Arylamino-functionalized fluorene- and carbazole-based copolymers: Color-tuning their CdTe nanocrystal composites from red to white

Article abstract of DOI:10.1002/pola.24438

Four alternating arylamino-functionalized copolymers were synthesized in a Suzuki copolymerization applying 4, 4′-(2,7-dibromo-9H-fluorene-9,9-diyl) dianiline, 4,4′-(2,7-dibromo-9H-fluorene-9,9-diyl)bis(N,N-diphenylaniline) , 4-(3,6-dibromo-9H- carbazol-9

Full text of DOI:10.1002/pola.24438

Arylamino-Functionalized Fluorene- and Carbazole-Based Copolymers:
Color-Tuning Their CdTe Nanocrystal Composites from Red to White
IOANNIS KANELIDIS,1 YI REN,1 VLADIMIR LESNYAK,2 JAN-CHRISTOPH GASSE,3 RONALD FRAHM,3
2
ALEXANDER EYCHMULLER, ELISABETH HOLDER1
¨
1Functional Polymers Group and Institute of Polymer Technology, University of Wuppertal,
Gaußstrasse 20, D-42097 Wuppertal, Germany
2Physical Chemistry/Electrochemistry, TU Dresden, Bergstrasse 66b, D-01062 Dresden, Germany
3Department of Physics, University of Wuppertal, Gaußstrasse 20, D-42097 Wuppertal, Germany
Received 23 July 2010; accepted 3 October 2010
DOI: 10.1002/pola.24438
Published online 29 November 2010 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: Four alternating arylamino-functionalized copoly-
mers were synthesized in a Suzuki copolymerization applying 4,
40-(2,7-dibromo-9H-fluorene-9,9-diyl)dianiline, 4,40-(2,7-dibromo-
9H-fluorene-9,9-diyl)bis(N,N-diphenylaniline), 4-(3,6-dibromo-9H-
carbazol-9-yl)aniline and 4-(3,6-dibromo-9H-carbazol-9-yl)-N,N-
diphenylaniline in combination with 2,20-(9,9-dioctyl-9H-fluorene-
2,7-diyl)bis(1,3,2-dioxaborinane). The resulting novel alternating
copolymers were fully characterized. The copolymers revealed
blue light emission and wide optical bandgaps of at least 2.93
eV for the fluorene-based and 3.07 eV for the carbazole-based
polymers. The amino-functions allow to tie semiconducting
CdTe nanocrystals (NCs) and to synthesize a series of compo-
sites with CdTe NCs. Moreover, tuning the emission color over
a wide range by tying these CdTe NCs results in a facile prepa-
ration of organic–inorganic semiconductor composites with
C
V
emission colors ‘‘a` la carte.’’
2010 Wiley Periodicals, Inc.
J Polym Sci Part A: Polym Chem 49: 392–402, 2011
KEYWORDS: conjugated polymers; fluorescence; nanocrystals;
synthesis
INTRODUCTION Semiconducting conjugated copolymers1
have been often described in a multitude of derivatives.2–6
Poly(fluorene)s (PFs)7 are especially of importance as light-
emitting materials used in polymer light-emitting diodes8–10
and are of particular significance due to their high-photolu-
minescence quantum yields3,9,10 and rather large bandgaps.
However, their major problem is their tendency to structur-
ally decompose due to oxidation over time in the solid-state
on heating, leading to color instability and green electrolumi-
nescence when incorporated in the light emitting diodes
(LEDs).11–14 Functionalization of the fluorene C-9 position by
introducing bulky aryl-groups7 allows to overcome stability
matters15 and to reduce the interchain interactions, thereby,
improving the optoelectronic properties of the resulting
polymers.16–18 The latter may be enhanced when the poly-
mer backbone comprises spirofluorene moieties19 and is fur-
ther furnished with electron-withdrawing cyano substituents
and carbazole segments to complement the rather inefficient
charge transport of PFs.20
to their high hole-transporting mobility, strong absorption in
the ultraviolet spectral region, and blue light emission.21,22
A
further benefit is that the carbazole unit can raise the high-
est occupied molecular orbital (HOMO) energy level of the
polymers.23 These bandgap variations are important to host
other semiconductor moieties and to, thus, tune the emission
color of the host–guest system.
Triarylamines are widely used as hole-transporting materials
in LEDs24,25 or incorporated in polymer backbones to
enhance the performance of LEDs.26–29 It was shown that
covalent attachment of triarylamine substituents in the 9-
position of carbazole repeating units of carbazole main chain
polymers led to polymers with low-ionization potential and
high-fluorescence quantum efficiencies.30,31 Apart from their
hole-transporting ability, triarylamines can act as chromo-
phores in an electrochemical system and be, furthermore,
used as linkers to be attached to nanocrystalline surfaces,
i.e., TiO2.32,33
As mentioned, further promising candidates for technological
applications are poly(carbazole)s. Polymers based on carba-
zole have good electroactive and photoactive properties due
To design and synthesize alternating PFs and poly(carba-
zole)s, palladium-interceded cross-coupling reactions such
as the Suzuki polycondensation34 are useful.35,36 Copolymer-
Correspondence to: E. Holder (E-mail: holder@uni-wuppertal.de)
C
V
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 49, 392–402 (2011) 2010 Wiley Periodicals, Inc.
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ARTICLE
SCHEME 1 The synthetic routes of monomers 2–8 as well as of alternating copolymers 9–12.
ization of functional monomers, that keep the wide bandgap
can be connected to other functional or light-emitting
species such as nanoparticles or semiconductor nanocrystals
(NCs)37 and are, therefore, of increasing impact in modern
light-emitting technology involving simple and efficient
color-tuning on demand mechanisms.
