Violet-blue-or pure-blue-emitting triphenylamine derivatives: Synthesis and properties

Article abstract of DOI:10.1139/cjc-2012-0473

We report the synthesis and optoelectronic properties of a series of nine triphenylamine derivatives. They were synthesized by Suzuki cross-coupling reactions and characterized by elemental analysis, nuclear magnetic resonance, ultraviolet visible absorpt

Full text of DOI:10.1139/cjc-2012-0473

1043
ARTICLE
Violet-blue- or pure-blue-emitting triphenylamine derivatives:
synthesis and properties
Zhi-Ping Wu, Gui-Jun Liu, Cai-Cai Zhu, Zhi-Mei Li, Xi-Cun Gao, and Qian-Yong Cao
Abstract: We report the synthesis and optoelectronic properties of a series of nine triphenylamine derivatives. They were
synthesized by Suzuki cross-coupling reactions and characterized by elemental analysis, nuclear magnetic resonance, ultraviolet
visible absorption spectra, fluorescence spectra, and cyclic voltammetry. All compounds exhibit reversibly electrochemical
behavior. In solid state, compounds 5 and 9 emit near violet blue and compounds 1, 2, 4, 6, 7, and 8 emit deep blue or pure blue
and compound 3 emits green. Of all of these compounds, compounds 1, 3, 4, and 8 exhibit high fluorescence quantum yields
(44%–68%) with the best coplanarity. Compared with them, compounds 5 and 9 have the lowest fluorescence quantum yields due
to the least coplanarity. With the similarity in structure with those reported in literature, these compounds can be potentially
useful for blue-emitting, host, and up-converting materials.
Key words: triphenylamine, violet blue, blue-emitting, quantum yield, electrochemistry.
Résumé : On présente la synthèse et les propriétés optoélectroniques d’une série de neuf dérivés de la triphénylamine. Ces
dérivés ont été synthétisés par des réactions de couplage de Suzuki et caractérisés en se basant sur l’analyse élémentaire, la
résonance magnétique nucléaire, les spectres d’absorption ultraviolet-visible, les spectres de fluorescence et la voltammétrie
cyclique. Tous les composés présentent un comportement électrochimique réversible. À l’état solide, les composés 5 et 9
émettent dans le bleu tirant sur le violet, les composés 1, 2, 4, 6, 7 et 8 émettent dans le bleu foncé ou le bleu pur, et le composé
3 émet dans le vert. Les composés 1, 3, 4 et 8 présentent un rendement quantique de fluorescence élevé (44%–68%) et la meilleure
coplanarité. Comparativement, les composés 5 et 9, qui possèdent le moins de coplanarité, donnent le rendement quantique de
fluorescence le plus faible. En raison de la similarité entre leur structure et celle des composés décrits dans la littérature, ces
composés pourraient être utiles a` titre de matériaux émettant dans le bleu, de matériaux hôtes et de matériaux convertisseurs
élévateurs de fréquence. [Traduit par la Rédaction]
Mots-clés : triphénylamine, bleu-violet, émettant dans le bleu, rendement quantique, électrochimie.
Triarylamine and its derivatives have often been used as the
Introduction
building blocks for efficient hole-transport, blue-emitting, and
Organic light-emitting diodes (OLEDs) have been widely recog-
host materials,32–41 e.g., triphenylamine itself has a high triplet
nized as the next-generation technology for flat panel displays
energy of 3.04 eV and good hole-transporting ability.42 Triphenyl-
and white lighting.1–5 In recent years, there has been considerable
amine/fluorene hybrid and triphenylamine/oxadiazole derivative
interest in developing organic electroluminescence devices with
are good host materials.43,44
high luminance for white lighting, with high efficiency and sta-
In this paper, we report the synthesis and properties of a series
bility for long-driving lifetime displays.6–12 Especially, blue elec-
of triphenylamine derivatives. Of the nine compounds synthe-
troluminescence materials attracted much attention.6,7,13–17 This
sized, eight compounds emit violet-blue or pure-blue light. With
is because on one hand, for full color applications, red, green, and
similar structures as those reported in literature, we are sure they
blue (RGB) emission are required.18 On the other hand, an efficient
can be potentially useful for blue-emitting, up-converting, or host
blue or violet-blue emission can be down-converted to other low-
energy colors, like green and red. However, the performance of
materials.
blue material was generally low compared with its red and green
Experimental
counterparts19 because it is more difficult to produce a blue emis-
Chemicals and instruments
sion due to its intrinsic characteristic of having a wide band gap
irrespective of the type of materials.
