Synthesis and Characterization of Near-Infrared Emissive Chiral π-Conjugated Polymers Incorporating Perylenyl Moieties with Visible-Light Absorption

Article abstract of DOI:10.1055/s-0035-1560206

A novel set of multifunctional optically active π-conjugated polymers incorporating perylenyl moieties, were designed and synthesized. Chirality transfer and amplification from chiral unit to the main-chain backbone in dilute solution was achieved, which was closely related to the stereocenter in the pendant of a π-conjugated polymer. In addition, annealed films of these polymers exhibited near-infrared emission by direct absorption of visible light, resulting from the introduction of a strong fluorophore perylenyl moiety. Such a design strategy opens up new perspectives for the future development of novel optically active materials with near-infrared emission for photonic applications.

Full text of DOI:10.1055/s-0035-1560206

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© Georg Thieme Verlag Stuttgart · New York
2015, 26, 2451–2456
letter
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Letter
Synlett
Synthesis and Characterization of Near-Infrared Emissive Chiral
π-Conjugated Polymers Incorporating Perylenyl Moieties with
Visible-Light Absorption
n-Bu
n-Bu
Junfeng Li*
O
O
Ying Chen
O
O
Chenglong Yang
Wen-Yong Lai*
n
annealed film state
near-infrared PL
solution state
Key Laboratory for Organic Electronics and Information
Displays (KLOEID) & Institute of Advanced Materials (IAM),
Jiangsu National Synergetic Innovation Center for Advanced
Materials (SICAM), Nanjing University of Posts & Telecommu-
nications, 9 Wenyuan Road, Nanjing 210023, P. R. of China
iamjfli@njupt.edu.cn
chirality amplification
N
O
O
O
O
n-Bu
n-Bu
iamwylai@njupt.edu.cn
Received: 09.06.2015
Accepted after revision: 02.08.2015
Published online: 04.09.2015
sized that these π-conjugated polymers aggregated stable
colloidal solutions in ‘poor solvents’ or in ‘poor solvent and
good solvent’ mixtures, specifically for polyfluorene deriva-
tives.7
DOI: 10.1055/s-0035-1560206; Art ID: st-2015-w0425-l
Abstract A novel set of multifunctional optically active π-conjugated
polymers incorporating perylenyl moieties, were designed and synthe-
sized. Chirality transfer and amplification from chiral unit to the main-
chain backbone in dilute solution was achieved, which was closely relat-
ed to the stereocenter in the pendant of a π-conjugated polymer. In ad-
dition, annealed films of these polymers exhibited near-infrared emis-
sion by direct absorption of visible light, resulting from the introduction
of a strong fluorophore perylenyl moiety. Such a design strategy opens
up new perspectives for the future development of novel optically ac-
tive materials with near-infrared emission for photonic applications.
π-System, owing to their delocalized π-electrons, has in-
trinsic electronic properties, which has been broadly uti-
lized as key building blocks to construct chemical sensors,
chiral catalysts, chiro-optical switches, nanotubes, etc.8 For
π-conjugated polymers, a long-term challenge in the supra-
molecular chemistry is to control the local stacking ar-
rangements, which, in turn, greatly affects the optoelec-
tronic properties of chromophores. In this regard, perylenyl
dyes have gained much attention owing to the wide range
of possibilities available for fine-tuning their properties by
the introduction of suitable functional groups at the core as
well as the periphery. Recently, the Kawai group reported
that perylene bis(imide) (PBI) derivatives, with the axial
binaphthyl moiety, formed helically associated species
through supramolecular assemblies and exhibited chiropti-
cal properties.9 So far, work on CD active π-conjugated poly-
mers incorporating perylenyl moieties in dilute solutions
has rarely been investigated.10
The stereocenter in the pendant/main chain of a π-con-
jugated polymer has played an important role in determin-
ing their conformation and optoelectronic properties. Our
previous study has demonstrated that π-conjugated poly-
mers with perylenyl moieties in an alternating system can
act as a mercury ion detector without interference from
other metal ions.8a Further research has reported that the
chromaticity of europium(III)-grafting polymer possessing
perylenyl moieties can be tuned by the selected excitation
wavelengths.11 Despite this progress, there is still little liter-
ature in terms of chirality amplification in dilute solution
and near-infrared emission in annealed films by absorbing
visible light. Alternating copolymers were thus designed
and synthesized to investigate their chiroptical properties
Key words π-conjugated polymers, near-infrared emission, visible-
light absorption, perylenyl moieties, circular dichroism
π-Conjugated polymers that can be deposited in large
areas via solution processing have attracted much interest
in organic electronics, such as organic light-emitting diodes
(OLED),1,2 organic field-effect transistors (OFET),3 photovol-
taic cells,4 and biosensors,5 due to their excellent conductiv-
ity, photo- and/or electroluminescence with high quantum
yields, and mechanical flexibility. Among these, helical con-
jugated polymers are attracting increasing attention be-
cause of their potential application in 3D optical displays,
circularly polarized luminescence (CPL), and nonlinear sec-
ond harmonic optics, which might be applied to next-gen-
eration plastic electronics.6 From a structural perspective,
the optical activity was elucidated as a consequence of a he-
lical conformation of the π-conjugated main chain that was
induced by the introduction of regio- and stereoregularity
of the substituents on the main chain. However, the de-
scribed circular dichroism (CD) effects were nearly ob-
served in the solid state or in ‘poor solvents’, and, therefore,
it was obvious a cooperative aggregation phenomenon. This
well-established interpretation of the CD effects empha-
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2451–2456

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J. Li et al.
