Nonlinear optical properties of symmetrical and asymmetrical porphyrin derivatives with click chemistry modification

Article abstract of DOI:10.1016/j.dyepig.2016.07.010

The novel kind of charge-transfer porphyrin complexes with symmetrical and asymmetrical side groups were synthesized by the high-yielding [2?+?2] click chemistry reaction involved a two-step procedure. Both electrochemical and UV–vis studies were characterized and proved that the side groups of the porphyrin complexes played an important role on optical properties and energy gaps. The novel series did show the narrower band gap and broader absorption in the visible and near infrared region. As the side groups, the click moieties also affected the third-order nonlinear optical responses, and all the compounds exhibited the expected nonlinear optical properties which were affected by the chemical structures. The optical-limiting performance had also been studied, which was in agreement with the result of Z-scan experiments.

Full text of DOI:10.1016/j.dyepig.2016.07.010

Dyes and Pigments 134 (2016) 155e163
Contents lists available at ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Nonlinear optical properties of symmetrical and asymmetrical
porphyrin derivatives with click chemistry modification
Xiong Liu , Dong Wang , Hong Gao b , Zhou Yang a , Yan Xing , Hui Cao ,
a
a
,
*
,
**
,
***
b
a
a
a
c
d
Wanli He , Huihui Wang , Jianming Gu , Huiying Hu
a
Department of Materials Physics and Chemistry, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing
1
00083, PR China
China Academy of Space Technology, Beijing 100094, PR China
Department of Adult Joint Reconstruction, Beijing Jishuitan Hospital, Beijing 100035, PR China
Department of Obsterics and Gynecology, Peking Union Medical College Hospital, Beijing 100730, PR China
b
c
d
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 25 February 2016
Received in revised form
The novel kind of charge-transfer porphyrin complexes with symmetrical and asymmetrical side groups
were synthesized by the high-yielding [2 þ 2] click chemistry reaction involved a two-step procedure.
Both electrochemical and UVevis studies were characterized and proved that the side groups of the
porphyrin complexes played an important role on optical properties and energy gaps. The novel series
did show the narrower band gap and broader absorption in the visible and near infrared region. As the
side groups, the click moieties also affected the third-order nonlinear optical responses, and all the
compounds exhibited the expected nonlinear optical properties which were affected by the chemical
structures. The optical-limiting performance had also been studied, which was in agreement with the
result of Z-scan experiments.
5
July 2016
Accepted 6 July 2016
Available online 7 July 2016
Keywords:
Porphyrin
Click chemistry
Nonlinear optics
Optical limiting
© 2016 Elsevier Ltd. All rights reserved.
1. Introduction
molecular structure [4,5]. From a more fundamental perspective,
many studies have concerned porphyrins [6,7], which offer great
Considerable attention has been concentrated dramatically on
organic third-order nonlinear optical (NLO) materials in recent
years for their promise in optical telecommunications, ultrahigh
speed signal processing, real-time target recognition, and
aberration-corrected imaging, where linear and nonlinear absorp-
tion must be minimized, and in optical power limiting (OPL), where
nonlinear absorption must be maximized [1e3]. The organic ma-
scope for imaginative molecular engineering with the aim of real-
izing new, multifunctional NLO materials. However, comparing
with the actually applications of inorganic materials, up to date,
search for new organic materials and studying on the factors
affecting the nonlinear optical properties of these organic com-
pounds as nonlinear optical materials are still necessary.
In order to solve these problems, the most attractive charac-
teristic of organic based materials derives from the versatility of
modern organic synthetic methods, which enable the chemist to
tune the photophysical properties of a material to enhance a
particular NLO effect simply by altering flexible synthetic routes.
terials with prominent
p-electron delocalization include porphy-
rins, phthalocyanines, fullerenes, and organometallic compounds.
Among them, porphyrins emerged as promising candidates are of
interest since a significant enhancement of hyperpolarizability can
be achieved through metal insertion at the ring center or by
functionalization at the peripheral positions. Usually, large
nonlinear optical properties are always accompanied with highly
While e theoretically e almost any desired b-substituted porphyrin
can be prepared based on historical contributions from eminent
chemists such as Willst a€ tter, Fischer, Woodward, Eschenmoser and
conjugated large
p-system or extended aromatic core of the
Smith [8e10] there were still limitations in the preparation of
asymmetrical
porphyrins
[11,12].
Meanwhile,
post-
functionalization may be a good method for designing and pre-
paring the asymmetric porphyrins. Recently, [2 þ 2] click chemistry
[13e19] became one of the most important techniques to attach
various chromophores to porphyrins or other derivatives, affording
*
Corresponding author.
*
*
* Corresponding author.
** Corresponding author.
E-mail address: wangdong@ustb.edu.cn (D. Wang).
http://dx.doi.org/10.1016/j.dyepig.2016.07.010
143-7208/© 2016 Elsevier Ltd. All rights reserved.
0

156
X. Liu et al. / Dyes and Pigments 134 (2016) 155e163
a variety of new organics in a straightforward way. The strong
polarizability and long conjugated system can be obtained at the
same time by [2 þ 2] click chemistry, and both the factors has been
proven effective to improve the NLO properties [20e26]. The
asymmetrical porphyrins were simply synthesized by the high-
yielding [2 þ 2] click reaction. It’s kind of a necessity that, the
field of nonlinear optics [20e26] has attracted substantial research
interest, with most of the attention being focused on establishing
the fundamental relationship between nonlinear optical response
and chemical structures. Furthermore, the design and preparation
of asymmetrical porphyrins would be more of a challenge.
porphyrin complexes. After the porphyrin (R) that branched
chain contained alkynyl needed to be synthesized, the synthesis of
symmetrical and asymmetrical porphyrins with different click
moieties involved a two-step procedure. First, by controlling the
reactant molar ratio, the series of single substituted R-X (R-1, R-2,
and R-3) was synthesized by the high-yielding [2 þ 2] click reaction
4
[27] using the first electron acceptors (TCNE, TCNQ, and F -TCNQ)
as click reagents [13e26]. Then the second electron acceptors were
appended by the similar way to obtain R-XY (R-11, R-12, R-13, R-22,
R-23, R-33). As far as we know, it is very difficult to synthesize the
asymmetrical porphyrin-system for enhancing the push-pull
character with highly asymmetrical substitution [28e31]. In this
paper, we try to synthesize the symmetrical porphyrins with two
same reactable groups first, then try to make one of the reactable
groups to react with click reagent by controlling the feed weight
ratio. The symmetrical porphyrins with two same click moieties
also can be synthesized by the one step method, and the excess of
click reagents were added. The asymmetrical porphyrins were
simply synthesized by the high-yielding [2 þ 2] click reaction here,
but the total yields still were limits in the yields of porphyrin (R)
itself and reactant that branched chain contained alkynyl. It is
significant to note that the mixtures of two products and one
reactant are obtained for synthesizing the asymmetric click prod-
ucts. In the experimental section, we showed different yields for
every chemical composition. Due to great difference in polarity
from the click moieties, all the porphyrin derivatives could be very
In this paper, the high-yielding [2 þ 2] click reaction was used to
design and prepare asymmetrical porphyrins, and a series of por-
phrins with the different click moieties were obtained. The
different conjugated
p-systems and electron-withdrawing prop-
erties of the novel porphyrins may be discussed based on the series
or amount of click moieties. Maybe, they had the potential appli-
cations as the nonlinear optical materials or optical-limiting
materials.