by introducing two phenylamine groups in the 9-position of
2,7-dibromo-9H-fluoren-9-one (2) using an excess of aniline
for this condensation reaction. 4,40-(2,7-Dibromo-9H-fluo-
rene-9,9-diyl)bis(N,N-diphenylaniline) (4)39 was synthesized
following a similar route, however, by applying an excess of
triphenylamine in the presence of methane sulfonic acid
(Scheme 1). To generate alternating carbazole-based copoly-
mers (Scheme 1, right side), 3,6-dibromo-9-(4-nitrophenyl)-
9H-carbazole (5) was synthesized from 3,6-dibromo-9H-
carbazole with addition of 1-fluoro-4-nitrobenzene in the
presence of potassium carbonate via a nucleophilic substitu-
tion.40,41 Through reduction via tin(II) chloride of monomer
5, 4-(3,6-dibromo-9H-carbazol-9-yl)aniline (6) was obtained
as a yellow crystalline solid.40,41 4-Iodo-N,N-diphenylaniline (7)
was synthesized by application of an Ullmann coupling reaction
of diphenylamine and 1,4-diiodobenzene under the presence of
copper(II) sulfate and potassium carbonate at a reaction tem-
In this work, we introduce the synthesis and characterization
of four alternating copolymers that were designed with 4,40-
(2,7-dibromo-9H-fluorene-9,9-diyl)dianiline and 4,40-(2,7-
dibromo-9H-fluorene-9,9-diyl)bis(N,N-diphenylaniline) as
monomers for the fluorene-based copolymers and with 4-
(3,6-dibromo-9H-carbazol-9-yl)aniline or 4-(3,6-dibromo-9H-
carbazol-9-yl)-N,N-diphenylaniline as monomers for the poly
(carbazole)s. The comonomers were copolymerized with
2,20-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(1,3,2-dioxaborinane)
following a classical Suzuki protocol. The resulting alter-
nating copolymers revealed blue-light emission with an
emission maximum at 418 nm. Because of their nitrogen-
containing side chains, they may function to attach to a vari-
ety of nanoparticles. Here, we show the interconnection of
the functional copolymers to CdTe semiconductor NCs indi-
cated by tuning the emission color of the host–guest system.
The composites possess a color change from blue (copoly-
mers) and green to orange–red (CdTe NCs) to a red, reddish-
white, or white (composites) emission color.
ꢀ
perature of 220 C. Precursor 7 was obtained as a white solid
and further used in an Ullmann coupling with 3,6-dibromo-9H-
carbazole by the aid of copper(I) iodide and [18]-crown-6 to
end up with 4-(3,6-dibromo-9H-carbazol-9-yl)-N,N-diphenyl
aniline (8) (Scheme 1). Subsequently, the copolymerizations
were performed according to a Pd(0)-mediated Suzuki CAC-
coupling protocol.42 Using 4,40-(2,7-dibromo-9H-fluorene-9,9-
diyl)dianiline (3) or 4,40-(2,7-dibromo-9H-fluorene-9,9-diyl)-
bis(N,N-diphenylaniline) (4) in combination with 2,20-(9,9-
dioctyl-9H-fluorene-2,7-diyl)bis(1,3,2-dioxaborinane) (1) the
fluorene-based alternating polymers 9 and 10 were obtained
(Scheme 1, left side). 4-(3,6-Dibromo-9H-carbazol-9-yl)ani-
line (6) or 4-(3,6-dibromo-9H-carbazol-9-yl)-N,N-diphenyla-
niline (8) in combination with comonomer 1 yielded the car-
bazole-based alternating copolymers 11 and 12 (Scheme 1,
RESULTS AND DISCUSSION
To obtain alternating copolymers based on 2,20-(9,9-dioctyl-
9H-fluorene-2,7-diyl)bis(1,3,2-dioxaborinane) (1) and aryla-
mino-functionalized fluorenes (Scheme 1, left side), 4,40-(2,7-
dibromo-9H-fluorene-9,9-diyl)dianiline (3)38 was synthesized
ARYLAMINO-FUNCTIONALIZED COPOLYMERS, KANELIDIS ET AL.
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TABLE 1 Monomer Ratio of 3,4,6, and 8 to 1, GPC Characterizaton and Thermal Properties of
9–12
Polymer
(Monomer
Ratio)
Monomer Ratio
(3, 4, 6, 8/1)
(molar %)
c
Mn
(g molꢂ1
Mw
(g molꢂ1
PDI
Td
Tg
(ꢀC)
)
)
Units
(ꢀC)
9 (M3/M1)
10 (M4/M1)
11 (M6/M1)
12 (M8/M1)
a
46/54a
48/52a
46/54a
46/54a
46/54b
47/53b
45/55b
46/54b
5,700
5,500
2,900
2,900
17,300
12,900
5,300
3.0
2.4
1.8
1.8
420
440
420
420
–
150
–
5,300
128
Calculated from 1H NMR.
b
c
Calculated from elemental analysis.
At 5% weight loss.
right side). The palladium(0)-catalyzed polycondensations
were conducted with tetrakis(triphenylphosphine)palladium(0)
as catalyst, K2CO3 of 2 M concentration as base and refluxing
toluene as the reaction medium. The crude yields obtained for
9–12 are in the range of 60–92%.
8 in the respective copolymers backbone 9–12. Likewise, the
copolymers were characterized by means of gel permeation
chromatography (GPC) (Table 1). In Figure 1, the molecular
weight distributions of the copolymers are illustrated.
The approximately by half-reduced molecular weights (Ta-
ble 1) for polymers 11 and 12 are typical for Suzuki-medi-
ated polycondensation reactions10,44 and not unusual for car-
bazoles participating in such kind of polymerizations44,46
even in the case of homopolymers.47 The nature of the N-
substituents in the palladium-catalyzed coupling polyconden-
sation influences the solubility of the polymers and can lead
to modest molecular weights of Mw ꢁ 104.48 Despite the fact
that the copolymers reveal modest molecular weights, the
low-polydispersity indices evidence the homogeneity of the
synthesized materials. As known from literature, the
However, to remove impurities and low-molecular-weight
species and to, thus, obtain unimodal molecular-weight dis-
tributions, the crude copolymers 9–12 were exhaustively
purified by continuous extractions with chloroform–isopropa-
nol mixture over 3 days by means of a Soxhlet-apparatus,
whereby the chloroform fraction was isolated and reprecipi-
tated from methanol/ethyl acetate mixtures, methanol/tetra-
hydrofuran ones, or acetone. After these extensive purifica-
tion procedures, the copolymers were obtained as yellowish
solids still in yields of 30–36%, well soluble in solvents of
medium polarity like toluene, chloroform, or dichloro-
methane. Moderate yields are not an uncommon occasion in
fluorene-based backbones43 and fluorene–carbazole systems
furnished with bulky side chains have led to middle-rate
yields as well.44,45
The 1H NMR spectrum of polymer 9 is confirming the
presence of the amine-group in the polymer backbone
from the resonance at 3.62 ppm. For copolymer 10, the
nitrogen content is evidenced by elemental analysis (N
2.55%). The 1H NMR spectrum of copolymer 11 indicates
the presence of the amino-functionalized carbazole deriva-
tive 6 in the backbone of the polymer by a resonance at
3.94 ppm. For copolymer 12, elemental analysis (N
3.09%) elucidated the successful copolymerization of the
two comonomers 1 and 8. Combination of 1H-NMR spec-
troscopy and elemental analysis allowed the determination
of the actual comonomer percentages in each of the
copolymers backbone.
