Synthesis and optical characterization of novel carbazole Schiff bases

DOI: 10.1016/j.molstruc.2017.09.109

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Journal of Molecular Structure p. 42 - 47 (2018)

Update date:2022-08-17

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Authors:

?i?ek, Baki

?al???r, ümit

Tavasl?, Mustafa

Tülek, Remziye

Teke, Ali

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Article abstract of DOI:10.1016/j.molstruc.2017.09.109

In this study, newly substituted carbazole derivatives of S1; (Z)-4-((9-isobutyl-9H-carbazol-3-ylimino)methyl)phenol, S2; (Z)-9-butyl- N-(2,3,4-trimethoxybenzylidine)-9H-carbazol-3-amine, S3; (Z)-4-((9-octyl-9H-carbazol-3-ylimino)methyl)benzene-1,2-diol and S4; (Z)-3-((9-octyl-9H-carbazol-3-ylimino)methyl)benzene-1,2-diol compounds are synthesized by using condensation reaction between carbazole amines and aromatic aldehydes. All synthesized carbazole Schiff bases are purified by crystallizing from chloroform. The structural and optical characterizations of synthesized compounds are investigated by FT-IR (Fourier Transform-Infrared Spectroscopy), ¹H NMR (Proton Nuclear Magnetic Resonance), ¹³C NMR (Carbon Nuclear Magnetic Resonance), LC-MS (Liquid Chromatography-Mass Spectrometry) and temperature dependent PL (Photoluminescence) measurements. The formations of synthesized Schiff bases were confirmed by FT-IR, NMR and microanalysis. Due to stronger π-conjugation and efficient charge transfer from host material, the broad and complex bands centered at about ～2.16 and ～1.76 eV are observed in PL spectra for all samples. Their relative intensities depend on functional groups associated with the carbazole. These newly synthesized Schiff bases could be considered as an active emissive layer for organic light emitting diodes.

Full text of DOI:10.1016/j.molstruc.2017.09.109

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Synthesis and optical characterization of novel carbazole Schiff bases

Baki Çiçek, Ümit Çalışır, Mustafa Tavaslı, Remziye Tülek, Ali Teke

PII:

S0022-2860(17)31320-0

10.1016/j.molstruc.2017.09.109

MOLSTR 24358

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To appear in: Journal of Molecular Structure

Received Date: 3 August 2017

Revised Date: 26 September 2017

Accepted Date: 27 September 2017

Please cite this article as: B. Çiçek, Ü. Çalışır, M. Tavaslı, R. Tülek, A. Teke, Synthesis and optical

characterization of novel carbazole Schiff bases, Journal of Molecular Structure (2017), doi: 10.1016/

j.molstruc.2017.09.109.

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Graphical abstract

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Synthesis and Optical Characterization of Novel Carbazole Schiff Bases

a,b

Baki Çiçek* , Ümit Çalışır , Mustafa Tavaslı , Remziye Tülek and Ali Teke

Chemistry Department, Faculty of Arts and Sciences, Balıkesir University, Balıkesir, Turkey bcicek@balikesir.edu.tr

Science and Technology Research and Application Center, Siirt University, Siirt, Turkey umitcalisir@siirt.edu.tr

Chemistry Department, Faculty of Arts and Sciences, Uludağ University, Bursa, Turkey mtavasli@uludag.edu.tr

Physics Department, Faculty of Arts and Sciences, Balıkesir University, Balıkesir, Turkey baran@balikesir.edu.tr

ateke@balikesir.edu.tr

Abstract: In this study, newly substituted carbazole derivatives of S1; (Z)-4-((9-isobutyl-9H-carbazol-3-

ylimino)methyl)phenol, S2; (Z)-9-butyl- N-(2,3,4-trimethoxybenzylidine)-9H-carbazol-3-amine, S3; (Z)-4-((9-octyl-9H-

carbazol-3-ylimino)methyl)benzene-1,2-diol and S4; (Z)-3-((9-octyl-9H-carbazol-3-ylimino)methyl)benzene-1,2-diol

compounds are synthesized by using condensation reaction between carbazole amines and aromatic aldehydes. All

synthesized carbazole Schiff bases are purified by crystallizing from chloroform. The structural and optical

characterizations of synthesized compounds are investigated by FT-IR (Fourier Transform-Infrared Spectroscopy), H-

NMR (Proton Nuclear Magnetic Resonance), C-NMR (Carbon Nuclear Magnetic Resonance), LC-MS (Liquid

Chromatography-Mass Spectrometry) and temperature dependent PL (Photoluminescence) measurements. The formations

of synthesized Schiff bases were confirmed by FT-IR, NMR and microanalysis. Due to stronger π-conjugation and

efficient charge transfer from host material, the broad and complex bands centered at about ~2.16 and ~1.76 eV are

observed in PL spectra for all samples. Their relative intensities depend on functional groups associated with the

carbazole. These newly synthesized Schiff bases could be considered as an active emissive layer for organic light emitting

diodes.