Letter
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to further elucidate structure–property relationships. In
this paper, perylene is chosen as a fluorophore, and carba-
zole or (R,R)-salen acts as an enantiomeric center. It is indi-
cated that, introduction of chiral moieties into main-chain
π-conjugated polymers (denoted as P-1 and P-2), can lead
to a chiral conformation in dilute solution. More important-
ly, annealed films of P-1 and P-2 emitted near-infrared
emission upon direct absorption of visible light.
The targets P-1 and P-2 were synthesized according to
the routes depicted in Scheme 1. The monomer S-M-1,
bearing a highly enantiopure alkyl side chain at the carba-
zole moiety, was synthesized in 90% yield by reaction of
3,6-dibromo-9H-carbazole with (S)-3,7-dimethyloctylbro-
mide (2) in DMF solution using NaH as the catalyst stirring
overnight at room temperature.12 The corresponding mono-
mer 1,7-diethynylperylene-3,4:9,10-tetracarboxylic tetra-
butylate (S-M-2) was synthesized by a four-step reaction
from the starting materials 3,4:9,10-perylene-tetracarbox-
ylic acid dianhyride (3).13 The starting material 5 was react-
ed with two equivalents of BF3·OEt2 in a mixed solution of
N-ethyldiisopropylamine and toluene to afford S-M-3 in
52% yield. The polymerization was carried out in anhydrous
THF via Sonogashira coupling by reaction of S-M-1 or S-M-
3 with S-M-2 at 70 °C for 48 hours to afford the deep-red
solids of P-1 and P-2 in yields of over 50%. According to gel
permeation chromatography (GPC) using THF as eluent and
polystyrene as standard, the number-average molecular
weights (Mn) of P-1 and P-2 are 9850 and 9120, respective-
ly, and the polydispersity indexes (PDI) are 1.8 and 1.6, re-
spectively. GPC results show a moderate molecular weight.
The specific optical rotations ([α]D25) of S-M-1 and S-M-3
were +45 and –26 (c 0.01, THF), respectively, and the corre-
sponding [α]D25 of P-1 and P-2 were +460 and –300 (c 0.01,
THF), respectively. The chemical structures of P-1 and P-2
were further confirmed by 1H NMR and IR spectroscopy. P-
1 and P-2 are readily soluble in common organic solvents,
such as CHCl3, CH2Cl2, THF, and toluene, due to the flexible
n-butoxy substituents in the polymers. The perylenyl moi-
ety acts as a chromophore, and the carbazole and (R,R)-
salen, as the well-known building blocks, are chosen as the
chiral induction center. Moreover, the ethynyl linker can re-
duce the steric hindrance between perylenyl and chiral
units, improving the stability of the resulting polymers.