FIGURE 1 Molecular weight distribution of polymers 9–12
determined by GPC. Concentration of 0.5 mg mLꢂ1 was applied
for all polymers and the analysis was performed on MZSD col-
umns of particle size 5 lm, using chloroform as eluent for
polymers 9, 10 (calibration based on polystyrene standards)
and on GRAM columns, using dimethyl formamide (DMF) as
eluent with ammonium hexafluorophosphate 5 mM as salt at a
temperature of 40 ꢀC for polymers 11 and 12 (calibration based
on poly (methyl methacrylate) standards).
The calculations by the two different methodologies revealed
the comonomers’ ratio in the backbone of the copolymers 9–
12, approximately determining a 50% ratio (Table 1) as typi-
cally expected for alternating copolymers. Both methodolo-
gies revealed almost similar results for 9–12 with an excess
of comonomer 1 (about one to two repeating units more)
compared to the values obtained for monomers 3, 4, 6, and
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ARTICLE
TABLE 2 Optical Properties of Copolymers 9-12
a
a,b
b
a,c
c
a,d
Abssol (nm)
Absfilm
(nm)
Emsol
(nm)
Emfilm
(nm)
Egsol
(eV)
Egfilm
(eV)
Usol
(Lg e [L molꢂ1 cmꢂ1])
P9
385 (6.28)
381 (6.34)
343 (6.68)
341 (6.10)
387
395
350
358
418/442
416/441
401/420
404/420
424/448
428/447
411/425
409/426
2.93
2.94
3.10
3.07
2.84
2.71
2.76
2.72
0.32
0.66
0.84
0.51
P10
P11
P12
a
In chloroform solution (10ꢂ6 mol Lꢂ1).
kexc 380 nm for 9/10, 360 nm for 11/12.
Calculated from the absorption band edge.
b
c
d
Determined according to Demas and Crosby by using PF (Usol 0.71) as a reference.52,53
presence of oligomers can degrade the quality of the final
product, a phenomenon which can come up in polymeriza-
tions based on fluorene comonomers.49 Moreover, precipita-
tion into acetone is known to induce an increased solubility
of the higher molecular weight fractions.50 Acetone seems to
be the optimal medium for amino-functionalized copolymers.
A previous study in our laboratories showed that more polar
solvents such as methanol reduce the yields of the amino-
functional copolymers drastically, even below 10%, due to
the alcohol solubility of the amino-functional side chain.51
This effect is certainly to a large extent undesired in terms
of yield optimization, however, highly desired when focusing
on multilayer thin-film processing using orthogonal solvents.
All copolymers 9–12 possessed favorable thermal stabilities
indicated by Td values at 5% weight-loss of 420 ꢀC or even
higher (Table 1). Thus, copolymers 9–12 feature thin-film
processing from high-boiling point solvents. While for
copolymers 9 and 11, no glass transitions could be obtained,
copolymers 10 and 12 revealed Tg values in the expected
rescence excitation experiments (kexc: 370 nm) of films of
the composites of CdTe NCs E with the carbazole-based
arylamino-functionalized copolymers 11 and 12 are
depicted. The pictures in Figure 3(b) (11, 11 þ CdTe, CdTe,
12, 12 þ CdTe, in that order left to right) visualize a color
change from blue or red in the bare polymer or NC solutions
compared with a reddish-white emission of the composites.
The morphology of the achieved composites, drop casted
from the polymer–CdTe mixtures onto glass substrates, was
investigated using atomic force microscopy (AFM) in the tap-
ping mode. In Figure 4(a), the topography of the respective
composite films, prepared by mixing DMF solutions of the
CdTe E NCs (8 mg mLꢂ1) with THF solutions of the polymers
(1 mg mLꢂ1) in a 1:1 (v/v) ratio is illustrated, indicating the
formation of CdTe nanoparticle clusters with a domain size
of ꢃ200 nm. CdTe NCs seem to form aggregates while being
overcoated with a layer of the individual polymer. The rough-
ness of the film surfaces is extreme and traversing from
CdTe composites built with polymer 9–12, following the
recorded values: 146.6, 322.8, 254.5, and 165.7 nm. In
Figure 4(b), the AFM images of the bare polymers 9–12 are
depicted. The big spots, most likely due to dewetting, vary
regarding their size from 5 to 16 lm, while the smaller spots
are polymer as well with a size in the scale of 0.8–2 lm. The
tailing of the latter and the repeating pattern is assigned to
artifacts arising due to material dragged from the cantilever
over the scanned surface. Finally, the AFM image [Fig. 4(c)]
of CdTe E NCs reveals an even larger aggregation tendency,
most likely due to large packed regions (10–21 lm) with a
roughness of 319.9 nm. The film of bare NCs is more uni-
form compared with those of composites and bare polymers
but cracked due to shrinkage by solvent evaporation.
ꢀ
range of 128–150 C (Table 1). The optical properties of the
copolymers were additionally determined and represented in
Figure 2(a) and Table 2. In solution and film, all of them
exhibit blue-light emission with a red shift of ꢃ5–12 nm for
the solid-state experiments. In Figure 2(b), the optical prop-
erties of the NCs are represented as well in combination to
an exemplary transmission electron microscopy (TEM) image
for the orange-emitting CdTe NCs E [Fig. 2(c)].
The spectral overlap between the blue emission of the
copolymers 9–12 and the absorption of the CdTe NCs
[Fig. 2(a,b)] fulfills basically the prerequisites for energy
transfer (ET) from the polymer backbones to the NCs. More-
over, 9–12 revealed wide bandgaps of 2.93–3.10 eV in
solution, whereas, in the films, the optical bandgaps were
slightly reduced to 2.71–2.84 eV (Table 2). Therefore, solid-
state measurements of the optical properties of bare NCs,
polymers, and NC-polymer systems were conducted.
