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POLYMER SCIENCE WWW.POLYMERCHEMISTRY.ORG ARTICLE

Synthesis, Characterization, and Electrogenerated Chemiluminescence of

Deep Blue Emitting Eumelanin-Inspired Poly(indoylenearylene)s for
Polymer Light Emitting Diodes

K. A. Niradha Sachinthani,1 Nelly Kaneza,2 Rajiv Kaudal,3 Eeshita Manna,3

Margaret A. Eastman,1 Bhishma Sedai,1 Shanlin Pan,2 Joseph Shinar,4 Ruth Shinar,5
Toby L. Nelson 1
1
Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078
2
Department of Chemistry, University of Alabama, Tuscaloosa, Alabama 35401
3
Ames Laboratory-USDOE and Electrical and Computer Engineering Department, Iowa State University, Ames, Iowa 50011
4
Ames Laboratory-USDOE and Physics and Astronomy Department, Iowa State University, Ames, Iowa 50011
5
Microelectronics Research Centre and Electrical and Computer Engineering Department, Iowa State University, Ames, Iowa
50011
Correspondence to: T. L. Nelson (E-mail: toby.nelson@okstate.edu)

Received 5 September 2017; accepted 26 September 2017; published online 00 Month 2017
DOI: 10.1002/pola.28881

ABSTRACT: Deep blue emitting copolymers were synthesized
by uniting the Eumelanin-inspired indole core with fluorene
and carbazole units via Suzuki polymerization. The resulting
polymers, PIF and PIC, showed deep blue emission in the
range of 416–418 nm and quantum yields of 0.39–0.60. Both
polymers exhibited an intense and stable electrogenerated
1 Cd/A, given that the photopic response at that wavelength is
0.0151. The electroluminescence of PIF displayed a Commis-
sion Internationale de l’Eclairage coordinates of (0.16, 0.07)
with a maximum external quantum efficiency of 1.1%. Hence,
these materials prove to be promising candidates for the fabri-
cation of deep blue PLEDs. V C 2017 Wiley Periodicals, Inc. J.

chemiluminescence. Interestingly, deep HOMO levels of 25.71 Polym. Sci., Part A: Polym. Chem. 2017, 00, 000–000
and 25.61 eV were observed for PIF and PIC, respectively.
Solution processed polymer light emitting diodes (PLEDs) were
fabricated using the PIF as a guest. PLEDs emitted deep blue KEYWORDS: conjugated polymers; deep blue; eumelanin-
light at 418 nm, with the luminous efficiency peaking at inspired core; fluorescence; light-emitting diodes

INTRODUCTION Conjugated polymers have attracted much
interest in the scientific community over the last three deca-
des due to their promise of low cost, lightweight, and large
area electronic devices.1,2 Such polymers have the potential
to create organic solar cells, organic light emitting diodes
(OLEDs), organic field effect transistors (OFETs),3–6 and
chemical and biological sensors using such OFETs or
OLEDs.7–10 Fluorene and carbazole containing conjugated
polymers are well-known as blue light emitters that show
promising results in the emissive layers of polymer light
emitting diodes (PLEDs).11–15 Among the three color emit-
ters, red, green, and blue in PLEDs, there is a great demand
for novel blue emitting materials.16–19
Our group was the first to introduce Eumelanin-inspired
conjugated polymers as new organic semiconductors.20
Eumelanin is the major form of Melanin,21,22 which is a
naturally occurring pigmentary macromolecule found in
most organisms including humans.23,24 It is understood to
be a biosynthesized molecule, which consists of two different
indole units, 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-
carboxylic acid.25–27 The optical, electronic, physical, metal
chelating, and structural properties of the natural and syn-
thetic Eumelanin have been studied extensively.26–30 To fur-
ther determine the structure-property relationships of this
biomolecule, we previously synthesized an eumelanin-
inspired indole core similar to the building blocks found in
natural eumelanin.31
Although the indole group has been used in several blue
emitting materials,32–36 to our knowledge there are no exam-
ples showing utilization of the indole moiety through its 4-
and 7-positions in the blue emitting copolymers. Our
approach was to synthesize deep blue emitting copolymers