2
. Result and discussion
2.1. Synthesis
The synthesis scheme of porphyrins was shown in Fig. 1, and the
highlight parts represented click structures of charge-transfer
Fig. 1. General scheme for the synthesis of porphyrins.

X. Liu et al. / Dyes and Pigments 134 (2016) 155e163
157
easily separated by column chromatography. There are two clear
advantages for the synthesis method, one is the simple, moreover
the porphyrins can contain the asymmetrical and strong the push-
pull character chemical structures from one step. The porphyrins
with symmetrical or asymmetrical groups had different charge
transfer system, which be supposed to generate different internal
interaction. All the newly synthesized compounds were fully
characterized by NMR, FTIR, and UVevis, mass and other spectro-
scopic methods. The porphyrins with different conjugation struc-
tures and electron-withdrawing groups were predicted to
represent different photoelectric properties, and then maybe
enhance the nonlinear optical properties.
2.2. UVevis spectroscopy
The click reaction of R was initially investigated by UVevis
spectroscopic titration experiments by adding acceptor molecule
TCNE to R in chlorinated solvents (Fig. 2a). On the whole, the ab-
sorption intensities of the precursor (R) started to decrease, while
the absorption intensities of the new compounds (R-1,R-11)
increased gradually. In the previous work [21e26], it has been
proved that the click chemistry reaction is quick and quantitative,
and the linear changing relationship between peak intensity and
titration volume were observed. In this titration experiments, the
intensities of all the new peaks increased with the titration volume,
but the linear changing relationship was hardly ever observed. It is
the reason that the click chemistry reaction is quantitative not se-
lective. The compound R had two clicked alkynyl groups, three
kinds of compounds (R, R-1, R-11) were co-exist after the TCNE
solution was added. The proportional relation of R, R-1, R-11 was an
indefinite quantity, so he linear changing relationship between
peak intensity and titration volume can not be observed here. The
3
new charge transfer (CT) band at 475 nm (l ) were shown due to
the occurrence of intermediate product (R-1) click product (R-11),
and the CT band at 347 nm disappeared from the spectrum due to
consumption of reagent R. The presence of the isosbestic point at
3
63 nm and 425 nm for R-11 indicated no side reactions. The
UVevis monitoring indicated that the reaction was a typical click-
type reaction [13e26], and the electronic state of the product was
modulated by TCNE.
UVevis absorption spectra of all mono-substitutedporphyrins
(
R, R-1, R-2, R-3), as shown in Fig. 2b, showed a similar absorp-
tion band in the range of 375e442 nm (the Soret band region) and
80e660 nm (the Q band region), which explained the porphyrins
had similar character. The porphyrins presented several similar
peaks, called , shown in Table 1. It is important that
the absorptions peaks and of click sections are red-shifted by
4
1 2 3 4 5
l , l , l , l , l
l
6
l
7
Fig. 2. UVevis absorption spectra of (a) titration with TCNE (0e1.1 equiv); (b) R, R-1, R-
around 232 nm for R-2 and 384 nm for R-3 compared R-1. The
reasons were dramatically facilitated by the elongation of conju-
gation lengths of molecular backbones and enhancement of elec-
tron affinities via introduction of strong electron-withdrawing
substitutes [32]. The different click groups modifying porphyrins
have specific ranges (number 1 was 478 nm, 2 was 710 nm, and 3
was 866 nm). Based on the above phenomenon, the similar com-
pounds demonstrated obviously different optical properties, sug-
gesting the different nonlinear optical properties will be presented,
especially the affect of conjugation system on nonlinear optical
response.
In addition, Fig. 2c showed the UVevis absorption spectra
measured for bis-substituted porphyrins (R-3, R-13, R-23, R-33) in
2 2 4
CH Cl solution. The porphyrins modified with F -TCNQ click
groups all have specific absorptions peak at about 860 nm and
similar cut-off adsorption wavelength, indicating that the other
branched chain had little impact on the click section. All the relative
absorption peak heights of curves in Fig. 2c were normalized at
2
2 2
, R-3; (c) R-3, R-13, R-23, R-33 in CH Cl solution at 298 K.
Table 1
Optical properties of the compounds.
Materials S band Q band
Click moieties
(nm) (nm)
l
1
(nm)
l
2
(nm)
l
3
(nm)
l
4
(nm)
l
5
(nm)
l
6
l
7
R
R-1
R-2
R-3
R-11
R-12
R-13
R-22
R-23
R-33
410
408
408
408
404
406
406
410
410
410
504
504
504
504
504
504
504
504
504
504
544
546
546
542
550
548
544
548
544
540
578
578
578
578
578
578
578
578
578
578
634
636
642
636
636
642
636
638
638
638
e
e
e
e
e
e
478
710
862
472
472
478
710
710
866
708
866
e
860
e

158
X. Liu et al. / Dyes and Pigments 134 (2016) 155e163
4
10 nm. Compared with R-3, R-33 presented the greater the rela-
Table 2
Electrochemistry properties of the compounds.
tive absorption peak height at 860 nm. The absorption peak of click
moieties undergone slightly bathochromic shifts. The reason of the
phenomenon should be electronic interactions between symmet-
rical groups. The phenomena suggested that the click moieties
becamenew independent conjugation systems after click reaction.
The UVevis absorption spectra of the other porphyrins were rep-
resented in Fig. S2 (a b c).
ox a
red a
Egb (eV)
Egc (eV)
Egd (eV)
Materials
E
on
(V)
E
on
(V)
R
R-1
R-2
R-3
R-11
R-12
R-13
R-22
R-23
R-33
0.71
0.71
0.73
0.70
1.01
0.81
0.68
0.78
0.68
0.68
ꢀ0.73
ꢀ0.40
ꢀ0.18
ꢀ0.08
ꢀ0.35
ꢀ0.12
ꢀ0.08
ꢀ0.14
ꢀ0.07
ꢀ0.06
1.44
1.11
0.91
0.78
1.36
0.93
0.76
0.92
0.75
0.74
1.88
1.78
1.17
0.93
1.73
1.12
0.88
0.89
0.89
0.93
2.52
1.81
1.35
1.00
2.20
1.80
1.46
1.80
1.49
1.20
2.3. Electrochemistry
Fig. 3a showed the cyclic voltammograms and energy levels
a
Obtained from the cyclic voltammograms, the onset of the oxidation and
results for the porphyrins (R, R-1, R-2, R-3). The onset reduction
potential, onset oxidation potential (correspond energy levels)
were also listed in Table 2. From R to R-3, the LUMO energy levels
and electrochemical band gaps were decreased because of the
reduction peak.
b
c
Electrochemical band gaps.
Optical band gaps obtained from UVevis absorption spectra.