Keywords: Carbazole, Carbazole Schiff Base, Synthesis, Optical Characterization, Photoluminescence, OLED.

. INTRODUCTION

For the synthesis of carbazole Schiff bases, a solvent free

method were used and showed luminescence properties [24].

Carbazoles and its derivatives have been received a great

deal of interest due to their specific optical and

electrochemical properties, which could potentially be

explored to some device applications, such as organic light-

emitting diodes (OLEDs) [1], organic photovoltaic devices

In current work, since Schiff bases containing carbazolyl

groups are expected to have stronger conjugated system,

higher intramolecular electron transfer efficiency and more

stable structure than the general Schiff bases, four novel

carbazole based Schiff bases referred as S1, S2, S3 and S4

were synthesized by condensation reaction between

carbazole amines and aromatic aldehydes, and characterized

by FT-IR, NMR, LC-MS, elemental analysis and

temperature dependent PL spectroscopy.

(

OPVs) [2], organic field-effect transistors (OFETs) [3], as

wells as fundamental points of view [4,5]. Since the

carbazole derivatives have high triplet energy and efficient

energy transfer processes from hosts to doped triplet

emitters, they can be used as host materials in highly

efficient blue, green, or red electro-phosphorescent devices

[

6-10]. Numerous ways of functionalization of carbazoles or

2. MATERIALS AND METHODS

covalently linking to other molecules such as 3,6- or 2,7-

linking of carbazole molecules into dimers, trimers or

oligomers [11,12], addition of enamine [13], and others [14-

.1. General

In this study, all starting materials were purchased from

8] are reported for the enhancement of their conjugated π-

Merck, Sigma-Aldrich and Fluka Co., and used after further

analytical purifications of solvents and chemical materials. A

silica gel with column chromatography was used for

chromatographic purifications. FT-IR spectra were taken

electron system and hence for the efficient light emitter.

Polycarbazoles and their nanocomposite

films

(

polycarbazole/nanoZn and polycarbazole/nanoclayfilms)

using Perkin Elmer BX 2 FTIR spectrometer. Both H-NMR

show protection of anodic corrosion on modified electrodes

to form metal conserved region [19].

(

400 MHz) and C-NMR (100 MHz) spectra were obtained

from CDCl , CD Cl or CD OD solvents. LC-MS spectra

Carbazole Schiff bases demonstrate that they have superior

were recorded on Agilent Technologies-1260 Infinity (LC)

6130 Quadropole (MS) Mass Spectrometry using acetonitrile

as a solvent. Microanalyses were performed with a Thermo

fluorescence emission and also their Co , Fe , Cr and

Cu complexes show extra fluorescence emission [20-23].

Address correspondence to this author at the Department of Chemistry, Faculty of Science and Literature, Balıkesir University, 10145 Balıkesir, Turkey;

phone: + 90 266 612 10 00-1108; e-mail: bcicek@balikesir.edu.tr

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Scientific Flash 2000 elemental analyzer. Finally,

temperature dependent photoluminescence measurements

were carried out on powders placed in a close-cycled

cryostat in the temperature range of 10–300 K and excitation

excitation. The luminescence was collected by suitable

lenses and then dispersed with a 500 mm spectrometer using

1200 line/mm grating and detected by Intensified Charge

Coupled Device (ICCD) camera.

densities between 0.01 and 1.04 W/cm . A frequency tripled

Nd:YLFQ-switched pulse laser at 349 nm were used for the

Figure 1: Synthesis of the original carbazole Schiff bases (S1, S2, S3 and S4)

.2. Experimental

S1 was obtained from p-hydroxybenzaldehyde and N-

isobutyl-3-amine carbazole (7) following the general

procedure for 5-6 h and then purified by recrystallization

General Procedure for Synthesis of Precursor Compounds:

The N-substituted carbazoles were prepared according to the

procedure reported in the literature [25]. Carbazole, alkyl

halide, tetra butyl ammonium iodide and 50 % sodium

-1

with chloroform (80%. m.p.: 223-224 C). FT-IR (γ cm ):

619 (conjugated) –CH=N- stretch, 1545 aromatic –C=C-

stretch, 743 1,2-disubstituted carbazolyl ring’s bend, 822 and

hydroxide are refluxed at 77 C. After a general work-up, the

58 1,2,4-trisubstituted carbazolyl ring’s bend. H-NMR (400

MHz, CD OD): δ (Chemical Shift) 0.92 (t, 6H), 1.83 (m, H),

.30 (t, 2H), 5.33 (s, H), 6.91 (d, 2H), 7.18 (m, 2H), 7.20

m, H), 7.40 (m, 2H), 7.77 (m, 3H), 7.95 (s, H), 8.07 (d, H),

crude products are obtained and then purified over a silica

gel column chromatography (1-3). The N-substituted

mononitrocarbazoles (4-6) were prepared according to the

procedure described in the literature [26]. The N-substituted

carbazolyl is nitrated with concentrated nitric acid below 10

(

.53 (s, H). C-NMR (100 MHz, CD OD):δ 20.33, 30.98,

53.20, 108.87, 109.07, 111.76, 115.62, 118.61, 119.61,

C. The N-substituted monoamine carbazoles (7-9) were

20.16, 122.68, 123.21, 125.73, 130.48, 139.05, 143.63,

53.8, 159.34, 160.38. Anal. Calc. for C H N O

synthesized by using Pd/C and hydrazine hydrate [27]. The

original carbazole Schiff bases were synthesized using N-

substituted monoamine carbazoles with aromatic aldehydes

by condensation reaction, Figure 1 (S1-S4).

(

MW=342.43): C, 80.67; H, 6.48; N, 8.18. Found: C, 80.10;

+ “

H, 6.60; N, 8.10%. LC-MS (m/z): 342.9 (M Molecular Ion

Peak”, CH CN, Error % = 0.1834).

General Procedure for Synthesis of Carbazole Schiff Bases:

The original carbazole Schiff bases were synthesized using

N-substituted monoamine carbazoles (7-9) with aromatic

-(imine-2,3,4-trimethoxybenzene)-N-butylcarbazole (S2).

S2 was obtained from 2,3,4-trimethoxybenzaldehyde and N-

butyl-3-amine carbazole (8) following the general procedure

5-6 h and then purified by recrystallization with chloroform

(71%, m.p.: 44-45 C). FT-IR (γ cm ): 1627 (conjugated) –

CH=N- stretch, 1601 aromatic –C=C- stretch, 745 1,2-

disubstituted carbazolyl ring’s bend, 834 and 894 1,2,4-

aldehydes by condensation reaction.

N-substituted

monoaminocarbazoles (7-9) (1.398 mmol) and aromatic

aldehyde (1.398 mmol) were dissolved in 10 ml THF

-1

(

Tetrahydrofuran) and refluxed in a 100 ml reaction flask for

4 hours. After that, one drop of acetic acid was added to

solvent as a catalyst. As a result of condensation reaction

reddish color was observed. The target compound was

separated by precipitation with the addition of water. The

crude product was filtered and washed with aqueous 5% of

trisubstituted carbazolyl ring’s bend. H-NMR (400 MHz,

CDCl ): δ 0.96 (t, 3H), 1.42 (m, 2H), 1.87 (m, 2H), 3.94 (s,

9H), 4.30 (t, 2H), 6.82 (d, H), 7.24 (m, 2H), 7.41 (d, H), 7.46

(m, 2H), 7.48 (m, H), 8.02 (m, H), 8.14 (d, H), 8.95 (s, H).

NaHCO

. The product was washed out with water and then

C-NMR (100 MHz, CDCl ): δ 13.92, 20.58, 31.18, 53.48,

dried. The final product was purified by recrystallization

with chloroform, Figure 1.

56.11, 60.99, 62.13, 108.0, 109.0, 112.4 (d), 118.8, 120.5,

122.5, 123.0, 123.5, 126.0, 139.1, 141.0, 142.0, 144.6, 153.8,

55.5, 156.1. Anal. Calc. for C H N O (MW=416.51): C,

26 28 2 3

-(imine-p-hydroxybenzen)-N-isobutylcarbazole (S1).