Additional Supporting Information may be found in the online version of this article.
C 2017 Wiley Periodicals, Inc.
V

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ARTICLE WWW.POLYMERCHEMISTRY.ORG
by incorporating an Eumelanin inspired indole core through
the 4- and 7-positions with fluorene and carbazole units. In
this article, we report the syntheses of novel Eumelanin-
inspired poly(indoylenearylene)s and their optical, electronic,
physical and electrogenerated chemiluminescence (ECL)
properties. These polymers were used in PLEDs demonstrat-
ing the first time use of Eumelanin-inspired materials in
organic electronic devices.
EXPERIMENTAL
Materials and General Experimental Details
9,9-Dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol)
ester and 9-(heptadecan-9-yl)-2,7-bis(4,4,5,5-tetramethyl-
1,3,2-dioxaborolan-2-yl)-9H-carbazole were purchased from
Sigma Aldrich and Ark Pham and were used as received.
Anhydrous tetrahydrofuran (THF) and chloroform (CHCl3)
were obtained from a solvent purification system under
ultrapure argon. Distilled water was degassed under the
argon atmosphere while sonicating the flask. DBI was syn-
thesized according to the previously reported procedure.31
All the other commercial reagents were used as received. 1H
and 13C NMR analyses confirmed the structures of the poly-
mers. All spectra were acquired on a Varian Inova 400 MHz
spectrometer using a OneNMR probe, with nominal tempera-
ture setting of 25 8C with chemical shifts given with respect
to TMS. FTIR experiments were evaluated on a Nicolet iS50
FTIR instrument using an ATR diamond. GPC was performed
using a Waters 1515 isocratic pump with a Waters 2410
refractive index detector. THF was used as the solvent at 35
8C with a flow rate of 1.0 mL/min and with reference to
polystyrene standards. UV–visible and fluorescence spectra
were recorded on a Cary 5000 UV–VIS-NIR spectrophotome-
ter and a Cary Eclipse fluorescence spectrophotometer,
respectively. Ultraviolet-Visible and fluorescence measure-
ments were obtained using polymer solutions in CHCl3, and
thin films were dropcasted from these solutions. Cyclic vol-
tammetry (CV) was performed on a BASI CV-50W Version
2.3 instrument with 0.1 M tetrabutylammonium hexafluoro-
phosphate (TBAPF6) as the supporting electrolyte in dry ace-
tonitrile (ACN) using a glassy carbon working electrode,
platinum (Pt) wire as the counter electrode, and Ag/AgCl as
the reference electrode with a scan rate of 100 mV s21. The
CV experiments were performed by dropcasting a thin film
of the polymer on the glassy carbon working electrode. TGA
measurements were performed using a high-resolution ther-
mogravimetric analyzer TA instrument Model Q-50, within
the temperature intervals of 30–800 8C, with a rate of 20
8C min21 under a continuous nitrogen flow. DSC was per-
formed using a TA Instruments Model Q-2000 from 280 to
300 8C at a heating rate of 3 8C min21 in a modulated mode.
The second thermal cycle (cooling cycle) was chosen to
observe the thermal transitions in polymers. All runs were
performed under a nitrogen environment.
Polymerization Procedure
Poly(indoylene-co-fluorene) (PIF)
In a 25-mL, oven-dried Schlenk flask were placed methyl
4,7-dibromo-5,6-dimethoxy-1-methyl-1H-indole-2-carboxylate
(100 mg, 0.24 mmol), 9,9-dioctylfluorene-2,7-diboronic acid
2 JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2017, 00, 000–000
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bis(1,3-propanediol) ester (141 mg, 0.24 mmol), and K2CO3
(566 mg, 4.09 mmol). The system was then kept under vac-
uum for 20 min, followed by Ar purged for 15 min. Then