Combining now the blue-emitting polymers 9–12 and a
yellow-emitting species prepared from the orange–red emit-
ting CdTe NCs E with the green-emitting CdTe NCs B, a
white-light emission in solution was approached, revealed by
the emission bands at ꢃ425 nm and ꢃ545 nm [Fig. 5(a)].
Thin-film experiments are illustrated in Figure 5(b). In these
solid-state measurements, the band of blue emission is
shifted to ꢃ420 nm while its complementary yellow band
needed for the achievement of white light is found at
ꢃ510 nm [Fig. 5(b)]. Figure 5(c) illustrates exemplarily the
achieved favorable white-light emission (10 þ CdTe NCs B
In Figure 3(a), the fluorescence spectra (kexc: 380 nm) of
films of the composites of CdTe NCs E (orange–red emission)
with polymers 9 and 10 are shown. The photographs (9, 9
þ CdTe, CdTe, 10, 10 þ CdTe, in that order left to right) of
the composites under UV illumination illustrate the color
change from blue to red in the case of 9 and to reddish-
white in the case of 10 [Fig. 3(a)]. In Figure 3(b), the fluo-
ARYLAMINO-FUNCTIONALIZED COPOLYMERS, KANELIDIS ET AL.
395

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
FIGURE 2 (a) Normalized absorption
and emission spectra of copolymers
9–12 in solution (chloroform, 10ꢂ6
mol Lꢂ1). (b) Absorption and emission
spectra of CdTe/HS-C6H4-Br NCs emit-
ting from green (CdTe A) to orange–
red (CdTe E) color. The particle con-
centration in DMF varied from 10ꢂ3 to
7.3 ꢄ 10ꢂ4 M. (c) TEM image of CdTe/
HS-C6H4-Br NCs emitting orange light
(CdTe E). Photographs of CdTe NCs
in DMF: daylight and under illumina-
tion of UV light (kexc: 366 nm),
respectively.
FIGURE 3 Normalized emission spectra (a) (kexc: 380 nm) of copolymers 9 þ CdTe E and 10 þ CdTe E and (b) (kexc: 370 nm) of
copolymers 11 þ CdTe E and 12 þ CdTe E drop casted from THF (spectra of films) and a DMF/THF (1/3) mixture (photographs:
daylight and under illumination of UV light (kexc: 366 nm), respectively.
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FIGURE 4 AFM images (tapping mode) of films of composites prepared by mixing DMF solutions of the CdTe E NCs (8 mg mLꢂ1
)
with THF solutions of the polymers (1 mg mLꢂ1) in a 1:1 (v/v) ratio (a), of films of the polymers (concentrations of 0.5 mg mLꢂ1 in
THF) (b) and film of the CdTe E NCs (4 mg mLꢂ1 concentration in DMF) (c) on glass substrates obtained by drop casting the
respective solutions. The AFM images have a scale of 30 ꢄ 30 lm2. [Color figure can be viewed in the online issue, which is
available at wileyonlinelibrary.com.]
FIGURE 5 (a) Emission spectra of copolymers 9, 10 þ CdTe (kexc: 380 nm) and copolymers 11, 12 þ CdTe (kexc: 370 nm) in DMF
solutions showing white-light emission. (b) Normalized emission spectra of copolymers 9, 10 þ CdTe (kexc: 380 nm) and copoly-
mers 11, 12 þ CdTe (kexc: 370 nm) in films drop casted from DMF. (c) Exemplary photograph of white-light emission under illumi-
nation of UV light (kexc: 366 nm). [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
and E) in DMF solution. More detailed measurements involv-
ing photo-physical and electro-optical investigations will be
carried out in our laboratories taking the possible fine color-
tuning process of differently labeled and colored NCs into
consideration. A potential target for the future will be pure
white-light emission from composite materials.
of 0.5 mg mLꢂ1 concentration in THF and a CdTe DMF solu-
tion of 4 mg mLꢂ1 concentration were prepared and drop
casted on glass as well. For the purification of the monomers
by means of column chromatography, silica gel of particle
size 50–200 mesh was used as the stationary phase.
Materials
All reactions were carried out under inert conditions (ar-
gon). 9-H-Fluorenone, methanesulfonic acid, 1-fluoro-4-nitro-
benzene, tin(II) chloride, 2,20-(9,9-dioctyl-9H-fluorene-2,7-
diyl)bis(1,3,2-dioxaborinane) were purchased from Aldrich,
triphenylamine, 1,4-diiodobenzene, diphenylamine, copper(II)
sulfate, and aniline hydrochloride from Acros, 3,6-dibromo-
9H-carbazole, tetrakis(triphenylphosphine)palladium(0) from
ABCR, [18]-crown-6 and copper(I) iodide from Alfa Aesar
and aniline from Merck. All polymerizations were performed
in extra dry toluene and freeze-pumped 2-M potassium car-
bonate solution according to literature known procedures.39
EXPERIMENTAL
Instrumentation
1H NMR and 13C NMR spectra were recorded in deuterated
chloroform (CDCl3) with TMS as internal standard on a
Bruker ARX 400 and 600 Fourier Transform nuclear reso-
nance spectrometer. The chemical shift d is given in ppm.