74.97; H, 6.78; N, 6.73. Found: C, 75.00; H, 6.75; N, 6.70%.

LC-MS (m/z): 415.0 (M , CH CN, Error % = 0.3625).

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-(imine-3,4-dihydroxybenzene)-N-octylcarbazole (S3).

carbonyl band of aldehyde peak expected at 191 ppm was

vanished. The formation of the syntheses Schiff bases were

confirmed by observing –CH=N- carbon band at ∼ 155.5-

S3 was obtained from 3,4-dihydroxybenzaldehyde and N-

octyl-3-amine carbazole (9) following the general procedure

for 5-6 h and then purified by recrystallization with

163.0 ppm for azomethine (see Figure 1a-f, Figure 2a-e,

-1

Figure 3a-c, Figure 4a-c of the supporting information for

S1, S2, S3 and S4, respectively).

chloroform (53%, m.p.: 126-127 C). FT-IR (γ cm ): 1625

conjugated) –CH=N- stretch, 1594 aromatic –C=C- stretch,

(

43 1,2-disubstituted carbazolyl ring’s bend, 867 and 900

,2,4-trisubstituted carbazolyl ring’s bend. H-NMR (400

Furthermore, in LC-MS spectra the molecular ion band were

observed at (M ) 342.17, 416.21, 414.23 and 414.23 g/mol

MHz, CD

): δ 0.87 (t, 3H), 1.28 (m, 10H), 1.84 (m, 2H),

for S1, S2, S3, and S4, respectively. Finally, elemental

analysis data verify the molecular structures of novel

carbazoly shift bases. Synthesized and characterized all of

the original carbazole Schiff bases have an uninterrupted

electron delocalization.

.24 (t, 2H), 5.32 (s, 2H), 6.92 (d, H), 7.14 (t, H), 7.24 (m,

H), 7.42 (m, 2H), 7.67 (d, 2H), 8.38 (d, H), 8.75 (s, H).

C-NMR (100 MHz, CD Cl ): δ 13.78, 22.56, 27.21, 28.93,

9.13, 29.32, 31.75, 43.20, 108.57, 109.26, 115.38 (2C),

17.80, 120.09, 125.30, 125.35, 125.78, 125.92, 126.06,

26.21, 135.0, 136.0, 139.0, 141.0, 145.0, 150.0, 163.0.

The pure powders placed in closed cycle cryostat were

examined by PL over the temperature range of 10 to 300 K

Anal. Calc. for C H N O (MW=414.54): C, 78.23; H,

and excitation power density of 0.01 and 1.04 W/cm . The

.29; N, 6.76. Found: C, 78.10; H, 7.15; N, 6.60%. LC-MS

PL spectra at 300K are shown in Figure 2 along with

reference sample containing only carbazole for comparison.

The reference sample has several relatively narrow peaks

over the spectral range between 2.5 and 3.3eV with the most

intense peak situated at 2.95 eV. The PL spectra of S1, S2,

S3 and S4 show completely different character compared to

reference carbazole. Due to stronger π-conjugation and

efficient charge transfer from host material to conjugated

part of compounds, broad and complex bands centered at

about ~2.16 and ~1.76 eV are observed in PL spectra for all

samples.

(

m/z): 414.23 (M , CH

CN, Error % = 0.0748).

-(imine-2,3-dihydroxybenzene)-N-octylcarbazole (S4).

S4 was obtained from 2,3-dihydroxybenzaldehyde and N-

octyl-3-amine carbazole (9) following the general

procedurefor 5-6 h and then purified by recrystallization

-1

with chloroform (78 %, m.p.: 105-106 C). FT-IR (γ cm ):

619 (conjugated) –CH=N- stretch, 1600 aromatic –C=C-

stretch, 740 1,2-disubstituted carbazolyl ring’s bend, 822 and

82 1,2,4-trisubstituted carbazolyl ring’s bend. H-NMR (400

MHz, CD Cl ): δ 0.88 (t, 3H), 1.30 (m, 10H), 1.90 (m,

H), 4.33 (t, 2H), 5.33 (s, 2H), 6.85 (m, 2H), 7.03 (d, H),

.26 (t, 3H), 7.50 (m, 3H), 8.12 (d, H), 8.14 (s, H), 8.81

(

s, H). C-NMR (100 MHz, CD

):δ 13.78, 22.57, 27.21,

8.91, 29.14, 29.31, 31.74, 43.27, 109.15, 109.43, 112.46,

16.64, 118.55, 118.71, 119.09, 119.29, 120.40, 122.60,

23.36, 126.18, 138.0, 139.0, 141.0, 145.0, 150.0, 159.0.