Thermogravimetric analysis (TGA) of P-1 and P-2 was
carried out under N2 atmosphere at a heating rate of 10 °C
min–1 (Figure S10, Supporting Information). P-1 has a high-
H
N
N
Br
Br
1) Pd/C, EtAc
dialyzed
Br
OH
P
Br
2) NBS, Ph3
NaH, DMF
Br
S-M-1
n-Bu
n-Bu
n-Bu
2
1
O
O
O
O
n-Bu
n-Bu
n-Bu
O
O
O
O
O
O
O
O
O
O
O
n
1) TMSA, Pd(PPh3)4
CuI, Et3N, THF
1) I2, Br2
concd H2SO4
S-M-1
Br
N
Br
2) KOH, H2O
HCl, TOAB
n-BuBr
Pd(PPh3)4
CuI, Et3N, THF
2) K2CO3, MeOH
O
O
O
O
n-Bu
n-Bu
O
O
O
n-Bu
O
O
O
O
O
O
O
n-Bu
S-M-2
O
n-Bu
n-Bu
3
4
P-1
n-Bu
O
n-Bu
O
O
O
Pd(PPh3)4
CuI, Et3N, THF
N
N
F
BF3⋅OEt2
F
F
N
O
N
O
B
B
toluene
S-M-2
Br
OH HO
Br
F
O
Br
Br
F
O
O
F
B
B
N
O
5
S-M-3
O
O
F
F
n-Bu
n-Bu
N
n
P-2
Scheme 1 Synthetic routes towards P-1 and P-2
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2451–2456

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J. Li et al.
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er thermal stability than P-2 and does not show weight loss
till 344 °C. Therefore, the resulting polymers can provide
desirable thermal properties for practical applications in
organic optoelectronic devices.
solution, we have measured their optical activity of P-1 and
P-2 by CD spectra (Figure 2). As depicted in Figure S12
(Supporting Information), S-M-1 displays a bisignate Cot-
ton effect with a negative wave at around 267 nm accompa-
nied by a pronounced wavelength at around 245 nm, and a
positive wave at around 277 nm. Meanwhile, a well-re-
solved bisignate CD signal of model S-M-3 was observed
with a positive maximum at around 380 nm and a negative
maximum at around 352 nm in THF solution (Figure S13,
Supporting Information). An additional moderate CD band
with a negative band situated at around 323 nm, with the
sign same to that of the band at around 278 nm, was ob-
served for S-M-3. Interestingly, P-1 and P-2 exhibited
prominent Cotton effects in the range of 450–600 nm at the
position of the π–π* band of π-conjugated backbones. Such
results suggested that the Cotton effects which were ob-
served in the polymers were induced by the chirality of the
main chain. Moreover, the existence of the main-chain chi-
rality was also supported by the CD data of the other opti-
cally active polyfluorenes and BODIPY molecules. For ex-
ample, Konishi’s optically active polyfluorene exhibited the
Cotton effect in the π–π* transition region duo to polymer
backbone.15 According to Moya’s report,10a the strong Cot-
ton effect observed for the BODIPY in visible region of CD
spectra demonstrated that BODIPY were present of the mo-
lecular scaffold chirality conformation. The Cotton effect
observed for P-1 and P-2 was indicative of exciton coupling
between obliquely oriented neighboring polymer back-
bones, suggesting the existence of a certain chiral confor-
mation such as helical conformation in the π–π* transition
region for π-conjugated polymers.16 Thus, analysis of CD
data demonstrates that the chirality amplification can be
achieved through chirality transfer from the chiral moiety
to the main chain of π-conjugated polymers.
The optical properties of P-1 and P-2 were investigated
in THF solution (1.0·10–5 mol·L–1) and in annealed films. As
shown in Figure S11 (Supporting Information), UV-vis ab-
sorption spectrum of S-M-2 showed prominent peaks at
483, 454, and 428 nm along with a weak shoulder around
405 nm, which were attributed to the 0–0, 0–1, 0–2, and 0–
3 transitions of the perylenyl moiety, respectively.14 The
fluorescence spectrum of S-M-2 exhibited a mirror image
of the absorption spectrum with a maximum at 506 nm. In
Figure 1 (a), P-1 and P-2 displayed well-defined absorption
bands with the characteristic π–π* transitions of PBI units
in the region from 450–550 nm, whereas the absorption
bands ranging from 550–600 nm corresponded to π–π*
transition of π-conjugated backbones. Figure 1 (b) shows
that annealed films of P-1 and P-2, fabricated by spin-coat-
ing from 1.0 mg/mL solution on quartz substrates, exhibited
a strong and broad absorption in the region of 550–700 nm,
originating from strong π–π stacking interaction of the rigid
conjugated polymers.
Figure 2 CD spectra of P-1 and P-2 in THF solution (1.0·10–5 mol L–1
)
Figure 1 a) Normalized UV-vis spectra of P-1 and P-2 in THF solution
(1.0·10–5 mol·L–1); b) Normalized UV-vis spectra of P-1 and P-2 in an-
nealed films.