DFT band gaps (See Figs. S1 and S2).
d
expanded
p-conjugation and strong electron withdrawing ability
[
ꢀ
20]. The HOMO energy levels were also calculated to be ꢀ5.33,
2
2
.4. Nonlinear optics
5.33, ꢀ5.35 and ꢀ5.32 eV, respectively. Compared with the data of
LUMO, the HOMO of the mono-substitutedporphyrins (R R-1 R-2 R-
.4.1. Z-scan experiments
3
) was less influenced by the side groups. The relatively lower
Z-scan experiments were utilized to verify the specific rela-
HOMO energy level of the compounds is beneficial to the better
stability against oxidation [32]. To provide further insight into the
fundamentals of molecular architecture, molecular simulation was
carried out with a chain length of n ¼ 1 at the DFTB3LYP/6-31G(d)
level with the Gaussian 03 program package (See Fig. 3c and
Fig. S3). The DFT calculations [33] gave satisfactory accuracy
comparing to the experiment results, and provided strong support
for this idea. The data from Fig 3c were calculated by the DFT, and
the data from Fig 3b were measured by cycle voltammograms and
UV spectra. On the existing difference between the experimental
value and the theoretical value here. Because of strong electron
withdrawing atom fluorine and cyano group, from the ground state
to the excited state, the electron density in the LUMO was located
on the click moiety (See Fig. S3). Furthermore, for R-XY series, the
electron density in the LUMO was located on the one side of click
moiety which had more strong electron-withdrawing ability. From
the electrochemical and optical studies, it can be proved that the
chemical structures of click moieties were the key factor on the
physical properties, and the symmetry of porphyrins is relatively
weak factor.
tionship between the chemical structures and nonlinear optical
response, with parameters summarized in Table 3. The normalized
open aperture Z-scan traces of the samples and a good fit between
the experimental data were shown in Fig. 4. The normalized close
aperture Z-scan traces of the samples were shown in Figs. S4 and
S5. The NLO absorption data was calculated according to the re-
ported equations (see Supporting).
As shown in Fig. 4a, compared with R, the compounds R-X series
presented the lower nonlinear absorption coefficient, which could
be ascribed that the electronic cloud density on the porphyrin ring
was greatly reduced by the strong electron withdrawing groups.
However, the coefficients of compounds with TCNQ click moieties
were higher than those of R and other compounds because of
introduction of longer conjugated structures. Furthermore, the
(3)
nonlinear absorption coefficients (
< R-2, which could be ascribed to the competitive relation be-
tween the elongation of conjugation length (benzene ring in TCNQ)
Compare R-1 and R-2) and introduction of strong electron with-
c ) were in the order of R-1 < R-
3
(
drawing atom fluorine (Compare R-2 and R-3). It is important
Fig. 3. (a) Cycle voltammograms of the porphyrins (R, R-1, R-2 and R-3) in CH
2
Cl
2
/Bu
4
NPF
6
at 298 K; (b) LUMO and HOMO energy levels and optical band gaps of the porphyrins; (c)
The optimized structures and electron distributions of HOMO and LUMO levels of R-1 models.

X. Liu et al. / Dyes and Pigments 134 (2016) 155e163
159
Table 3
NLO properties of the porphyrin derivatives.
ꢁ 10ꢀ (m/W)
12
n
2
ꢁ 10ꢀ19 (m /W)
2
c(3) ꢁ 10ꢀ13 (esu)
Materials
b
ꢁ 10ꢀ12 (m/W)
n
2
ꢁ 10ꢀ19 (m /W)
2
c(3) ꢁ 10ꢀ13 (esu)
Materials
b
R
6.8
1.8
2.1
0.6
0.05
1.2
1.60
0.63
2.77
1.14
0.51
R-12
R-13
R-22
R-23
R-33
0.68
ꢀ1.9
1.3
1.4
ꢀ2.2
2.0
2.0
2.9
3.6
2.6
1.04
1.11
1.52
1.87
1.42
R-1
R-2
R-3
R-11
ꢀ0.96
5.3
2.2
1.0
Fig. 4. Normalized open aperture Z-scan traces measured for the porphyrins (a) R, R-1,
R-2, R-3; (b) R-1, R-11, R-12, R-13.
Fig. 5. The nonlinear transmission results for the porphyrins at 532 nm.
showed the very special trace. The optical-limiting performance of
the R (Fig. 5a) was found to be much better than others, which was
in complete agreement with the result of Z-scan experiments. For
the R, the transmittance decreased with input intensity first, then
the plateau region was observed. The transmittance increased
suggestion that if the electronic cloud density in the ring conju-
gated system was greatly reduced, maybe it will be reduce the
nonlinear absorption coefficients. However, the nonlinear absorp-
tion coefficients showed the same order of magnitude as those in
the references [21e26]. Moreover, most of the prepared phorphyrin
complexes here showed the nonlinear reverse saturable absorption
again when the input intensity was bigger than 0.2 mj. The optical-
limiting performances of R and R-1 preferably showed a tendency
from the nonlinear reverse saturable absorption to nonlinear
saturable absorption at 532 nm, and the laser intensity of turning
(
RSA), and it is obvious advantage for the nonlinear optical appli-
cation (such as the optical limiting materials) comparing the pre-
vious reference. Based on the assumption, the strong electron
withdrawing groups maybe limit the effective charge transfer
greatly, and impaired reverse saturable absorption properties, even
showed a change from RSA to nonlinear saturable absorption (SA)
point was about 0.2
mj. Indeed the transmittance decrease with
respect to the linear behavior was ascribed to reverse saturable
absorption (RSA), while the opposite behavior was referred to
saturable absorption (SA) [33e36]. The operating mechanism is
reverse saturable absorption (RSA) as the effective excited-state
absorption cross-section was found higher than ground state ab-
sorption cross-section as well as the magnitude of nonlinear ab-
sorption coefficient was found decreasing with on-axis input
(
see Fig. 4b).
2.4.2. Optical limiting properties
Fig. 5 and Fig. S6 displayed the nonlinear transmittance of the
porphyrins in CH Cl with 21 ps pulses at 532 nm, and all the curves
2 2

160
X. Liu et al. / Dyes and Pigments 134 (2016) 155e163
intensity [37,38]. The tendency from the nonlinear reverse satu-
rable absorption to nonlinear saturable absorption may be ascribed
to the difference saturable absorption of difference absorption
removed in vacuo and the product was purified by column chro-
matography (SiO
the compound D (493.1 mg, 73%) as a white solid.
2
, petroleum ether/ethyl acetate ¼ 10: 1)) to give
cross-section. When the laser intensity is lower than 0.2 mj, the first
effective excited-state absorption cross-section was higher than
that of ground state, so that the nonlinear reverse saturable ab-
4.2. Synthesis of the compound P (5,15-bis(4-iodophenyl)
porphyrin)
sorption was observed. If the laser intensity is higher than 0.2 mj,
the first effective excited-state absorption cross-section would
become saturated.