Pd(PPh3)4 (14 mg, 5 mol %) was added to the flask inside
the glovebox followed by dry THF (4 mL) and degassed
water (4 mL). The reaction mixture was heated to reflux for
48 h under Ar atmosphere and then cooled to room temper-
ature. Hydrochloric acid (6 N, 15 mL) was added and the
mixture was stirred 15 min. The polymer was extracted with
CHCl3 (3 3 40 mL), washed with brine (2 3 50 mL), and
dried (Na2SO4). The solvent was evaporated, and the solid
was redissolved in THF (2 mL), and the solution was added
dropwise to methanol (25 mL) to precipitate the polymer.
The resulting precipitate was redissolved in CHCl3 (2 mL)
and reprecipitated in methanol (25 mL). The off white poly-
mer (122 mg, 78%) was collected and subjected to high vac-
uum exposure. 1H NMR (400 MHz, CDCl3) d 7.93 (s, 2H),
7.70 (s, 2H), 7.53 (s, 2H), 7.29 (d, J 5 22.3 Hz, 2H), 3.83 (s,
3H), 3.71 (s, 6H), 3.55 (s, 3H), 2.09 (s, 4H), 1.13 (s, 23H),
0.82 (s, 11H). 13C NMR (101 MHz, CDCl3) d 162.3, 150.7,
145.6, 140.6, 140.2, 134.8, 134.0, 133.7, 129.5, 129.1, 128.8,
128.7, 125.3, 125.0, 123.0, 121.2, 119.4, 77.3, 77.0, 61.3,
55.3, 51.5, 40.9, 34.9, 31.8, 30.2, 29.5, 29.5, 29.3, 24.0, 22.6,
14.0. Mn 5 18.8 kDa and PDI 5 1.99
Poly(indoylene-co-carbazole) (PIC)
PIC was also synthesized according to the same procedure of
PIF using DBI (49.5 mg, 0.14 mmol), 9-(heptadecan-9-yl)-
2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carba-
zole (80.0 mg, 0.14 mmol), K2CO3 (280 mg, 2.28 mmol), and
Pd(PPh3)4 (7 mg, 5 mol %) with THF (3.1 mL) and distilled
water (3.1 mL). An off white precipitate resulted (57 mg,
64%). 1H NMR (400 MHz, CDCl3) d 8.31 (s, 2H), 7.87 (d,
J 5 70.4 Hz, 2H), 7.59 (s, 1H), 7.38 (d, J 5 8.7 Hz, 2H), 4.66
(s, 1H), 3.78 (d, J 5 25.9 Hz, 6H), 3.51 (s, 3H), 2.40 (s, 2H),
1.97 (s, 2H), 1.15 (s, 20H), 0.81 (s, 6H). 13C NMR (101 MHz,
CDCl3) d 162.2, 159.7, 150.7, 145.6, 142.0, 138.9, 134.9,
129.0, 128.4, 123.1, 121.7, 119.8, 111.1, 77.2, 77.1, 76.9,
76.8, 76.6, 61.3, 61.1, 51.3, 34.5, 33.8, 31.7, 31.6, 29.3, 29.1,
29.1, 26.9, 22.5, 13.9. Mn 5 11.0 kDa and PDI 5 3.65.
Electrogenerated Chemiluminescence
PIF and PIC polymers (0.3 mg/mL) were dissolved in THF or
dichloromethane (DCM) and characterized electrochemically
in solution or as a thin film dropcasted onto the working
electrode. Electrochemical and ECL measurements were per-
formed using a bipotentionstat CHI760C (CH Instruments,
Austin, TX) connected to a 1931C high performance, low-
power optical meter (Newport Corporation, Irvine, CA). The
ECL signal was detected and amplified by a photomultiplier.
A three electrode system was employed including a glassy
carbon or a Pt electrode as the working electrode, a graphite
counter electrode, a silver wire as the reference electrode,
0.1 M lithium perchlorate (LiClO4) or TBAPF6 as the support-
ing electrolyte and ACN as the solvent. The fluorescence
spectra were measured using a fluoromax-3 (Jobin Yvon
Horiba). The ECL signal was then measured using a liquid
nitrogen cooled digital CCD spectroscopy system (Acton
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SCHEME 1 Synthesis of PIF and PIC.
Spec-10:100B Princeton Instruments, Trenton, NJ), coupled
with an Acton SP2500 monochromator (Princeton Instru-
ments, Trenton, NJ).
Fabrication and Characterization of PLEDs
PLEDs were fabricated on nominally 20 X/sq, 140 nm
thick ITO-coated glass substrates (Colorado Concept Coat-
ings). These ITO glass plates (100 3 100 ) were cleaned in a
detergent bath, washed with distilled water, isopropanol and
acetone, dried under N2 and treated with UV/ozone to
increase the work function, and consequently improve hole