As shown in Figure 3 (a), the maximum emission wave-
length of P-1 appeared at 617 nm with the excitation of 460
nm, which was red-shifted about 10 nm with respect to
that of P-2 in THF solution. Such a red-shift emission was
ascribed to excitation extending over π-conjugated chromo-
phores. Moreover, the internal fluorescent quantum yields
Generally, π-conjugated polymers possess a high ten-
dency for molecular random conformation via aromatic π-
stack interactions. To get a deeper insight into the nature of
structure information in ground states, preferably in dilute
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(ΦEM) of P-1 and P-2 estimated using an integrating sphere
were 14% and 10%, respectively. Furthermore, when P-1
and P-2 in THF were irradiated by 365 nm, the color fluo-
rescence of P-1 and P-2 was red and orange, respectively.
The nature of different emitting species was investigated by
means of time-resolved single-photon counting (TCSPC)
measurements. The luminescent decay profiles curves of P-
1 and P-2 were fitted with two-ordered exponential decay
as shown in Figures S14 and S15 (Supporting Information).
A short-lived species with a lifetime of 1.3 ns (31.2%) and a
relatively long-lived species with a lifetime of 5.0 ns (68.8%)
were observed for P-1 in dilute solution, whereas P-2 ex-
hibited the corresponding species with lifetimes of 1.7 ns
(51.1%) and 4.7 ns (48.9%) for emission monitored at 607
nm. Based on the luminescent decay, P-1 and P-2 demon-
strated rather high chiroptical anisotropies within the delo-
calized π–π* transition band. In addition, P-1 and P-2, in
annealed films, exhibited a relatively weak near-infrared
emission centered at 734 nm when excited at 637 nm with
a low quantum yield of 6%, suggesting direct formation of
molecular aggregates driven by interchain interactions.17
In order to investigate the electrochemical properties of
P-1 and P-2 and estimate the highest occupied molecular
orbital (HOMO) and the lowest unoccupied molecular or-
bital (LUMO) energy levels, cyclic voltammetry (CV) were
carried out. The results are shown in Figure 4, and their
electrochemical data are summarized in Table 1. Their HO-
MO/LUMO energy levels of P-1 and P-2 were estimated
from the corresponding onsets of the oxidation/reduction
waves by the empirical formula.18 The HOMO energy levels
of P-1 and P-2 are –5.27 and –5.15 eV, and the correspond-
ing LUMO energy levels are –4.27 and –4.01 eV, respective-
ly. Calculated band gaps (Eg) of P-1 and P-2 are 1.00 and
1.14 eV, respectively. Especially, P-1 exhibited a lower-lying
HOMO level with respect to P-2, suggesting that the chiral
moiety played an important role in π-conjugated polymer’s
configuration and even the electrical distribution over poly-
mer’s backbone.
Figure 4 CV curves of P-1 and P-2
To theoretically support the optical and electrochemical
behaviors of π-conjugated polymers, density functional
theory (DFT) calculations were carried out. Herein, the al-
kyl chains of the repeating units were replaced by methyl or
ethyl groups to simplify the calculation. As depicted in Fig-
ure 5, the LUMO of repeating units of P-1 is primarily dis-
tributed over π-conjugated moieties. The HOMO of the re-
peating units of P-2 mainly centers on the perylenyl moi-
eties and alkynes. As shown in Table 1,DFT calculations
showed that the HOMO energy level of P-1 was higher than
that of P-2, although the CV data gave the opposite trend. In
fact, DFT calculations simulate the single-molecule energy
levels and band gaps of the repeating unit rather than the
polymer, while CV measurements reflects the electrical en-
ergy levels and band gaps of the polymer in condensed
states. Moreover, the existence of chiral units in the poly-
mer can lead to the different main-chain configuration,
which exerted influence on the electrical distribution over
the polymer’s backbone. Thus, it is suggested that the ener-
gy levels of HOMO should be strongly affected by the π-con-
jugated polymers’ configuration. It is therefore believed that
such a difference is the origin for the difference of energy
levels between DFT calculations and CV measurements.
Figure 3 (a) Normalized emission spectra of P-1and P-2 in THF solu-
tion (1.0·10–5 mol L–1); (b) normalized emission spectra of P-1 and P-2
in annealed films. Inset: The photographs show P-1 and P-2 emission in
THF solution (1.0·10–5 mol L–1) with UV lamp (λex = 365 nm).