Compound di(1H-pyrrol-2-yl)methane (185 mg, 2.0 mmol)
and 4-iodobenzaldehyde (464 mg, 2.0 mmol) were dissolved in
Compared with R without click moiety, most of the click prod-
ucts showed more special phenomenon which with increasing the
laser intensity, the transmittance were increased at the early stage,
and then gradually declined during the second stage, furthermore
increased again. The optical limiting curves look like squiggly lines
and a cause of the phenomenon was the introduction of click
moieties. However, the phenomenon is another proof that the
strong electron withdrawing groups greatly influence reverse
saturable absorption properties, even showed a change from RSA to
SA.
anhydrous CH
degassed with Ar for 15 min. Trifluoroacetic acid (20
was added, and the mixture was stirred for 2 d at RT. Then, DDQ
(898 mg, 4.0 mmol) was added in one portion, and the mixture was
stirred for 2 h at RT. The resulting mixture was concentrated,
rediluted with CH
solvent was removed in vacuo and the product was purified by
column chromatography (SiO
(143 mg, 10%) as dark purple solid.
2
Cl
2
(100 mL) under Ar, and the mixture was
L, 0.27 mmol)
m
2 2
Cl , and filtered through a plug of silica gel. The
2
, CH
2
Cl
2
) to give compound P
0
4.3. Synthesis of the compound R (4,4 -((porphyrin-5,15-
3
. Conclusions
diylbis(4,1-phenylene))bis(ethyne-2,1-diyl))bis(N,N-
dihexadecylaniline))
We addressed the significance of third-order nonlinear optical
properties in symmetrical and asymmetrical porphyrin complexes
obtained by click chemistry. Computational studies of DFT pre-
dicted the enlargement of conjugation lengths and electron-
withdrawing abilities can modify the energy level and optical
properties of those derivatives. The nonlinear optical properties
acted many special phenomena, especially absorption cross-section
from RSA to SA. Both electrochemical and UVevis spectra studies
reveals the origin of such nonlinear absorption coefficients and
suggests that the click moieties can change the properties of ab-
sorption cross-section from RSA to SA.
4-Ethynyl-N,N-dihexadecylaniline (621.5 mg, 1.1 mmol) ob-
tained by previous work [24], Pd(PPh
CuI (4.2 mg, 0.022 mmol), and PPh
3
)
2
Cl
2
(15.4 mg, 0.022 mmol),
3
(16.2 mg, 0.060 mmol) were
added to a degassed solution of triethylamine (6 mL) and THF
(10 mL) under argon. Meanwhile 5,15-bis(4-iodophenyl)porphyrin
(500.0 mg, 0.54 mmol) were added. After 15 min of stirring at this
ꢂ
temperature, the reaction was heated to 80 C and stirred overnight
under argon atmosphere. The cooled reaction mixture was diluted
with CH
over MgSO
2
Cl
2
and extracted with water. The organic phase was dried
, and the solvent was removed under reduced pressure.
4
The crude product was purified by column chromatography (silica
1
4
. Experimental section
gel, petroleum ether) to afford purple powder R (86.2 mg, 81%). H
NMR (CDCl
3
, 500 MHz):
d
¼ ꢀ3.06(2H, s), 0.90(12H, m), 1.28(96H,
Reagents were purchased from commercial sources (Aladdin)
and used without further purification. 1H NMR spectra were
m), 1.39(8H, m), 1.67(8H, m), 3.35(8H, t), 6.69(4H, d, J ¼ 8.5 Hz),
7.56(4H, d, J ¼ 8.5 Hz), 7.96(4H, d, J ¼ 8.0 Hz), 8.26(4H, d, J ¼ 8.0 Hz),
measured on a BRUKER AVANCE III HD NMR spectrometer
9.14(4H, d, J ¼ 9.5 Hz), 9.44(4H, d, J ¼ 4.5 Hz), 10.36(2H, s) ppm. FT-
ꢂ
ꢀ1
(
500 MHZ) at 20 C. Chemical shifts are reported in ppm downfield
IR (KBr, cm ):
n
¼ 2921, 2852, 2208, 1609, 1522, 1468, 1401, 1369,
from SiMe
4
, using the solvent’s residual signal as an internal
1197, 9556, 856, 797, 720, 540. MALDI-TOF-MS (dithranol): m/z:
calcd for C112H N : 1590.55 g mol , found: 1590.8 g mol [M];
160 6
ꢀ
1
ꢀ1
reference. FT-IR was recorded on a Perkin Elmer LR-64912C Fourier
transform infrared spectrometer. All MALDI-TOF-MS spectra were
measured on a Shimadzu AXIMA-CFR mass spectrometer. The
operation was performed at an accelerating potential of 20 kV by a
linear positive ion mode with dithranol as a matrix. UV/Vis spectra
were recorded in a quartz cuvette on a JASCO V-570 spectropho-
tometer. Cyclic voltammetric measurements were carried out in a
conventional three-electrode cell using Glassy Carbon working
electrodes, a platinum wire counter electrode, and an Ag/AgCl
reference electrode on a computer-controlled CHI 660C instrument
at room temperature. The nonlinear optical properties (NLO)
response by means of Z-scan technique and the optical limiting
performance (OL) was measured, employing 21 ps laser pulses at
elemental analysis calcd (%) for C124H160N14 (1590.55): C 84.58, H
10.14, N 5.28; found: C 84.55, H 10.15, N 5.30.
4.4. Synthesis of the compound R-1 (2-(4-(dihexadecylamino)
phenyl)-3-(4-(15-(4-((4-(dihexadecylamino)phenyl)ethynyl)
phenyl)porphyrin-5-yl)phenyl)buta-1,3-diene-1,1,4,4-
tetracarbonitrile)
To a solution of the click compound R (158.8 mg, 0.1 mmol) in
THF (50 mL) was added click reagent TCNE (12.8 mg, 0.1 mmol), and
ꢂ
the resulting mixture was then stirred at 30 C for 1 h under Ar. The
solvent was concentrated under reduced pressure and the crude
5
32 nm and 1064 nm delivered by a mode-locked Nd:YAG laser.
.1. Synthesis of the compound D (di(1H-pyrrol-2-yl)methane)
A suspension of paraformaldehyde (3 g, 0.1 mol, 1 equiv.) in
product was purified by column chromatography using CH
2 2
Cl as
the eluent to give R-1 (104.7 mg, 61%), R-11 (27.8 mg,15%) as a black
1
4
solid, and the click compound R (20.7 mg, 13%). H NMR (CDCl
00 MHz):
3
,
5
d
¼ ꢀ3.07(2H, s), 0.88(12H, m), 1.27(96H, m), 1.39(8H,
m), 1.67(8H, m), 3.34(4H, t), 3.47(4H, t), 6.69(2H, d, J ¼ 9.0 Hz),
6.84(2H, d, J ¼ 9.0 Hz), 7.56(2H, d, J ¼ 8.0 Hz), 7.97(2H, d, J ¼ 7.5 Hz),
pyrrole (150 mL, 2.2 mol) was degassed with Ar for 15 min. The
mixture was heated to 55 C for 10 min before the addition of InCl
ꢂ
3
8.06(2H, d, J ¼ 9.5 Hz), 8.23(4H, m), 8.48(2H, d, J ¼ 8.0 Hz), 9.07(4H,
ꢂ
ꢀ1
(
2.2 g, 9.9 mmol). The mixture was stirred at 55 C for 3 h, cooled
m), 9.44(4H, m), 10.38(2H, s) ppm. FT-IR (KBr, cm ):
n
¼ 2924,
down, and treated with powdered NaOH (8.0 g, 0.2 mol). After
h at RT, The resulting mixture was concentrated, rediluted with
CH Cl , and filtered through a plug of silica gel. The solvent was
2853, 2215, 1727, 1602, 1523, 1489, 1457, 1417, 1346, 1287, 1184, 957,
160 10
792, 742. MALDI-TOF-MS (dithranol): m/z: calcd for C118H N :
1718.65 g mol , found: 1718.8 g mol [M]; elemental analysis
1
ꢀ
1
ꢀ1
2
2

X. Liu et al. / Dyes and Pigments 134 (2016) 155e163
161
calcd (%) for C118H160N10 (1718.65): C 82.47, H 9.38, N 8.15; found:
C 82.44, H 9.40, N 8.16.