All chemicals were used as purchased from commercial
sources. All solvents were carefully dried according to common
laboratory techniques. Melting point was recorded on an X-4 mi-
croscopic melting point instrument. 1H NMR data were collected
on a Bruker Avance DRX-400 NMR spectrometer in CDCl3. Absorp-
tion spectra were recorded on a Perkin-Elmer Lambda-35 UV-Vis
spectrophotometer. Fluorescent spectra were recorded on a Hita-
chi F-4500 spectrophotometer. Cyclic voltammograms were car-
ried out in 0.10 mol L−1 n-Bu4NClO4 dissolved in freshly dried
In addition, violet-blue- and blue-emitting materials have been
used for hosts to other blue/green/red-emitting fluorescent and
phosphorescent materials based on the “overlap” principle.20–24
Although there are a number of efficient blue dyes that have been
developed in the past several years,25–31 efficient violet-blue- or
blue-emitting materials are still a bottleneck to the development
of OLEDs, which encourages us to do research in seeking good
blue-emitting materials.
Received 3 December 2012. Accepted 28 March 2013.
Z.-P. Wu,* G.-J. Liu,* C.-C. Zhu, Z.-M. Li, X.-C. Gao, and Q.-Y. Cao. Department of Chemistry, School of Science, Nanchang University, Xue-Fu Road 999, Hong-Gu-Tan New District,
Nanchang 330031, China.
Corresponding authors: Xi-Cun Gao (e-mail: xcgao@ncu.edu.cn) and Qian-Yong Cao (e-mail: cqyong@ncu.edu.cn).
*These authors contributed equally to this work.
Can. J. Chem. 91: 1043–1047 (2013) dx.doi.org/10.1139/cjc-2012-0473
Published at www.nrcresearchpress.com/cjc on 3 June 2013.

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Can. J. Chem. Vol. 91, 2013
Scheme 1. Synthetic routes of compounds 1–9.
dichloromethane on an Autolab Potentiostat 30. All potentials
Synthesis of 9-(4=-(N,N-diphenylamino)phenyl)anthracene (3)
were quoted against an F+c/F− couple, unless otherwise stated,
The synthetic and purification procedure is similar to that of
compound 1 and gives a blue acicular crystal; yield 42.47%, mp
188–190 °C. 1H NMR (400 MHz, CDCl3) ␦: 8.424 (s, 5H), 7.99–8.01 (m,
9H), 7.44–7.47 (m, 9H). Anal. calcd. for C32H23N: C 91.92, H 5.46,
N 3.33; found: C 90.76, H 5.43, N 3.34.
c
whose half-wave potential is 0.55 0.01 V against the above Ag/
AgCl reference electrode. All experimental manipulations and
data collections were performed at room temperature, unless oth-
erwise stated.
Synthesis of 1-(4=-(N,N-diphenylamino)phenyl)naphthalene (4)
The synthetic and purification procedure is similar to that of
compound 1 and gives a white acicular crystal; yield 61.38%, mp
138–140 °C. 1H NMR (400 MHz, CDCl3) ␦: 8.01 (s, 1H), 7.84–7.91 (m,
3H), 7.72–7.75 (d, 1H, J = 8.8 Hz), 7.60–7.62 (d, 2H, J = 8.8 Hz),
7.46–7.50 (m, 2H), 7.26–7.31 (t, 4H, J = 8.0 Hz), 7.15–7.20 (t, 6H, J =
10 Hz), 7.03–7.07 (t, 2H, J = 7.2 Hz). Anal. calcd. for C28H21N: C 90.57,
H 5.66, N 3.81; found: C 90.61, H 5.23, N 3.81.
Synthesis
The chemical structure and the synthetic procedure for the
target compounds 1–9 are illustrated in Scheme 1. Suzuki cou-
pling reactions were used as a key technique to construct the
intermediates and the target compounds. References are listed for
the intermediates.
Synthesis of 4-(N,N-diphenylamino)-4=-phenyl-1,1=-biphenyl (1)
4-Bromobiphenyl (0.48 g, 2.08 mmol), 4-(N,N-diphenylamino)
benzeneboronic acid45 (0.5 g, 1.74 mmol), Pd (PPh3)4 (0.06 g, 0.5 mmol),
aqueous Na2CO3 (2.0 mol L−1, 15 mL), toluene (30 mL), and ethanol
(6 mL) were mixed in a three-necked round-bottom flask (100 mL).
