecture additionally to enhance the HE-2PA band, it maintains the near-IR
2PA cross-section with a high magnitude, which, in general, is low for molecular
systems.

4 – FINAL REMARKS
We have shown that branched π-conjugated polymers composed by a
triphenylamine-core connected to chiral binaphthalene units and strong EWG
generate a push-pull molecular architecture with a high 2PA cross-section in the
near-IR region (900-1300 nm). 2PA values between 300-565 GM were obtained
depending on EWG strength. By employing the two-level model for the lowest-
energy 2PA band, we observed that the transition dipole moment increases
while the static dipole moment change between the ground and the first excited
state fluctuates as a function of the effective number of π-electron. However,
we found the lowest and highest 2PA cross-section for the IR transition for the
polymer 2 and polymer 3, respectively, in agreement with the charge separation
values obtained. At the same time, we have observed an increase in the ratio

 2 PA /   2 PA
 HE
between the HE-2PA and LE-2PA cross-section ( LE ). Such results
pointed out that the stronger EWG enhances the octupolar character for this
supramolecular (helical) rodlike structure, becoming the higher-energy 2PA
band with a larger 2PA cross-section. However, such molecular strategy allows
maintaining the high 2PA cross-section in the IR region, whose behavior is not
observed for random coil polymers. These results suggest this molecular
architecture as an effective mechanism to obtain a high third-order nonlinear
optical response in the near-IR region.

ACKNOWLEDGMENTS

Financial supportfrom FAPESP (Fundação de Amparo à Pesquisa do Estado

de São Paulo, grants 2018/11283-7 and2015/20032-0), FAPEMIG (Fundação

12
de Amparo à Pesquisa do Estado de Minas Gerais, APQ-01469-18), CNPq
(Conselho Nacional de Desenvolvimento Científico e Tecnológico),
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and
the Air Force Office ofScientificResearch (FA9550-15-1-0521) are
acknowledged.

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16
 Supramolecular (helical)
rodlike structure
Ohex
hexO

n
N
ICT   / e
ICT  50  70%

2PA wave le ngth (nm)

ICT 2PA wav elength (nm)
EWG
600 700 800 900 1000 1100 600 800 1000 1200 1400
8 1000 12 1000

Molar A bs or ptivity (10 4 M -1cm -1)

1PA spectrum 1PA spectrum

Molar absorptivity(104 M-1cm -1)

2PA spectrum 2PA spectrum

(c)

2PA cross section (GM)

2LM fit ting

(a)
800 2LM fit ting 800

2 PA Cross s ection (GM)

O
6 9

600 600

NO2
4 6

2
400

3
400
S
200 200

0
300 350 400 450
1PA wavelength (nm)
500
0
550
0
300 400 500
1PA wav elength (nm)
600
0
700 O N
ICT N
IR region band O

S
2PA wavelength (nm) 2PA wa velength (nm)
700 900 1100 1300 1500 600 800 1000 1200 1400 1600
9 1000 10 1000

S
1PA spectrum
Molar Absorptiv ity (10 M cm )

Molar a bs or ptiv ity (1 04 M-1c m-1)

300-565 GM
1PA spetrum
-1

2PA spect rum

2PA spectrum
2LM fit ting 800
(b) 8
(d) 2LM f itting
800
-1

2 PA cross s ection (GM)

2PA c ross s ection (GM)

N
4

6
600 6 600

400 4 400

O
3

0
350 450 550 650
200

0
750
2

0 0
200
O
300 400 500 600 700 800
1PA wavelength (nm) 1PA wa velength (nm)

O CN CN
CN

17