1212, 1184, 956, 855, 790, 719. MALDI-TOF-MS (dithranol): m/z:
ꢀ ꢀ1
1
calcd for C124H N14: 1846.74 g mol , found: 1847.0 g mol [M];
160
elemental analysis calcd (%) for C124H160N14 (1846.74): C 80.65, H
8.73, N 10.62; found: C 80.64, H 8.73, N 10.63.
4.5. Synthesis of the compound R-2 (2-(4-(3,3-dicyano-1-(4-
(
dihexadecylamino)phenyl)-2-(4-(15-(4-((4-(dihexadecylamino)
phenyl)ethynyl)phenyl)porphyrin-5-yl)phenyl)allylidene)
cyclohexa-2,5-dien-1-ylidene)malononitrile)
4.8. Synthesis of the compound R-12 (2-(4-(15-(4-(1,1-dicyano-3-
(4-(dicyanomethylene)cyclohexa-2,5-dien-1-ylidene)-3-(4-
(dihexadecylamino)phenyl)prop-1-en-2-yl)phenyl)porphyrin-5-yl)
To a solution of the click compound R (158.8 mg, 0.1 mmol) in
THF (50 mL) was added click reagent TCNQ (20.4 mg, 0.1 mmol),
and the resulting mixture was then stirred at 50 C for 4 h under Ar.
phenyl)-3-(4-(dihexadecylamino)phenyl)buta-1,3-diene-1,1,4,4-
tetracarbonitrile)
ꢂ
The solvent was concentrated under reduced pressure and the
crude product was purified by column chromatography using
To a solution of the compound R-1 (85.8 mg, 0.05 mmol) in THF
(50 mL) was added click reagent TCNQ (10.2 mg, 0.05 mmol), and
the resulting mixture was then stirred at 50 C for 3 h under Ar. The
ꢂ
CH
8%) as a black solid, and the click compound R (27.0 mg, 17%). H
NMR (CDCl , 500 MHz):
2
Cl
2
as the eluent to give R-2 (100.4 mg, 56%), R-22 (36.0 mg,
1
1
solvent was concentrated under reduced pressure and the crude
3
d
¼ ꢀ3.08(2H, s), 0.89(12H, m), 1.28(96H,
product was purified by column chromatography using CH
2
Cl
2
as
the eluent to give R-12 (82.6 mg, 86%) as a black solid. H NMR
(CDCl , 500 MHz):
1
m), 1.46(8H, m), 1.73(8H, m), 3.34(4H, t), 3.48(4H, m), 6.69(2H, d,
J ¼ 8.5 Hz), 6.86(2H, d, J ¼ 9.0 Hz), 7.31(1H, m), 7.41(2H, m), 7.55(4H,
d, J ¼ 7.5 Hz), 7.73(1H, m), 7.96(2H, d, J ¼ 8.0 Hz), 8.17(2H, d,
J ¼ 8.0 Hz), 8.24(2H, d, J ¼ 8.0 Hz), 9.00(2H, d, J ¼ 4.5 Hz), 9.15(2H, d,
3
d
¼ ꢀ3.15(2H, s), 0.89(12H, m), 1.28(96H, m),
1.42(8H, m), 1.74(8H, m), 3.49(8H, m), 6.85(4H, m), 7.30(1H, m),
7.41(2H, m), 7.55(4H, d, J ¼ 9.0 Hz), 7.72(1H, m), 8.06(2H, d,
J ¼ 9.0 Hz), 8.17(4H, m), 8.42(4H, m), 9.01(4H, m), 9.46(4H, m),
ꢀ1
J ¼ 4.5 Hz), 9.44(4H, m), 10.37(2H, s) ppm. FT-IR (KBr, cm ):
ꢀ
1
n
¼ 2923, 2853, 2205, 1582, 1523, 1403, 1348, 1180, 793. MALDI-
10.39(2H, s) ppm. FT-IR (KBr, cm ):
n
¼ 2923, 2853, 2205, 1603,
ꢀ
1
TOF-MS (dithranol): m/z: calcd for C124
H
164
N
10: 1794.75 g mol
,
1582, 1403, 1348, 1180, 797. MALDI-TOF-MS (dithranol): m/z: calcd
ꢀ
1
þ
ꢀ1
ꢀ1
þ
found: 1795.6 g mol
[MH] ; elemental analysis calcd (%) for
164
for C130H N14: 1922.84 g mol , found: 1923.8 g mol [MH] ;
C124H164N10 (1794.75): C 82.98, H 9.21, N 7.80; found: C 82.98, H
elemental analysis calcd (%) for C130H164N14 (1922.84): C 81.20, H
8.60, N 10.20; found: C 81.23, H 8.61, N 10.22.
9
.22, N 7.80.
4
.6. Synthesis of the compound R-3 (2-(4-(3,3-dicyano-1-(4-
4.9. Synthesis of the compound R-13 (2-(4-(15-(4-(1,1-dicyano-3-
(4-(dicyanomethylene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-
ylidene)-3-(4-(dihexadecylamino)phenyl)prop-1-en-2-yl)phenyl)
porphyrin-5-yl)phenyl)-3-(4-(dihexadecylamino)phenyl)buta-1,3-
diene-1,1,4,4-tetracarbonitrile)
(
dihexadecylamino)phenyl)-2-(4-(15-(4-((4-(dihexadecylamino)
phenyl)ethynyl)phenyl)porphyrin-5-yl)phenyl)allylidene)-2,3,5,6-
tetrafluorocyclohexa-2,5-dien-1-ylidene)malononitrile)
To a solution of the click compound R (158.8 mg, 0.1 mmol) in
THF (50 mL) was added click reagent F4-TCNQ (27.6 mg, 0.1 mmol),
and the resulting mixture was then stirred at 70 C for 8 h under Ar.
To a solution of the compound R-1 (85.8 mg, 0.05 mmol) in THF
(50 mL) was added click reagent F4-TCNQ (13.8 mg, 0.05 mmol),
and the resulting mixture was then stirred at 70 C for 8 h under Ar.