The mixture was degassed and refluxed for 24 h under a nitrogen
atmosphere. Upon completion, the organic phase was separated
and extracted several times with toluene and then evaporated
under reduced pressure. The pure product was obtained as a white
acicular crystal by column chromatography (silica gel: 200–
400 mesh, petroleum ether − dichloromethane = 10:1) and crystal-
lized from ethanol; yield 75.64%, mp 211–212 °C. 1H NMR (400 MHz,
CDCl3) ␦: 7.66–7.71 (m, 4H), 7.63–7.6 (t, 2H), 7.51–7.53 (d, 2H, J =
8.4 Hz), 7.44–7.48 (t, 2H), 7.34–7.37 (t, 1H), 7.27–7.30 (t, 4H), 7.16 (d,
4H, J = 2.4 Hz), 7.14 (d, 2H, J = 1.2 Hz), 7.02–7.06 (t, 2H). Anal. calcd.
for C30H23N: C 90.68, H 5.79, N 3.53; found: C 90.29, H 5.58, N 3.62.
Synthesis of 4=-(N,N-diphenylamino)-1-phenyl-2,4,6-
trimethylbenzene (5)
The synthetic and purification procedure is similar to that of
compound 1 and gives a white acicular crystal; yield 68.18%, mp
113–115 °C. 1H NMR (400 MHz, CDCl3), ␦: 7.25ϳ7.29 (m, 4H),
7.13ϳ7.15 (m, 6H), 7.00ϳ7.04 (m, 4H), 6.95 (s, 2H), 2.33 (s, 3H), 2.07
(s, 6H). Anal. calcd. for C27H25N: C 89.26, H 6.89, N 3.86; found:
C 88.79, H 7.79, N 3.81.
Synthesis of 9,9-dimethyl-2-(4=-(N,N-diphenylamino)
phenyl)fluorine (6)
Synthesis of 2-bromio-9,9-dimethylfluorene46
1
Yield 91.25%; mp 56–57 °C. H NMR (400 MHz, CDCl3) ␦: 7.67–
7.69 (t, 1H), 7.56–7.58 (s, 1H), 7.55–7.56 (d, 1H, J = 4.4 Hz), 7.46 (d, 1H,
J = 2.0 Hz), 7.40–7.42 (m, 1H), 7.31–7.34 (m, 2H), 1.48 (s, 6H).
Synthesis of 4-(N,N-diphenylamino)-1-(4-fluorinephenyl)benzene
(2)
Synthesis of 6
The synthetic and purification procedure is similar to that of
compound 1 and gives a white acicular crystal; yield 86.58%, mp
174–175 °C. 1H NMR (400 MHz, CDCl3) ␦: 7.73–7.77 (t, 2H, J = 8.0 Hz),
7.63 (s, 1H), 7.54–7.56 (d, 3H, J = 8.8 Hz), 7.44–7.46 (d, 1H, J = 8.0 Hz),
7.26–7.35 (m, 6H), 7.14–7.18 (t, 6H, J = 5.2 Hz), 7.02–7.06 (t, 2H, J =
7.6 Hz), 1.53 (s, 6H). Anal. calcd. for C32H27N: C 90.35, H 6.35, N 3.29;
found: C 90.27, H 6.31, N 2.97.
The synthetic and purification procedure is similar to that of
compound 1 and gives a white acicular crystal; yield 84.43%, mp
94–95 °C. 1H NMR (400 MHz, CDCl3) ␦: 7.55–7.57 (d, 2H, J = 7.2 Hz),
7.45–7.47 (d, 2H, J = 8.8 Hz), 7.39–7.43 (t, 2H), 7.25–7.31 (m, 4H),
7.11–7.14 (d, 6H), 7.99–7.04 (m, 2H). Anal. calcd. for C24H18NF:
C 84.96, H 5.31, N 4.13; found: C 85.30, H 5.39, N 4.21.
Published by NRC Research Press

Wu et al.
1045
Fig. 1. UV-Vis absorption spectra of 1–9 in dichloromethane at room
temperature.
Synthesis of 6-(4=-(N,N-diphenylamino)phenyl)-
1,2,3,4,5-pentafluorine benzene (7)
The synthetic and purification procedure is similar to that of
compound 1 and gives a white acicular crystal; yield 82.0%, mp
1
130–132 °C. H NMR (400 MHz, CDCl3) ␦: 7.25–7.32 (m, 6H), 7.16–
7.17 (d, 4H, J = 7.6 Hz), 7.07–7.13 (m, 4H). Anal. calcd. for C24H14NF:
C 70.07, H 3.41, N 3.41; found: C 70.38, H 2.86, N 3.37.
Synthesis of 3,5-di(p-methylphenyl)-4=-N,N-diphenylamio-1-phenyl
benzene (8)
The synthetic and purification procedure is similar to that of
compound 1 and gives a white acicular crystal; yield 41.32%, mp
115–117 °C. 1H NMR (400 MHz, CDCl3) ␦: 7.72 (s, 3H), 7.56–7.61 (m,
6H), 7.26–7.30 (t, 8H), 7.15–7.06 (t, 6H), 7.03–7.06 (t, 2H), 2.42 (s, 6H).