Infrared studies were conducted on a JASCO FT/IR-4200
Fourier-transform-spectrometer. Mass spectra were obtained
using a Bruker micrOTOF instrument equipped with an elec-
trospray ionization source (ESI-MS). For the electron impact
ionization (EI) mass spectra, the device MAT 311A from Var-
ian was utilized. GPC analysis of polymers 9 and 10 was car-
ried out on a Jasco AS950 apparatus using Jasco UV-2070,
Jasco RI-930, and Viscotek T60 as detectors (column MZSD
of particle size 5 lm, eluent chloroform). For the determina-
tion of the molecular weights, a calibration based on polysty-
rene standards was applied. For polymers 11 and 12, GPC
analysis was performed by means of a Jasco AS2055 Plus ap-
paratus using Jasco UV/VIS-2070/75 and Jasco RI-2031 as
detectors (GRAM columns, DMF as eluent with ammonium
hexafluorophosphate 5 mM as salt). For the determination of
the molecular weights, a calibration based on poly (methyl
methacrylate) standards was applied. The elemental analyses
were performed by means of the Vario Elemental EL ana-
lyzer. Ultraviolet–visible measurements (UV–vis) were per-
formed on a Jasco V-550 spectrophotometer (1-cm cuvettes,
chloroform), while fluorescence spectroscopic measurements
were done on a Cary Eclipse fluorescence spectrophotometer
(1-cm cuvettes, chloroform). For the measurements in solu-
tion, concentrations of 10ꢂ4 mol Lꢂ1 were utilized for com-
pounds 2, 4–8, whereas monomer 3 and all polymers were
measured in concentrations of 10ꢂ6 mol Lꢂ1. The film meas-
urements were performed with concentrations of 1 mg mLꢂ1
for the polymers while the ET experiments by drop casting 1
mg mLꢂ1 polymer solutions mixed in a 1:1 ratio with THF-
diluted CdTe NCs. Thermal gravimetric analysis (TGA) was
performed under argon with a Mettler Toledo TGA/DSC 1
Monomer Synthesis
2,7-Dibromo-9H-fluoren-9-one (2)
Compound 2 was obtained as a yellow solid (24.77 g, 76%)
from 9H-fluoren-9-one (38.99 g, 17.40 mmol) by addition of
bromine (2 mL, 38.99 mmol) in water using a literature
precedure.54 1H NMR (CDCl3): d ¼ 7.40 (d, J ¼ 7.9 Hz, 2H),
7.65 (dd, J ¼ 7.9/1.8, 2H), 7.79 (d, J ¼ 1.8, 2H). 13C NMR
(CDCl3): d ¼ 190.8, 142.2, 137.4, 135.3, 127.8, 123.3, 121.8.
IR (cmꢂ1): 3407 (w, C¼¼O, stretching), 3080 (w, CAH,
stretching), 3055 (w, CAH, stretching), 1720 (s, C¼¼O,
stretching), 1051 (m, CABr, stretching). GC-MS m/z Calcd.
for C13H6Br2O 337.9; found 338. Anal. Calcd. for C13H6Br2O:
C, 46.20; H, 1.79. Found: C, 46.42; H, 2.79. UV–vis: kmax (lg e
[L molꢂ1 cmꢂ1]) 299 nm (2.59), 311 nm (2.50). Emission:
kmax 387 and 399 nm.
4,40-(2,7-Dibromo-9H-fluorene-9,9-diyl)dianiline (3)
Compound 3 (4.30 g, 70%) was prepared from 2,7-dibromo-
9H-fluoren-9-one (4.2 g, 12.4 mmol), aniline hydrochloride
(2 g, 15.3 mmol), and aniline (10 ml, 109 mmol) using a
literature procedure.38 The product was isolated after col-
umn chromatography (n-hexane/ethyl acetate 4:1) as a grey
1
solid). H NMR (CDCl3): d ¼ 3.64 (s, 4H), 6.58 (d, J ¼ 8.6 Hz,
4H), 6.96 (d, J ¼ 8.6 Hz, 4H), 7.47 (dd, J ¼ 8.1/1.8 Hz, 2H),
7.49 (d, J ¼ 1.6 Hz, 2H), 7.57 (d, J ¼8.1 Hz, 2H). 13C NMR
(CDCl3): d ¼ 154.1, 145.3, 137.8, 134.4, 130.5, 129.2, 128.9,
121.7, 121.4, 115.0, 64.4. IR (cmꢂ1): 3457–3339 (w, NAH,
stretching), 3030 (w, CAH, stretching), 1616 (s, NAC, defor-
mation), 1049 (s, CABr, skeleton). ESI-MS m/z Calcd for
with a heating correspondingly cooling rate of 10 K minꢂ1
.
TEM was performed on a Tecnai T20 microscope operating
at 200 kV (FEI). The TEM specimens were prepared by drop-
ping diluted NC solutions onto copper grids coated with a
thin Formvar-carbon film with subsequent evaporation of
the solvent. AFM was performed on a Q-ScopeTM 250 (Ques-
ant Instrument Corporation). A scan head was utilized of 1-
nm lateral resolution, 9-lm maximal vertical range, 0.1-nm
vertical resolution, and a four-quadrant photodiode. In the
case of composites, samples were prepared by mixing DMF
solutions of the CdTe NCs (8 mg mLꢂ1) with THF solutions
of the polymers (1 mg mLꢂ1) in a 1:1 (v/v) ratio and subse-
quently drop casted on glass substrates. Polymer solutions
C
25H18Br2N2 506.2; found 507. Anal. Calcd for C25H18Br2N2:
C, 59.31; H, 3.58; N, 5.53. Found: C, 59.32; H, 3.53; N, 5.52.
UV–vis: kmax (lg e [L molꢂ1 cmꢂ1]) 293 nm (6.20), 319 nm
(6.18). Emission: kmax 335 nm.
4,40-(2,7-Dibromo-9H-fluorene-9,9-diyl)bis(N,N-
diphenylaniline) (4)
Compound 4 (white solid, 4.8 g, 81%) was prepared from
2,7-dibromo-9H-fluoren-9-one (2.46 g, 7.28 mmol), triphenyl-
amine (25 g, 102 mmol) and methane sulfonic acid (1.4 g,
14.56 mmol) following a literature procedure.39 1H NMR
(CDCl3): d ¼ 6.95 (d, J ¼ 8.8 Hz, 4H), 7.01–7.06 (m, 4H),
398
WILEYONLINELIBRARY.COM/JOURNAL/JPOLA

ARTICLE
7.11 (dd, J ¼ 8.4/0.8 Hz, 8H), 7.24–7.30 (m, 12H), 7.51 (dd,
J ¼ 8.1/1.7 Hz, 2H), 7.56 (d, J ¼ 1.7 Hz, 2H), 7.60 (d, J ¼ 8.1
Hz, 2H). 13C NMR (CDCl3): d ¼ 153.4, 147.5, 146.7, 137.9,
137.6, 130.8, 129.3, 129.2, 129.1, 128.6, 124.6, 124.4, 123.0,
122.9, 122.8, 122.7, 121.7, 121.5, 64.6. IR (cmꢂ1): 3030 (w,
CAH, stretching), 1270 (s, CAN, stretching). ESI-MS m/z
Calcd. for C49H34Br2N2 810.1; found 810.6. Anal. Calcd. for
4-(3,6-Dibromo-9H-carbazol-9-yl)-N,N-diphenylaniline (8)
Compound 8 (0.402 g, 57%) was obtained from 4-iodo-N,N-
diphenylaniline (0.557 g, 1.50 mmol), 3,6-dibromo-9H-carba-
zole (0.4 g, 1.23 mmol), copper(I) iodide (0.05 g, 0.263
mmol), [18]-crown-6 (0.03 g, 0.114 mmol), and potassium
carbonate (0.8 g, 5.80 mmol) in DMSO following a literature
procedure.56 Purification by column chromatography (petrol
ether/ethyl acetate 15:1) gave a white solid as isolated prod-
C
49H34Br2N2: C, 72.60; H, 4.23; N, 3.46. Found: C, 72.28; H,
3.95; N, 3.23. UV–vis: kmax (lg e [L molꢂ1 cmꢂ1]) 295 nm
(3.19), 308 nm (3.23). Emission: kmax 388 nm, 399 nm.