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2451–2456

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Table 1 Electrochemical Data of P-1 and P-2 and the Calculated HOMO, LUMO Energy Values
From CVa
From calculation
HOMOe (eV)
HOMOc (eV)
LUMOc (eV)
Egd (eV)
LUMOe (eV)
Ege (eV)
onset
E
(V)b
Eonset (eV)b
ox
red
P-1
P-2
0.47
0.35
–5.27
–5.15
–0.53
–0.79
–4.27
–4.01
1.00
1.14
–5.14
–5.49
–2.58
–2.86
2.56
2.63
a Ferrocence couple (Fc+/Fc) was used as the internal reference and under our experimental conditions, E(Fc+/Fc) = 0.42 V vs. Ag/AgCl.
b Eox and Ered were determined from the onset potentials of the oxidation and reduction waves.
c HOMO = –(Eoxonset + 4.8) eV and LUMO = –(Eredonset + 4.8) eV.
d Eg = LUMO – HOMO.
e DFT quantum mechanical calculations (B3LYP/6-31G*).
Furthermore, the HOMO–LUMO band gaps and each energy
level estimated from the DFT calculations show similar
trends to the experimental data estimated from CV mea-
surements.
Acknowledgment
We acknowledge financial support from the National Key Basic Re-
search Program of China (973 Program, 2014CB648300), National
Natural Science Foundation of China (No. 21404059, 21422402), Nat-
ural Science Foundation of Jiangsu Province (No. BK20140867,
BK20140060, BK20130037), Program for Jiangsu Specially-Appointed
Professor (RK030STP15001), Program for New Century Excellent Tal-
ents in University (NCET-13-0872), and Scientific Research Founda-
tion of Nanjing University of Posts & Telecommunications (No.
NY213100).
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0035-1560206.
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References and Notes
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(19) Synthesis Procedures for the Perylenyl-Based Chiral Conju-
gated Polymers
Synthesis of P-1
The monomer S-M-1 (46.52 mg, 0.10 mmol), S-M-2 (70.08 mg,
0.10 mmol), Pd(PPh3)4 (5.78 mg, 5 mol%), and CuI (1.90 mg, 10
mol%) were added to a mixture of THF (6 mL) and Et3N (2 mL) in
a 20 mL Schlenk tube. The reaction mixture was stirred at 70 °C
for 3 d under N2 atmosphere. After being cooled to r.t., the
mixture was filtered through a short silica gel column in MeOH
(50 mL) to precipitate the polymer. The solid was filtered and
washed with MeOH several times and dried under vacuum to
afford 62.06 mg of
a
dark-red solid in 60% yield. GPC:
25
Mw = 17730; Mn = 9850; PDI = 1.8. [α]D +460 (c 0.01, THF). 1H
NMR (300 MHz, CDCl3): δ = 9.44 (d, J = 8.1 Hz), 8.41–8.16 (m),
7.62–7.55 (m), 7.29 (m), 7.26 (m), 4.39 (m), 2.06 (m), 1.81 (m),
1.51 (m), 1.27 (m), 1.02 (m), 0.87 (m) ppm. FT-IR (KBr): 2956,
2929, 2869, 1718, 1276, 1258, 1165, 1063, 1016, 801 cm–1
.
Synthesis of P-2
A mixture of THF (6 mL) and Et3N (2 mL) was repeatedly
degassed by purging with nitrogen gas, and then the compound
S-M-2 (70.08 mg, 0.10 mmol), S-M-3 (57.58 mg, 0.10 mmol),
and CuI (1.90 mg, 10 mol%) along with Pd(PPh3)4 (5.78 mg, 5
mol%) were added and refluxed over 3 d under a N2 atmosphere.
After being cooled to r.t., the reaction mixture was filtered
through a short silica gel column in MeOH (50 mL) to precipi-
tate out the polymer. The resulting polymer was filtered and
washed with MeOH several times and dried under vacuum to
afford 62.97 mg of
a
dark-red solid in 55% yield. GPC:
25
Mw = 14470; Mn = 9120; PDI = 1.6. [α]D –300 (c 0.01, THF). 1H
NMR (300 MHz, CDCl3): δ = 9.47 (m), 8.87 (m), 8.62 (m), 8.37–
8.28 (m), 7.74–7.41 (m), 6.83 (m), 6.80 (m), 4.38 (s), 2.05 (m),
1.81 (m), 1.53 (m), 1.27 (m), 1.02 (m) ppm. FT-IR (KBr): 2956,
2931, 2870, 1721, 1629, 1455, 1278, 1164, 1063, 1022, 804 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2451–2456