Anal. calcd. for C38H31N: C 91.02, H 6.19, N 2.79; found: C 89.22,
H 5.78, N 2.65.
Synthesis of 4,4=,4== -trimesityltriphenylamine (9)
Tri(4-iodophenyl)amine (1.0 g, 1.61 mmol), 2,4,6-trimethyl-
benzeneboronic acid47 (1.06 g,6.44 mmol), benzene (50 mL), and
ethanol (10 mL) were mixed in a three-necked round-bottom flask
(100 mL) under a nitrogen atmospherefor 0.5 h.. Pd(PPh3)4 (0.18 g,
0.16 mmol) and Ba(OH)2 saturated solution (3.05 g, 9.66 mmol)
were added into the above solution and stirred. The mixture was
refluxed for 40 h under a nitrogen atmosphere and then cooled to
room temperature and much precipitate was filtered off and di-
luted with saturated aqueous NH4Cl solution. Then the solution
was extracted with dichloromethane. The organic portions
were combined and evaporated under reduced pressure. The
pure product was obtained as a white acicular crystal by column
chromatography (silica gel: 200–400 mesh, petroleum ether −
dichloromethane = 8:1) and crystallized from n-hexane; yield
cene to the ground state of 9-phenyl carbazole, resulting in a
red-shifted excimer emission or vice versa. However, this intramo-
lecular excimer was excluded by Fig. 5, which is the emission of 3
in different concentrations. With the increase in concentration,
the 495 nm emission increases, while the 400 nm emission de-
creases. This is strong evidence that the 495 nm emission is caused
by an intermolecular excimer emission. Structurally, the anthra-
cene group with a large conjugative ␲-system in 3 can easily cause
face–face intermolecular interaction in favor of excimer emission.
From the ␲−␲* transition and n−␲* transition of <380 nm, the
short stokes shift, and because of the similarity of the chemical
structures of the molecules reported here with those already re-
ported for fluorescent molecules,39,42,43 we can definitely exclude
the possibility of phosphorescence emission of these molecules.
1
81.77%. H NMR (400 MHz, CDCl3) ␦: 7.20–7.23 (d, 2H, J = 8 Hz),
7.04–7.06 (d, 2H, J = 8 Hz), 6.96 (s, 2H), 2.28 (s, 3H), 2.10 (s, 6H). Anal.
calcd. for C45H45N: C 90.15, H 7.51, N 2.34; found: C 89.89, H 7.62,
N 2.04.
Results and discussion
Absorption and emission spectra
The quantum yield
The UV-Vis absorption spectra of compound 1–9 in CH2Cl2 solu-
tion at room temperature are given in Fig. 1. Other photophysical
data are listed in Table 1. All compounds have characteristic
strong absorptions at the high-energy 240–280 nm region due to
the spin-allowed ␲−␲* transition. The weaker absorption at the
lower energy 285–380 nm region corresponds to the forbidden
n−␲* absorption localized at the nitrogen atoms. It should be
noted that the absorption of 3 has fine structures in the 340–
400 nm region. This will be explained by consulting its emission
in the next paragraph. The energy gap, HOMO (highest occupied
molecular orbital), and LUMO (lowest unoccupied molecular or-
bital) can be estimated based on the lowest energy absorption
edge of the UV absorption spectrum and electrochemical data
(Table 1).
In both CH2Cl2 and solid state (see Figs. 2 and 3), the emission of
5 and 9 is violet blue. In CH2Cl2, the emission of 2, 6, and 8 is deep
blue and that of 1, 4, and 7 is pure blue. In solid state, the emission
is bathochromically shifted compared with that in CH2Cl2. Again,
it should be noted that the emission of 3 is much different from
the others. This is a rather complicated phenomenon. A simple
3D-chemdraw can give us a deeper look to detect the reason
(Fig. 4). From Fig. 4, it can be concluded that the mesityl group in
5 and the anthracene group in 3 are in a poorer coplanarity than
the biphenyl group in 1. Poorer coplanarity results in a hypsochro-
mic shift as proven for in 5. However, in 3, the emission is greatly
bathochromically shifted. This may be caused by an excimer emis-
sion. In 3, both anthracene and the 9-phenyl carbazole group are
chromophores; poorer coplanarity may result in an intramolucu-
lar excimer, i.e., electrons transit from the excited state of anthra-
The quantum yield was determined by excitation at 313 nm in
CH2Cl2 and using quinine sulfate as the standard.48 The results
coincide with the trend in emission spectra, i.e., compounds 5 and
9 exhibit the least quantum yield with the least coplanarity and
compounds 1, 4, and 8 have the highest quantum yield with the
best coplanarity. As for 3, the value is also high; this is because,
first, the green emission is the most sensitive region to naked eye
and, second, the excimer emission itself is of special meaning.