uct. H NMR (CDCl3): d ¼ 7.13 (t, J ¼ 7.4 Hz, 2H), 7.23–7.27
1
(m, 14H), 7.53 (dd, J ¼ 6.7/2.0 Hz, 2H), 8.21 (d, J ¼ 1.8 Hz,
2H). 13C NMR (CDCl3): d ¼ 147.7, 147.3, 140.1, 130.0, 129.5,
127.6, 125.0, 123.8, 123.7, 123.5, 123.1, 112.8, 111.6. IR
(cmꢂ1): 3055 (w, CAH, stretching), 3038 (w, CAH, stretch-
ing), 1585 (s, C¼¼C, stretching), 1054 (s, CABr, skeleton).
ESI-MS m/z Calcd. for C30H20Br2N2 568.3; found 568. Anal.
Calcd. for C30H20Br2N2: C, 63.40; H, 3.55; N, 4.93. Found: C,
63.21; H, 3.38; N, 4.87. UV–vis: kmax (lg e [L molꢂ1 cmꢂ1])
305nm (3.00). Emission: kmax 387 and 399 nm.
3,6-Dibromo-9-(4-nitrophenyl)-9H-carbazole (5)
Compound 5 (yellow crystals, 4.3 g, 76%) was prepared
from 3,6-dibromo-9H-carbazole (4.09 g, 12.6 mmol), potas-
sium carbonate (8.71 g, 62.02 mmol) and 1-fluoro-4-nitro-
benzene (7.11 g, 50.42 mmol) in DMF using literature proce-
dures.40,41 1H NMR (CDCl3): d ¼ 7.33 (d, J ¼ 8.7 Hz, 2H),
7.56 (d, J ¼ 8.7 Hz, 2H), 7.74 (d, J ¼ 8.6 Hz, 2H), 8.21 (s,
2H), 8.50 (d, J ¼ 8.5 Hz, 2H). 13C NMR (CDCl3): d ¼ 146.4,
142.8, 138.9, 129.9, 126.8, 125.7, 124.7, 123.6, 114.3, 111.2.
IR (cmꢂ1): 1498 (s, N¼¼O, asymmetric stretching), 1325 (s,
N¼¼O, symmetric stretching), 1054 (m, CABr, skeleton). ESI-
MS m/z Calcd for C18H10Br2N2O2 446.1; found 446. Anal.
Calcd for C18H10Br2N2O2: C, 48.46; H, 2.26; N, 6.28. Found:
C, 48.41; H, 1.46; N, 6.29. UV–vis: kmax (lg e [L molꢂ1 cmꢂ1])
374 nm (2.44). Emission: kmax 388 and 398 nm.
Synthesis of the Copolymers—General Procedure
Comonomers 3 or 4 (see Scheme 1), 6 or 8 (see Scheme 1)
were added together with 2,20-(9,9-dioctyl-9H-fluorene-2,7-
diyl)bis(1,3,2-dioxaborinane) (1) and Pd(0)(PPh3)4 in
a
Schlenk tube. Subsequently, freeze-pump degassed toluene
(3 mL) and Na2CO3 solution (1 mL) were added, and the
ꢀ
reaction system was allowed to stir for 3 days at 120 C. Af-
ter cooling down to room temperature, the reaction solution
was extracted with chloroform and washed with saturated
NaEDTA solution (1 ꢄ 50 mL), brine (1 ꢄ 100 mL), and
water (1 ꢄ 50 mL). The organic phase was dried over
MgSO4 and the solvent was removed by reduced pressure.
The residue was dissolved in chloroform (1–2 mL), precipi-
tated in methanol-THF-ethyl acetate mixtures, or into acetone
(400 mL), and the polymers further purified by Soxhlet
extraction using isopropanol or chloroform as a solvent.
4-(3,6-Dibromo-9H-carbazol-9-yl)aniline (6)
Compound 6 (1.02 g, 87%) was prepared from 3,6-dibromo-
9-(4-nitrophenyl)-9H-carbazole (1.25 g, 2.80 mmol) by addi-
tion of tin(II) chloride (3.16 g, 14.01 mmol) in ethanol
according to literature procedures.40,41 After recrystallization
1
from toluene, white crystals were obtained. H NMR (CDCl3):
d ¼ 6.88 (d, J ¼ 1.6 Hz, 2H), 7.17–7.29 (m, 4H), 7.50 (dd,
J ¼ 8.7/1.7 Hz, 2H), 8.20 (d, J ¼ 1.6 Hz, 2H). 13C NMR
(CDCl3): d ¼ 146.4, 140.4, 129.1, 128.3, 127.0, 123.5, 123.0,
115.9, 112.5, 111.5. IR (cmꢂ1): 3443–3357 (m, NAH, stretch-
ing), 3048 (m, CAH, stretching), 1619 (s, CAN, deformation),
1271 (s, CAN, stretching), 1051 (m, CABr, skeleton). ESI-MS
m/z Calcd for C18H12Br2N2 416.1; found 416. Anal. Calcd. for
C18H10Br2N2: C, 51.96; H, 2.91; N, 6.73. Found: C, 52; H,
2.55; N, 6.73. UV–vis: kmax (lg e [L molꢂ1 cmꢂ1]) 346 nm
(2.04), 358 nm (2.05). Emission: kmax 387 and 398 nm.