injection. A 60 nm layer of high conductivity (900 S cm21)
PEDOT:PSS was spin-coated on the cleaned ITO at 1000 rpm
for 60 s and annealed for 1 h at 120 8C in air, followed by
1 h at 120 8C in a glovebox. The emissive layer was prepared
in the glovebox by dissolving PIF and the host compound in
chlorobenzene (9 mg mL21) and then spin-coating the mix-
ture at 4000 rpm for 60 s on top of the PEDOT: PSS layer
(resulting in a 30–40 nm-thick layer). The fabricated struc-
ture was then annealed for 1 h at 60 8C. The devices were
transferred to a thermal evaporator within the glovebox to
deposit sequentially TmPyPb (40 nm), LiF (1 nm), and Al
(100 nm) layers at a base pressure of 5 x 1027 mbar. The
PLEDs were characterized by monitoring their electrolumi-
nescence spectra, brightness as a function of the applied
voltage, and luminous and external quantum efficiencies.
RESULTS AND DISCUSSION
Polymer Synthesis and Structural Characterization
The synthesis of PIF and PIC were carried out under Suzuki-
Miyaura conditions as shown in Scheme 1. The percent yield
of PIF and PIC, after reprecipitation, was 78 and 64%,
respectively.
The structures of the two polymers was confirmed with 1H
NMR, 13C NMR, and FTIR analyses. The characteristic FTIR
peak (Supporting Information Figure S1) of the carbonyl
group at 1710 cm21 (ester group) confirmed the incorpora-
tion of the Eumelanin-inspired indole core in both polymers.
ARTICLE
The polymers were completely soluble in CHCl3, THF, and
chlorobenzene. The number average molecular weight (Mn)
and polydispersity index (Ð) were estimated using gel per-
meation chromatography. The results are summarized in
Table 1. Both polymers have moderate molecular weights.
Thermal Properties
The thermal properties and stabilities of the two polymers
were investigated by differential scanning calorimetry (DSC)
and thermal gravimetric analysis (TGA), which can be found
in the Supporting Information Figures S2 and S3. In DSC
thermograms, the derivative of reversible heat flow as a
function of temperature showed distinct peaks at 256 8C for
both PIF and PIC. These peaks are the glass transition tem-
peratures (Tg) of the polymers. Crystallization and melting
transitions were not observed in the scanned temperature
range, which suggested that the polymers are amorphous in
nature. The TGA plot showed that both polymers exhibit
good thermal stabilities under N2, indicating 5% decomposi-
tion at 431 8C for PIF and 427 8C for PIC. The rigid backbone
of these polymers may be attributed to the higher thermal
stabilities.
Optical and Electronic Properties
The optical properties of PIF and PIC were evaluated using
UV–vis absorption and fluorescence spectroscopy, both in
solution and in thin films. The normalized absorption and
photoluminescence (PL) spectra of the polymers are shown
in Figure 1, and the results are summarized in Table 2. Both
TABLE 1 Structural and Thermal Properties of Polymers
Polymer Mna (kDa) Mwa (kDa) Ða Tdb (8C) Tgb (8C)
PIF 18.8 37.5 1.99 431 256
PIC 11.0 40.4 3.65 427 256
a
Determined by GPC in THF using polystyrene standards.
b
5% weight loss temperature by TGA under N2.
c
Data from second scan reported, heating rate 3 8C min21 under N2.
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FIGURE 1 A: Absorption spectra of the polymers in solution (CHCl3, solid lines) and thin film (cast from CHCl3, dashed lines). B:
PL spectra in solution (CHCl3, solid lines) and thin film (cast from CHCl3, dashed lines). The polymers were excited at 360 nm for
both solution and film. [Color figure can be viewed at wileyonlinelibrary.com]