Electrochemical characterization
By cyclic voltammetry, not only the energy levels but also the
electrochemical stability can be roughly determined. “Roughly”
means that the real energy levels may only be determined in thin
film state on the layered OLED device. The stability of an OLED
device is a very complicated matter defined not only by the stabil-
ity of the materials but also by other chemical and physical fac-
tors. Figure 6 outlines the cyclic voltammetric curves of all nine
compounds. It was recorded with a glassy-carbon electrode in
CH2Cl2 solutions containing 0.001 mol L−1 of the compounds and
0.10 mol L−1 n-Bu4NClO4 against Ag/AgCl using ferrocene as the
internal standard. All compounds exhibit reversible electrochem-
ical behavior with oxidation potentials of around 1–1.2 V.
According to the literature,49,50 the HOMO energy level can be
estimated from the onset potentials (Eox (onset)) through the fol-
lowing equation: EHOMO = −(4.8 + Eref + Eox (onset)) eV, where Eref is
the potential of the ferrocene reference. The energy levels of
LUMO and the HOMO/LUMO energy gap were calculated from the
spectroscopic and electrochemical data,51–55 as shown in Table 1.
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Can. J. Chem. Vol. 91, 2013
LUMO (eV)e
Table. 1. Optoelectronic data of compounds 1–9.
Compound
Eg (eV)a
␭
maxem (nm)b
␭
maxabs (nm)
⌽ (%)c
Edox (V)
HOMO (eV)d
1
2
3
4
5
6
7
8
9
3.22
3.40
2.97
3.22
3.59
3.40
3.40
3.32
3.54
436
401
491
430
368
399
479
411
343
68.25
29.53
48.29
58.26
4.74
29.85
21.24
44.78
6.41
1.16
1.16
1.17
1.16
1.18
1.11
1.25
1.18
1.14
−5.41
−5.41
−5.42
−5.41
−5.43
−5.36
−5.50
−5.43
−5.39
−2.19
−2.10
−2.45
−2.19
−1.84
−1.96
−2.10
−2.11
−1.85
314
387, 258
341, 246
305
320
327
333, 254
312
377
aCalculated based on the lowest energy absorption edge of the UV absorption spectrum.
bExcited at 313 nm in CH2Cl2.
)
cCalculated by ⌽f = ⌽ref(⌿f/⌿ref)(Aref/Af)(nf/nref 2 where ⌽f is the quantum yield of the unknown, ⌽ref is that of the standard, Aref is the
absorbance of the standard, Af is that of the unknown, ⌿ref is the integrated area of the fluorescence intensity of the standard, ⌿f is that
of the unknown, and nf and nref are the refractive indices of the solvent used for the unknown and standard, respectively.
dFc+/Fc− is the inner reference, EHOMO = −[4.8 + Eox(onset) − E(Fc−/Fc+)] eV, E(Fc+/Fc−) = 0.55 eV, and Eox (onset) is the onset oxidation potential.
eLUMO = HOMO + energy gap (eV).
Fig. 2. Emission spectra of 1–9 excited at 313 nm in dichlorometh-
Fig. 4. 3D-chemdraw of compounds 5, 1, and 3.
ane based on the solutions made as in Fig. 1.
Fig. 3. Emission spectra of 1–9 excited at 313 nm in solid state. The
value on the y-axis does not mean emission intensity because it
changes with slit and filter, etc.
Fig. 5. Emission spectra of compound 3 in different concentrations;
it was excited at 313 nm in dichloromethane at room temperature.
Inset: the enlarged region.
Conclusion
A series of triphenylamine derivatives were synthesized. All
compounds exhibit reversible electrochemical behavior. In both
CH2Cl2 and solid state, the emission of 5 and 9 is violet blue. In
CH2Cl2, the emission of 2, 6, and 8 is deep blue and that of 1, 4, and
Published by NRC Research Press

Wu et al.
1047
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7 is pure blue. Compounds 1, 4, and 8 have the best coplanarity as
a result, creating the highest quantum yield (44%–68%). Com-
pound 3 emits green, which is assigned as an intermolecular exci-
mer emission. In general, with the properties reported above and
the structural similarity with those reported in the literature,
these compounds can be potentially useful for blue-emitting, up-
converting, and host materials.
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