Polymer 9
Compound 3 (0.0254 g, 0.5 mmol), 1 (0.28 g, 0.5 mmol),
Pd(0)(PPh3)4 (0.05 g, 0.043 mmol). Polymer 9 was precipi-
tated into methanol, Soxhlet extracted with isopropanol and
chloroform, while the chloroform fraction was precipitated
from a 1:1 (v:v) methanol/ethyl acetate and 3:1 (v:v) metha-
nol/THF mixture yielding a yellow solid (99 mg, 30%). 1H
NMR (CDCl3): d ¼ 0.78 (b, 6H), 0.9–1.3 (b, 20H.), 1.99 (b,
4H), 3.62 (s, NH2, 4H), 6.58 (m, 8H), 7–7.9 (m, 12H). IR
(cmꢂ1): 2919 (s, CH2, stretching), 2847 (m, CH2, stretching),
1616 (m, C¼¼C, stretching), 1511 (s, ¼¼CH, stretching), 1461
(m, CAH, deformation), 1278 (m, CAC, skeletal vibration),
1185 (m, CAN, stretching), 815 (s, ¼¼CAH, out-of-plane de-
formation). GPC (g molꢂ1): Mn ¼ 5660, Mw ¼ 17300, PDI
3.06. Anal Calcd. for (C56H64N2)x: C, 87.91; H, 8.4ꢀ3; N, 3.66.
Found: C, 87.99; H, 8.74; N, 3.35. TGA: Td5%: 420 C. UV–vis:
kmax (lg e [L molꢂ1 cmꢂ1]) 385 nm (6.28). Emission: kmax
418 nm.
4-Iodo-N,N-diphenylaniline (7)
Compound 7 was obtained as a white solid (2.2 g, 42%)
from 1,4-diiodobenzene (8.8 g, 26 mmol), diphenylamine
(2.4 g, 14.10 mmol), copper(II) sulfate (0.176 g, 0.705
mmol), and potassium carbonate (1.95 g, 14.1 mmol) using a
literature-known procedure.55 1H NMR (CDCl3): d ¼ 6.86 (d, J
¼ 8.9 Hz, 2H), 7.07 (dd, J ¼ 7.8/6.9, 2H), 7.11 (dd, J ¼ 8.5/
1.0 Hz, 4H), 7.29 (dd, J ¼ 8.5/7.5 Hz, 4H), 7.53 (d, J ¼ 8.9,
2H). 13C NMR (CDCl3): d ¼ 147.7, 147.2, 138.0, 129.3, 125.2,
124.5, 123.3, 84.7. IR (cmꢂ1): 3059 (w, CAH, stretching),
3030 (w, CAH, stretching), 1583 (s, C¼¼C, stretching), 1060 (s,
CAI, skeleton). GC-MS m/z Calcd. for C18H14NI 371.21; found
371. Anal. Calcd. for C18H14NI: C, 58.24; H, 3.80; N, 3.77.
Found: C, 58.67; H, 3.13; N, 3.81. UV–vis: kmax (lg e [L molꢂ1
cmꢂ1]) 307 nm (2.72). Emission: kmax 387 and 398 nm.
Polymer 10
Compound 4 (0.406 g, 0.5 mmol), 1 (0.28 g, 0.5 mmol),
Pd(0)(PPh3)4 (0.05 g, 0.043 mmol). Polymer 10 was precipi-
tated from methanol, Soxhlet extracted with isopropanol-
ARYLAMINO-FUNCTIONALIZED COPOLYMERS, KANELIDIS ET AL.
399

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
chloroform mixture, whereas the chloroform fraction was
once more precipitated from acetone. A yellow solid was
obtained (171 mg, 33%). 1H NMR (CDCl3): d ¼ 0.9 (b, 6H),
1.02–1.30 (m, 16H), 1.96 (b, 4H.), 2.06 (b, 4H), 6.93–7.27
(m, 28H), 7.50–7.95 (m, 12H). IR (cmꢂ1): 2919 (m, CH2,
stretching), 2847 (w, CH2, stretching), 1587 (m, C¼¼C,
stretching), 1490 (s, ¼¼CH, stretching), 1447 (m, CAH, defor-
mation), 1271 (s, ¼¼CH, in-plane deformation), 1178 (w,
CAN, stretching), 1024 (w, ¼¼CAH, in-plane deformation),
808 (s, ¼¼CAH, out-of-plane deformation), 747 (m, CAC,
skeleton). GPC (g molꢂ1): Mn ¼ 5520, Mw ¼ 12900, PDI
2.47. Anal. Calcd. for (C80H80N2)x: C, 89.84; H, 7.54; N, 2.62.
in ref. 57. Briefly, 0.53 g (2.3 mmol) of Cd(OOCH3)2 and
0.57 g (3 mmol) of 4-bromthiophenol were dissolved in
120 mL of DMF. This solution was deaerated by bubbling
with Ar for 30 min. Under stirring, H2Te gas, generated by
the reaction of 0.67 g (1.5 mmol) of Al2Te3 with an excess
of 0.5 M H2SO4 solution, was injected into the reaction mix-
ture with a slow argon flow. The molar ratio of Cd2þ/Te2ꢂ
/
HS-C6H4-Br was 1/2/1.3. Formation and growth of the NCs
proceeded on reflux under open-air conditions. Colloidal
fractions A–E containing NCs of different sizes emitting green
(2.1 nm) to orange (2.9 nm) were taken during the reaction
after 20 min, 1, 2, 4, and 6 h of reflux, respectively.
ꢀ
Found: C, 88.92; H, 6.84; N, 2.55. TGA: Td5%: 440 C. DSC: Tg:
The colloids obtained were purified by reprecipitation.58
After removal of ꢃ90% of the solvent with a rotor evapora-
tor, the nanoparticles were precipitated by addition of an
excess of methanol. The precipitates were separated by
centrifugation and dissolved in DMF, yielding nanocrystal
concentrations varying from 1 ꢄ 10ꢂ3 to 7.3 ꢄ 10ꢂ4 M.
Optical properties of CdTe/HS-C6H4-Br NCs are shown in
Figure 2(b). The UV–vis absorption spectra were recorded
using a Cary 50 spectrophotometer (Varian, Palo Alto, CA).
Fluorescence spectra were acquired with a FluoroMax-4
spectrofluorometer (HORIBA Jobin Yvon, Edison, NJ).