polymers exhibited light absorption from medium UV to the
visible region in solution and via a thin film. This light
absorption is attributed to strong featureless p–p* transi-
tions with a maximum of 360–361 nm.
The absorption spectrum of each polymer in solution was
very similar to the absorption in film, indicating reduced p-
stacking of the polymer chains in the solid state due to the
reduced coplanarity of the aromatic rings in polyarylenes. In
addition, there was no significant difference between the
absorption of PIF and PIC polymers, either in their solution
or in thin films. This is a common trend for copolymers con-
taining fluorene and carbazole units attached to the same
arylene group.11 The PL spectra of the polymers in CHCl3
and solid state, excited at 360 nm, are shown in Figure 1(B).
Both PIF and PIC emit in the deep blue range with a peak
emission of 416–418 nm. Polyfluorenes and polycarbazoles
have red-shifted PL values compared with our polymers.11,12
The PL quantum yields of PIF and PIC in dilute CHCl3 were
calculated to be 60 and 39%, respectively, referenced to the
standard, quinine sulfate. Although PIF and PIC emit in the
same range, the PL quantum yield of PIF was greater than
that of PIC, possibly due to the self aggregation of PIC. The
optical bandgaps ( E opt
g ) were calculated from the absorption
onset. The absorption onsets of PIF and PIC are 395 and
396 nm, respectively, resulting in respective optical bandgaps
of 3.14 and 3.13 eV. The electronic properties were mea-
sured by CV of thin films deposited on the working elec-
trode. The results are summarized in Table 2. The HOMO
energy values were calculated from the onset of the first oxi-
dation from the equations HOMO (eV) 5 [Eoxonset – E1/2
(Fc/Fc1) 1 4.8], where E1/2 (Fc/Fc1) is the cell correction.
Since the onset oxidation potentials of PIF and PIC occur at
1.30 and 1.20 V against Ag/AgCl as shown in Figure 2, the
HOMO levels of PIF and PIC were calculated to be 25.71
and 25.61 eV. Both polymers showed irreversible oxidation
potentials and the reduction peaks were not observed (Sup-
porting Information Figure S4). Therefore, the LUMO energy
values were calculated to be 22.57 and 22.48 eV from the
equation of LUMO 5 (E opt
g 2HOMOÞ:

TABLE 2 The Optical and Electronic Properties of the Polymers

Polymer Media kabsa (nm) kemsa (nm) ub Egopt (eV)c Eox (V)d HOMO (eV)e LUMO (eV)d

PIF CHCl3 361 416 0.60 – – – –

Film 360 416 3.14 1.30 25.71 22.57
PIC CHCl3 361 417 0.39 – – – –
Film 360 418 3.13 1.20 25.61 22.48

a d
Measured in dilute CHCl3. Measured from the onset of oxidation wave.
b e
Quantum yields measured in dilute CHCl3 solutions relative to stan- Calculated from the onset of the first oxidation using the equations
dard quinine sulfate. EHOMO (eV) 5 –[Eoxonset – E1/2 (Fc/Fc1) 1 4.8] where E1/2 (Fc/Fc1) is the
c
Measured (extrapolated) from the tangent drawn at the onset of cell correction.
f
absorption. Calculated from the equation LUMO 5 (Egopt – HOMO).

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FIGURE 3 Emission spectrum (green) and ECL spectrum (black)

FIGURE 2 ECL spectra of 0.3 mg/mL PIF and PIC dissolved in
THF and dropcasted on glassy carbon disk electrode. Potentials
were scanned in the negative direction first and two full cycles
are shown. Scan rate: 100 mV/s. Supporting electrolyte: 0.1 M
LiClO4 in ACN. [Color figure can be viewed at wileyonline-
library.com]
Electrogenerated Chemiluminescence
ECL generally consists of radical annihilation between a radi-
cal anion and a radical cation, produced on an electrode sur-
face to form an excited-state that emits light.37,38 If this
annihilation energy is sufficient to populate the singlet state,
then the ECL generates an excited state via a singlet-singlet
annihilation (S-route).39 The excited state formed during ECL
is the same as that in PL. A proposed ECL generation mecha-
nism for PIF and PIC is shown below with P representing
the polymer (eq (1–4))
P2e2 ! P:1 (1)
of 0.3 mg/mL PIF recorded for 60 s by changing potential step-
wise between 2 and 22 V. Working electrode: Pt wire at a scan
rate of 100 mV/s. Supporting electrolyte: 0.1 M TBAPF6 in
DCM. [Color figure can be viewed at wileyonlinelibrary.com]
species were present, and therefore they reacted to form an
excited state that emitted blue light. The observed ECL inten-
sity increased as more radical species were generated and it
was relatively stable over time as shown in Supporting Infor-
mation Figure S5. The ECL of these polymers in THF solu-
tions was also investigated (Supporting Information Figure
S6). Both PIF and PIC emitted light after a complete cycle
with both the oxidized and the reduced species, but the
additional ECL around 21.2 V was not observed in both
polymer solutions, possibly due to the low stability of the
generated species as well as mass transfer of these species
in the electrolyte. Compared with the PL spectrum of PIF
(kmax 5 422 nm), the ECL spectrum showed a red-shifted

P1e2 ! P:2 (2)

P :1 1P :2 ! 2P  (3)

2P ! 2P12hv (4)

ECL generation requires both the radical cation and the radi-
cal anion. Therefore, ECL was only observed after the poly-
mers were both reduced and oxidized. In Figure 2, the
polymer thin films, which were dropcasted from THF
solutions onto the working electrode, were first reduced by
scanning to negative potentials (1) and then oxidized by
scanning to positive potentials (2). The oxidized species
were relatively stable and therefore reacted with the reduced
species after the ECL observed around 1.8 V vs. SCE (3) to
produce an addition ECL emission around 21.2 V vs. SCE
(4). PIF showed a more intense ECL around 21.2 V vs. SCE
compared with PIC.

The electrode potential was then stepped between 2 and 22

V for 0.5 s to test the ECL stability. During the first step, FIGURE 4 The device structure of PLEDs fabricated with PIF
only one reagent species was formed, hence no ECL was polymer. [Color figure can be viewed at wileyonlinelibrary.
observed. During the second step both oxidized and reduced com]