ꢂ
ꢂ
The solvent was concentrated under reduced pressure and the
crude product was purified by column chromatography using
The solvent was concentrated under reduced pressure and the
CH
as a black solid, and the click compound R (31.8 mg, 20%). H NMR
CDCl , 500 MHz):
¼ ꢀ3.07(2H, s), 0.88(12H, m), 1.27(96H, m),
.45(8H, m), 1.67(8H, m), 3.35(4H, t), 3.68(4H, m), 6.69(2H, d,
2
Cl
2
as the eluent to give R-3 (87.6 mg, 47%), R-33 (45.0 mg, 21%)
crude product was purified by column chromatography using
1
1
CH
2
Cl
2
as the eluent to give R-13 (76.7 mg, 77%) as a black solid. H
(
1
3
d
NMR (CDCl
3
, 500 MHz):
d
¼ ꢀ3.15(2H, s), 0.88(12H, m), 1.27(96H,
m), 1.41(8H, m), 1.75(8H, m), 3.47(4H, t), 3.64(4H, t), 6.85(2H, d,
J ¼ 9.5 Hz), 6.97(2H, d, J ¼ 9.5 Hz), 7.61(2H, d, J ¼ 9.0 Hz), 8.06(4H,
m), 8.23(2H, d, J ¼ 8.0 Hz), 8.43(4H, m), 9.00(4H, m), 9.46(4H, m),
J ¼ 8.5 Hz), 6.98(2H, d, J ¼ 9.5 Hz), 7.56(2H, d, J ¼ 9.0 Hz), 7.96(2H, d,
J ¼ 8.0 Hz), 8.10(2H, d, J ¼ 9.0 Hz), 8.24(2H, d, J ¼ 8.0 Hz), 8.45(2H,
m), 9.00(2H, d, J ¼ 4 Hz), 9.15(2H, d, J ¼ 4.5 Hz), 9.44(4H, m),
ꢀ1
10.40(2H, s) ppm. FT-IR (KBr, cm ):
n
¼ 2923, 2852, 2200, 1633,
ꢀ
1
1
1
C
0.38(2H, s) ppm. FT-IR (KBr, cm ):
n
¼ 2922, 2852, 2200, 1632,
1601, 1388, 1348, 1187, 973, 789. MALDI-TOF-MS (dithranol): m/z:
calcd for C130H F N14: 1994.80 g mol , found: 1994.6 g mol
160 4
ꢀ1
ꢀ1
598, 1388, 1192, 799. MALDI-TOF-MS (dithranol): m/z: calcd for
ꢀ
1
ꢀ1
H
124 160
F
4
N
10: 1866.71 g mol , found: 1867.5 g mol [M];
[M]; elemental analysis calcd (%) for C130H160F4N14 (1994.80): C
78.27, H 8.09, N 9.83; found: C 78.33, H 8.10, N 9.84.
elemental analysis calcd (%) for C124H160F4N10 (1866.71): C 79.79,
H 8.64, N 7.50; found: C 79.78, H 8.64, N 7.51.
0
4
.10. Synthesis of the compound R-22 (2,2 -((porphyrin-5,15-
0
4
.7. Synthesis of the compound R-11 (3,3 -(porphyrin-5,15-
diylbis(4,1-phenylene))bis(2-(4-(dicyanomethylene)cyclohexa-2,5-
dien-1-ylidene)-2-(4-(dihexadecylamino)phenyl)ethan-1-yl-1-
ylidene))dimalononitrile)
diylbis(4,1-phenylene))bis(2-(4-(dihexadecylamino)phenyl)buta-
,3-diene-1,1,4,4-tetracarbonitrile))
1
To a solution of the compound R-1 (85.8 mg, 0.05 mmol) in THF
To a solution of the compound R-2 (89.6 mg, 0.05 mmol) in THF
(50 mL) was added click reagent TCNQ (10.2 mg, 0.05 mmol), and
the resulting mixture was then stirred at 50 C for 3 h under Ar. The
(
50 mL) was added click reagent TCNE (6.4 mg, 0.05 mmol), and the
ꢂ
ꢂ
resulting mixture was then stirred at 30 C for 1 h under Ar. The
solvent was concentrated under reduced pressure and the crude
solvent was concentrated under reduced pressure and the crude
product was purified by column chromatography using CH
2
Cl
2
as
the eluent to give R-11 (83.9 mg, 91%) as a black solid. H NMR
CDCl , 500 MHz):
product was purified by column chromatography using CH
2
Cl
2
as
the eluent to give R-22 (71.9 mg, 71%) as a black solid. H NMR
(CDCl , 500 MHz):
1
1
(
3
d
¼ ꢀ3.09(2H, s), 0.88(12H, m), 1.26(96H, m),
3
d
¼ ꢀ3.15(2H, s), 0.89(12H, m), 1.25(96H, m),
1
8
9
.47(8H, m), 1.73(8H, m), 3.47(8H, t), 6.84(4H, d, J ¼ 9.0 Hz),
1.43(8H, m), 1.75(8H, m), 3.48(8H, t), 6.86(4H, d, J ¼ 9.0 Hz),
7.29(2H, d, J ¼ 9.0 Hz), 7.38(4H, m), 7.55(4H, d, J ¼ 9.0 Hz), 7.71(2H,
m), 8.17(4H, d, J ¼ 8.0 Hz), 8.42(2H, d, J ¼ 8.0 Hz), 9.01(4H, d,
J ¼ 9.5 Hz), 9.46(4H, d, J ¼ 9.5 Hz), 10.40(2H, s) ppm. FT-IR (KBr,
.06(4H, d, J ¼ 9.0 Hz), 8.23(4H, d, J ¼ 8.0 Hz), 8.48(4H, d, J ¼ 8.0 Hz),
.09(4H, d, J ¼ 9.5 Hz), 9.43(4H, d, J ¼ 4.5 Hz), 10.34(2H, s) ppm. FT-
ꢀ
1
IR (KBr, cm ):
n
¼ 2925, 2854, 2216, 1604, 1488, 1471, 1417, 1346,

162
X. Liu et al. / Dyes and Pigments 134 (2016) 155e163
cmꢀ1):
MALDI-TOF-MS (dithranol): m/z: calcd for
n
¼ 2924, 2853, 2204, 1582, 1403, 1349, 1180, 797, 743.
References
C
136 168 14
H N :
ꢀ1
ꢀ1
[1] Marek S. Third-order nonlinear optical materials: practical issues and theo-
1998.94 g mol , found: 1998.6 g mol [M]; elemental analysis
retical challenges. J Mol Model 2011;17:2183e9.
calcd (%) for C136H168N14 (1998.94): C 81.72, H 8.47, N 9.81;
found: C 81.74, H 8.48, N 9.82.
[
2] Pawlicki M, Collins HA, Denning RG, Anderson HL. Two-photon absorption
and the design of two-photon dyes. Angew Chem Int Ed 2009;48:3244e66.
3] He GS, Tan LS, Zheng QD, Prasad PN. Multiphoton absorbing materials: mo-
lecular designs, characterizations, and Applications. Chem Rev 2008;108:
[
4.11. Synthesis of the compound R-23 (2-(4-(3,3-dicyano-2-(4-(15-
1245e330.