150 ꢀC. UV–vis: kmax (lg e [L molꢂ1 cmꢂ1]) 381 nm (6.34).
Emission: kmax 416 nm.
Polymer 11
Compound 6 (0.209 g, 0.5 mmol), 1 (0.28 g, 0.5 mmol),
Pd(0)(PPh3)4 (0.05 g, 0.043 mmol). Polymer 11 was precipi-
tated from methanol, Soxhlet extracted with isopropanol–
chloroform mixture, whereas the chloroform fraction was
once more precipitated from a 1:1 (v:v) methanol/ethyl ace-
tate and a 3:1 (v:v) methanol/THF mixture. A yellow solid
was obtained (109 mg, 34%). 1H NMR (CDCl3): d ¼ 0.8 (b,
6H), 1.0–1.30 (m, 24H), 2.12 (b, 4H), 3.94 (dist. s, 2H), 6.95
(s, 4H), 7.3–7.9 (m, 10H), 8.55 (m, 2H). IR (cmꢂ1): 2969 (w,
CH2, stretching), 2922 (m, CH2, stretching), 2855 (w, CH2,
stretching), 2359 (s, NAH, stretching), 1619 (m, C¼¼C,
stretching), 1511 (s, ¼¼CH, stretching), 1454 (s, CAH, defor-
mation), 1274 (m, CAC, skeletal), 1174 (m, CAN, stretching),
1131 (w, ¼¼CH, in-plane deformation), 955 (w, ¼¼CAH,
in-plane-deformation), 801 (s, ¼¼CAH, out-of-plane deforma-
tion). GPC (g molꢂ1): Mn ¼ 2890, Mw ¼ 5340, PDI 1.85.
Anal. Calcd for (C47H52N2)x: C, 87.26; H, 8.41; N, 4.33. Found:
C, 85.44; H, 6.98; N, 3.87. TGA: Td5%: 420 ꢀC. DSC: Tg:
152 ꢀC. UV–vis: kmax (lg e [L molꢂ1 cmꢂ1]) 343 nm (6.68).
Emission: kmax 401 nm.
Preparation of White-Light-Emitting Composites
(Solutions and Films)
The solutions for the achievement of white light were pre-
pared by combining yellow-emitting NCs with blue-emitting
polymers and fine tuning the color by addition of orange-
emitting NCs and green–yellow ones. In general, a 2.5–2.8
ratio of yellow (CdTe B) to orange (CdTe E) NCs was used.
Films were prepared by drop casting the nanocrystal and
polymer containing DMF solutions on glass. For this purpose,
CdTe B NCs were used in a concentration of 1.08 ꢄ 10ꢂ4 M,
CdTe E in a concentration of 2.4 ꢄ 10ꢂ5 M and polymers 9–
12 in a 1 mg mLꢂ1 concentration.
CONCLUSIONS
Polymer 12
Compound 8 (0.285 g, 0.5 mmol), 1 (0.28 g, 0.5 mmol),
Pd(0)(PPh3)4 (0.05 g, 0.043 mmol). Polymer 12 was precipi-
tated from methanol, Soxhlet extracted with isopropanol-
chloroform mixture, whereas the chloroform fraction was
once more precipitated from acetone. A yellow solid was
obtained (143 mg, 36%). 1H NMR (CDCl3): d ¼ 0.8 (b, 6H),
1.0–1.50 (m, 24H), 2.16 (b, 4H), 7.31–7.90 (m, 24H), 8.55
(m, 2H). IR (cmꢂ1): 2980 (m, CH2, stretching), 2915 (m, CH2,
stretching), 2359 (m, C¼¼NHþ, stretching), 1587 (m, C¼¼C,
stretching), 1501 (s, ¼¼CH, stretching), 1457 (m, CAH, defor-
mation), 1274 (m, CAC, skeletal), 1178 (m, CAN, stretching),
808 (s, ¼¼CAH, out-of-plane deformation). GPC (g molꢂ1): Mn
¼ 2920, Mw ¼ 5290, PDI 1.81. Anal. Calcd for (C59H60N2)x:
C, 88.67; H, 7.82; N, 3.51. Found: C, 85.60; H, 4.47; N, 3.09.
TGA: Td5%: 420 ꢀC. DSC: Tg: 128 ꢀC. UV–vis: kmax (lg e [L
molꢂ1 cmꢂ1]) 341 nm (6.10). Emission: kmax 404 nm.
We prepared two fluorene-based and two carbazole-based
copolymers using a Suzuki protocol. The copolymers were
comprised of 4,40-(2,7-dibromo-9H-fluorene-9,9-diyl)diani-
line, 4,40-(2,7-dibromo-9H-fluorene-9,9-diyl)bis(N,N-dipheny-
laniline), 4-(3,6-dibromo-9H-carbazol-9-yl)aniline, and 4-(3,6-
dibromo-9H-carbazol-9-yl)-N,N-diphenylaniline each copoly-
merized with 2,20-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(1,3,2-
dioxaborinane). The four alternating copolymers revealed
wide bandgaps of at least 2.93 eV in chloroform solutions
and proved themselves as excellent host materials for CdTe
NCs in thin films enabling approving and facile color-tuning
over a wide range even to favorable white-light emission
within these organic–inorganic composites.
The Deutsche Forschungsgemeinschaft (DFG) is acknowledged
for financial support within the grant application HO3911/2-1:
‘‘Hybrid polymer/nanocrystals structures: fabrication and
studies of energy transfer, charge generation and transport.’’
Prof. Ullrich Scherf is acknowledged for granting access to the
tools of the Macromolecular Chemistry at the University of
Synthesis of CdTe/HS-C6H4-Br NCs
A
colloidal solution of 4-bromthiophenol (HS-C6H4-Br)-
capped CdTe NCs was prepared using the approach reported
400
WILEYONLINELIBRARY.COM/JOURNAL/JPOLA

ARTICLE
24 Casalbore-Miceli, G.; Esposti, A. D.; Fattori, V.; Marconi, G.;
Wuppertal (BUW). Anke Helfer is especially acknowledged for
her help with the GPC, TGA, and DSC measurements.
Sabatini, C. Phys Chem Chem Phys 2004, 6, 3092–3096.
25 Huang, Q.; Li, J.; Evmenenko, G. A.; Dutta, P.; Marks, T. J.
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