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TABLE 3 The PLED Device Performance Data for PIF
Weight %
Polymer in host Host Vona (V)
PIF 2.0 CBP 5.4
5.0 CBP 5.2
5.0 mCP 5.6
100.0 – 8.8
a b
Turn-on voltage (at which EL is visible to the eyes).
emission (kmax 5 460 nm; Fig. 3.). The emission at a longer
wavelength in the ECL spectrum is probably due to the for-
mation of excimers after ion annihilation.40 An excimer,
which is an excited state dimer, is unstable in the ground
state, and its emission usually results structure less and
broad bands at longer wavelengths.4
PLED Fabrication
PLEDs with the structure: ITO/PEDOT:PSS (60 nm)/(poly-
mer 1 host)/TmPyPB (40 nm)/LiF (1 nm)/Al (100 nm)
(shown in Fig. 4) were fabricated using different emissive
layers. PIF or PIC as the guest in either 1,3-bis(N-carbazolyl)-
benzene (mCP) or 4,40 -bis(N-carbazolyl)-1,10 -biphenyl (CBP)
were used as the emissive layers in the devices. Devices pre-
pared with PIC as the guest showed very poor performance,
and thus are not shown here.
The performance of PLEDs fabricated with PIF as a guest are
summarized in Table 3. In comparison, devices fabricated
with neat PIF showed a very poor performance. This may be
due to the strong concentration quenching of the polymer in
its solid state.41,42 The highest brightness (200 Cd/m2)
was achieved for a device with 5.0 wt % of PIF in mCP (Sup-
porting Information Figure S7). This brightness seems to be
very low when compared to the brightness of a typical green
emitting PLEDs. However, this brightness is significant for
deep blue emitting PLEDs, where the measured brightness is
FIGURE 5 The electroluminescence spectra of PLEDs with PIF.
[Color figure can be viewed at wileyonlinelibrary.com]
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Current density Brightness Efficiency
(J, mA/cm2) (Cd/m2) [Cd/A, (% EQE)b] kmaxEL (nm)
361 148 0.40 (0.79) 416
324 137 0.50 (0.95) 418
279 199 1.02 (1.09) 417
94 141 0.30 (0.31) 418
EQE: external quantum efficiency.
greatly limited by the drastically reduced deep blue photopic
response factor, which is only 0.014 at 417 nm.43
The highest luminous efficiency was 1.0 Cd/A for the
device with 5 wt % PIF in mCP as the emissive layer. The
corresponding external quantum efficiency (EQE), that is, the
ratio between the number of emitted photons to the number
of injected electrons, was 1.1%. The electroluminescence
spectra of the devices are shown in Figure 5. All spectra are
similar with the emission maxima at 416–417 nm. This value
is similar to the thin film fluorescence emission. The Com-
mission Internationale de l’Eclairage (CIE) coordinates of all
the devices were (0.16, 0.07), very close to the National Tele-
vision System Committee (NTSC) standards value (0.14,
0.08) of the blue electroluminescence for full color displays.
CONCLUSIONS
Two deep blue emitting eumelanin-inspired poly(indoyle-
nearylene)s have been synthesized by coupling the
Eumelanin-inspired indole core with well-known blue emit-
ting arylenes, fluorine, and carbazole, via Suzuki polymeriza-
tion. Both polymers had good solubility in various organic
solvents and were thermally stable. Both PIF and PIC sys-
tems exhibited absorption in the near UV and a deep blue
emission in its solid state at 416 and 418 nm, respectively.
The fluorescence quantum yields of PIF and PIC in dilute
CHCl3 solution were 0.60 and 0.39, respectively. The light
emitting properties of the polymers were further investi-
gated by ECL analysis and showed a stable, intense ECL at
21.2 V. Both PIF and PIC exhibited deep HOMO levels of
25.71 and 25.61 eV, indicating the electronic stability of
these polymers. PLEDs were fabricated with PIF and resulted
in a luminous efficiency of 1 Cd/A and EQE of 1.1% with
peak emission at 418 nm. The CIE coordinates of the devices
(0.16, 0.07) closely match the standard value of blue electro-
luminescence for full color displays. Further work is ongoing
to optimize the parameters for improving the device
performance.
AUTHOR CONTRIBUTIONS
Dr. Sachinthani synthesized the polymers, characterized the
polymers’ structural, optical and electronic properties and
wrote the sections related to the synthesis and characteriza-
tion. Ms. Kaneza performed the electrogenerated chemilumi-
nescence (ECL) studies and wrote the ECL section of the
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manuscript. Dr. Pan supervised the ECL studies and wrote
the ECL section, Dr. Manna and Mr. Kaudal fabricated and
tested the PLEDs. Dr. J. Shinar and Dr. R. Shinar supervised
the PLED fabrication and contributed to the writing. Dr.
Sedai performed the TGA and DSC experiments and wrote
the thermal properties section. Dr. Eastman performed the
1
H and 13C NMR studies of the polymers and wrote related
section. Dr. Nelson supervised the whole research project
and wrote the manuscript.
ACKNOWLEDGMENT
The authors gratefully acknowledge support for this work from
Oklahoma State University Division of Institutional Diversity.
The Ames Laboratory is operated by Iowa State University for
the US Department of Energy (USDOE) under Contract No. DE-AC
02–07CH11358. The research at the Ames Laboratory was par-
tially supported by Basic Energy Sciences, Division of Materials
Science and Engineering, USDOE. Shanlin Pan and Nelly Kaneza
acknowledge the support of National Science Foundation (NSF)
under award numbers OIA-1539035 and CHE-1508192.
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