(
4-(1,1-dicyano-3-(4-(dicyanomethylene)-2,3,5,6-
[4] Ray PC, Sainudeen Z. Very large infrared two-photon absorption cross section
of asymmetric zinc porphyrin aggregates: role of intermolecular interaction
and donor-acceptor strengths. J Phys Chem A 2006;110:12342e7.
tetrafluorocyclohexa-2,5-dien-1-ylidene)-3-(4-(dihexadecylamino)
phenyl)prop-1-en-2-yl)phenyl)porphyrin-5-yl)phenyl)-1-(4-
[
5] Zhou GJ, Wong WY, Lin ZY. Amorphous diphenylaminofluorene-
functionalized iridium complexes for high-efficiency electrophosphorescent
light-emitting diodes. Angew Chem Int Ed 2006;45:6189e93.
(
dihexadecylamino)phenyl)allylidene)cyclohexa-2,5-dien-1-
ylidene)malononitrile)
[
6] Narendran NKS, Soman R, Sankar P, Arunkumar C, Chandrasekharan K. Ul-
trafast and short pulse optical nonlinearities of meso-tetrakis-(2,3,5,6-
tetrafluoro-N, N,N-trimethyl-4-aniliniumyl) porphyrin and its metal com-
plexes. Opt Mater 2015;49:59e66.
To a solution of the compound R-2 (89.6 mg, 0.05 mmol) in THF
(
50 mL) was added click reagent F4-TCNQ (13.8 mg, 0.05 mmol),
ꢂ
[7] Zheng C, Li YB, Huang L, Li W, Chen WZ. Facile assembly of tetragonal Pt
clusters on graphene oxide for enhanced nonlinear optical properties. Opt
Mater 2015;49:152e7.
and the resulting mixture was then stirred at 70 C for 8 h under Ar.
The solvent was concentrated under reduced pressure and the
crude product was purified by column chromatography using
[8] Smith KM. In: Kadish KM, Smith KM, Guilard R, editors. The porphyrin
handbook, 1. San Diego: Academic Press; 2000. p. 1e44.
1
CH
2
Cl
2
as the eluent to give R-23 (75.5 mg, 73%) as a black solid. H
[
9] Kandasamy K, Shetty SJ, Puntambekar PN, Srivastava TS, Kundu T, Singh BP.
Effects of metal substitution on third-order optical non-linearity of porphyrin
macrocycle. J Porphyr Phthalocya 1999;3:81e7.
NMR (CDCl
3
, 500 MHz):
d
¼ ꢀ3.15(2H, s), 0.89(12H, m), 1.28(96H,
m), 1.48(8H, m), 1.78(8H, m), 3.49(4H, t), 3.66(4H, t), 6.88(2H, d,
J ¼ 9.0 Hz), 7.00(2H, d, J ¼ 9.5 Hz), 7.30(1H, d, J ¼ 9.5 Hz),7.39(2H,
m), 7.58(5H, m), 8.07(2H, d, J ¼ 8.0 Hz), 8.15(2H, d, J ¼ 8.0 Hz),
[
10] Morotti T, Pizzotti M, Ugo R, Quici S, Bruschi M, Mussini P, et al. Electronic
characterisation and significant second-order NLO response of 10,20-
diphenylporphyrins and their ZnII complexes substituted in the meso posi-
8
.39(4H, d, J ¼ 7.5 Hz), 8.97(4H, m), 9.42(4H, m), 10.34(2H, s) ppm.
tion with
p-delocalised linkers carrying push or pull groups. Eur J Inorg Chem
ꢀ1
2006;9:1743e57.
FT-IR (KBr, cm ):
n
¼ 2925, 2851, 2201, 1633, 1598, 1582, 1388,
[
11] Beratan DN. Predicting the frequency dispersion of electronic hyper-
polarizabilities on the basis of absorption data and thomasꢀkuhn sum tules.
J Phys Chem C 2010;114:2349e59.
1349, 1180, 1038, 973, 797. MALDI-TOF-MS (dithranol): m/z: calcd
ꢀ1 ꢀ1 þ
for C136H F N14: 2070.90 g mol , found: 2071.8 g mol [MH] ;
164 4
elemental analysis calcd (%) for C136H164F4N14 (2070.90): C 78.88,
H 7.98, N 9.47; found: C 78.90, H 7.99, N 9.48.
[12] Reeve JE, Collins HA, Mey KD, Kohl MM, Thorley KJ, Paulsen O, et al.
Amphiphilic porphyrins for second harmonic generation imaging. J Am Chem
Soc 2009;131:2758e9.
[
13] Michinobu T, Li YR, Hyakutake T. Polymeric ion sensors with multiple
detection modes achieved by a new type of click chemistry reaction. Phys
Chem Chem Phys 2013;8:2623e31.
0
4
.12. Synthesis of the compound R-33 (2,2 -((porphyrin-5,15-
diylbis(4,1-phenylene))bis(2-(4-(dicyanomethylene)-2,3,5,6-
tetrafluorocyclohexa-2,5-dien-1-ylidene)-2-(4-(dihexadecylamino)
phenyl)ethan-1-yl-1-ylidene))dimalononitrile)
[14] Michinobu T. Adapting semiconducting polymer doping techniques to create
new types of click postfunctionalization. Chem Soc Rev 2011;40:2306e16.
[15] Zhang WS, Wang D, Cao H, Yang H. Energy-level tunable click functionaliza-
tion of [60]fullerene for nonlinear optics. Tetrahedron 2014;21:573e7.
[
16] Mi YS, Liang PX, Yang Z, Wang D, Cao H, He WL, et al. Effects of donor and
acceptor on optoelectronic performance for porphyrin derivatives: nonlinear
optical properties and dye-sensitized solar cells. Chem Res Chin Univ
2015;31:992e6.
To a solution of the compound R-3 (93.2 mg, 0.05 mmol) in THF
(
50 mL) was added click reagent F4-TCNQ (13.8 mg, 0.05 mmol),
ꢂ
and the resulting mixture was then stirred at 70 C for 8 h under Ar.
The solvent was concentrated under reduced pressure and the
[
[
17] Wang D, Michinobu T. One-step synthesis of ladder-type fused poly(-
benzopentalene) derivatives with tunable energy levels by variable sub-
stituents. J Polym Sci Part A Polym Chem 2011;49:72e81.
18] Yuan YP, Michinobu T, Ashizawa M, Mori T. Microwave-assisted TCNE/TCNQ
addition to poly(thienyleneethynylene) derivative for construction of
donoreacceptor chromophores. J Polym Sci Part A Polym Chem 2011;49:
1013e20.
crude product was purified by column chromatography using
1
CH
NMR (CDCl
m), 1.34(8H, m), 1.82(8H, m), 3.66(8H, t), 6.98(4H, d, J ¼ 9.0 Hz),
.61(4H, d, J ¼ 9.0 Hz), 8.07(4H, d, J ¼ 8.0 Hz), 8.39(4H, d, J ¼ 8.0 Hz),
.97(4H, d, J ¼ 9.5 Hz), 9.43(4H, d, J ¼ 4.5 Hz), 10.34(2H, s) ppm. FT-
2
Cl
2
as the eluent to give R-33 (61.0 mg, 57%) as a black solid. H
3
, 500 MHz):
d
¼ ꢀ3.16(2H, s), 0.90(12H, m), 1.28(96H,
7
8
[19] Xu AP, Han HH, Lu J, Yang PP, Gao YJ, An HW, et al. Charge transfer NIR dyes
for improved photoacoustic effect. Dyes Pigments 2016;125:392e8.
[
20] Li YR, Tsuboi K, Michinobu T. Double click synthesis and second-order non-
linearities of polystyrenes bearing donorꢀacceptor chromophores. Macro-
molecules 2010;43:5277e86.
ꢀ
1
IR (KBr, cm ):
n
¼ 2925, 2853, 2199, 1633, 1599, 1434, 1387, 1349,
1
313, 1238, 1190, 1038, 973, 776, 638. MALDI-TOF-MS (dithranol):
m/z: calcd for
143.7 g mol
ꢀ
1
[21] Jin ZK, Wang D, Wang XK, Liang PX, Mi YS, Yang H. Efficient modification of
pyrene-derivative featuring third-order nonlinear optics via the click post-
functionalization. Tetrahedron Lett 2013;54:4859e64.
C
136
H
160
F
8
N
14
:
2142.86
g
mol
,
found:
ꢀ
1
þ
2
[MH] ; elemental analysis calcd (%) for
C136H160F8N14 (2142.86): C 76.23, H 7.53, N 9.15; found: C 76.24,
H 7.53, N 9.16.
[22] Liu X, Wang D, Gao H, Yang Z, Xing Y, Cao H, et al. Click chemistry func-
tionalization improving the wideband optical-limiting performance of
fullerene derivatives. Phys Chem Chem Phys 2016;18:7341e8.
[
[
[
23] Mi YS, Liang PX, Jin ZK, Wang D, Yang Z. Synthesis and third-order nonlinear
optical properties of triphenylene derivatives modified by click chemistry.
ChemPhysChem 2013;14:4102e8.
Acknowledgments
24] Wang D, Guo QS, Gao H, Yang Z, Xing Y, Cao H, et al. The application of double
This work was supported by the National Key Basic Research
Program of China (2014CB931804), the National Natural Science
Foundation of China (Grant No. 51473020, 61370048, 51333001,
click to synthesize
a
third-order nonlinear polymer containing
donoreacceptor chromophores. Polym Chem 2016;7:3714e21.
25] Miao ZC, Han HH, Wang D, Gao H, Gu JM, Hu HY. Nonlinear optical and
energy-level modulation of organic alkynes by click chemistry. Tetrahedron
51373024), the Beijing Higher Education Young Elite Teacher Proj-
2016;72:4039e46.
ect (Grant No. YETP0356), the Fundamental Research Funds for the
Central Universities (Grant No. FRF-TP-15-003A3).
[26] Wang D, Zhang RR, Gao H, Wang XK, Wang HH, Yang Z, et al. Energy-level
tuning of poly(p-phenylenebutadiynylene) derivatives by click chemistry-
type postfunctionalization of side-chain alkynes. React Funct Polym
2
016;105:114e21.
Appendix A. Supplementary data
[
27] Zhou GJ, Wong WY, Cui DM, Ye C. Large optical-limiting response in some
solution-processable polyplatinaynes. Chem Mater 2005;17:5209e17.
[28] Mozhchil RN, Menushenkov AP, Ionov AM, Mironov AF, Rumyantseva VD. XPS
study of asymmetrical tetraarylporphyrins and their ytterbium complexes.
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.dyepig.2016.07.010.

X. Liu et al. / Dyes and Pigments 134 (2016) 155e163
163
Macroheterocycles 2015;8:252e8.
optical susceptibility in epitaxial vanadyl-phthalocyanine films grown on KBr.
Appl Phys Lett 1996;69:767.
[
[
29] Yedukondalu M, Maity DK, Ravikanth M. beta,meso-Acetylenyl-bridged,
asymmetrical, porphyrin dyads - synthesis, spectral, electrochemical and
computational studies. Eur J Org Chem 2010;8:1544e61.
30] Qiu NN, Liu DJ, Han SL, He XQ, Cui GH, Duan Q. Synthesis of the end-
functionalized polymethyl methacrylate incorporated with an asymmetrical
porphyrin group via atom transfer radical polymerization and investigation
on the third-order nonlinear optical properties. J Photoch Pnotobio 2013;272:
[34] Li ZG, Gao F, Xiao ZG, Ao GH, Wu XZ, Fang Y, et al. Synthesis and third-order
nonlinear optical properties of a sandwichtype mixed (phthalocyaninato)(-
schiff-base) triple-decker complexes. Dyes Pigments 2015;119:70e4.
[35] Zhu PH, Kan LL, Han XY, Feng JJ, Jia JN, Zhang XM. Organic nanostructures with
controllable morphology fabricated from ferroceneeporphyrin derivatives:
effect of metal-ligand coordination on the morphology, dimension and
nonlinear optical properties. Dyes Pigments 2015;113:55e60.
65e72.
[
[
31] Kurotobi K, Toude Y, Kawamoto K, Fujimori Y, Ito S, Chabera P, et al. Highly
asymmetrical porphyrins with enhanced push-pull character for dye-
sensitized solar cells. Chem Eur J 2013;19:17075e81.
32] a) Varotto A, Nam CY, Radivojevic I, Tome JPC, Cavaleiro JAS, Black CT, et al.
Phthalocyanine blends improve bulk heterojunction solar cells. J Am Chem
Soc 2010;132:2552e4.
[36] Iliopoulos K, Guezguez I, Kerasidou AP, El-Ghayoury A, Branzea D, Nita G, et al.
Effect of metal cation complexation on the nonlinear optical response of an
electroactive bisiminopyridine ligand. Dyes Pigments 2014;101:229e33.
[37] Zhang F, Miao JT, Fang Y, Sun R, Guo XZ, Song YL, et al. Aggregation induced
convertible third-order nonlinear optical absorptions of the phenoxazinium
containing films prepared by solegel method. Dyes Pigments 2015;113:
496e501.
[38] Narendran NKS, Soman R, Arunkumar C, Chandrasekharan K. Third-order
nonlinear optical investigations of meso-tetrakis(2,3,5,6-tetrafluoro-N,N-
dimethyl-4-anilinyl)porphyrin and its metal complexes. Spectrochim ACTA A
2015;136:838e44.
b) Yue W, Zhao Y, Shao SY, Tian HK, Xie ZY, Geng YH, et al. Novel NIR-
absorbing conjugated polymers for efficient polymer solar cells: effect of
alkyl chain length on device performance. J Mater Chem 2009;19:2199e206.
33] a) Parr RG, Yang W. Density-functional theory of the electronic structure of
molecules. Annu Rev Phys Chem 1995;46:701e28.
[
b) Fang SL, Tada H, Mashiko S. Enhancement of the third-order nonlinear