Anal. Calc. for C27

30 2 2

H N O (MW=414.54): C, 78.23; H,

.29; N, 6.76. Found: C, 78.12; H, 7.16; N, 6.80%. LC-MS

(

m/z): 414.23 (M , CH CN, Error % = 0.0748).

. RESULTS

The synthesized novel substituted carbazole derivatives (S1,

S2, S3 and S4) by condensation reaction as described above

are characterized by FT-IR, H-NMR, C-NMR, LC-MS

and temperature dependent PL measurements.

In FT-IR spectra, while the N-H stretch of Alkylated

carbazolyl amine and aromatic aldehite carbonyl C=O

expected at 3355 cm and 1800 cm , respectively were

disappeared, typical azomethine –CH=N- bond stretch at

Figure 2: PL spectra of S1-S4 compared to carbazole taken

at room temparature.

-1

625±10 cm associated with carbazole Schiff base were

The temperature and excitation density dependency of PL

spectra were examined for all four samples, and the results

are shown in Figure 3. As seen from the figures, the overall

emission characters such as peak positions and shape of

spectra do not significantly change with temperature. The

peak intensities of two broad bands of samples S1, S3

remain almost constant over the entire temperature ranges.

On the other hand, they increase very slightly as the

temperature increases for sample S2. For sample S4, the

peak intensity of the first broad peak centered at about

clearly observed indicating their formation (see Figure 1g-h,

Figure 2f-g, Figure 3d-e, Figure 4d-e in supporting

information for S1, S2, S3 and S4, respectively). In addition,

aldehyde’s carbonyl stretch (1723 cm ) and amine’s –NH

stretch (3300 cm ) which seems a double band disappeared.

-1

These compounds showed H-NMR peaks for different kinds

of protons on their spectral data. In H-NMR spectra, –CHO

proton band of aldehyde and -NH proton band of amine

peaks expected at 9.88 ppm and 6.58 ppm were vanished.

The formation of syntheses Schiff bases were confirmed by

observing –CH=N- proton band at ∼ 8.5-8.9 ppm (singlet) for

2.16eV decreases, whereas that of second broad peak

centered at about ~1.76 eV increases slightly initially from

10 K to 60 K.

azomethine proton. Similarly, in C-NMR spectra, –CHO

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(a)

(b)

(c)

(d)

Figure 3. Temperature dependent PL spectra for S1 (a), S2 (b), S3 (c) and S4 (d). The inset shows an example of Gauss fitting

used for peak identification.

The total integrated intensities as a function of temperature

and excitation density are shown in Figure 4 of all samples.

As seen from the Figure 4 (a) although the total integrated

intensities remain almost constant for sample S1, S3 and S4,

it increases steadily for sample S2 as the temperature rises.

As seen from Figure 4(b), the total integrated PL intensities

increase almost linearly for samples S2, S3 and S4 and the

The decomposed peaks are realized at 1.58, 1.78, 2.04, 2.28

and 2.74 eV with varied peak and hence integrated

intensities contribute to total integrated intensities depending

on samples. From these peak positions the spectra can be

divided into three spectral regions as near infrared (785-690

nm), red-orange-yellow (620-540 nm) and blue (450 nm). As

clearly seen from the Figure 5, whereas the relative

integrated intensity of one of the dominant emission band

centered at about 2.28 eV decreases, the other dominant

emission band peaked at 2.04 eV increases from sample S1

to sample S4.

power of x for sample S4 as the excitation density

increase.

To resolve these broad spectra that are composed of various

emission bands, they were fitted using multiple Gaussian

fittings. The best fits are obtained by assigning 5 Gaussian

peaks as shown in the insets of Figure 3. The decomposed

peaks and their relative integrated intensities normalized to

total integrated intensity for the spectra taken at room

temperature are shown in Figure 5.

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(a)

(b)

Figure 4. The total integrated intensity versus excitation power density (a) and temperature (b) for all samples.

The normalized integrated intensity of the second most

dominant emission band observed at 1.78 eV also depend on

samples, hence the functional group connected to carbazole.

The other lower intensity emission bands 1.58 and 2.74 have

relatively lesser dependence on samples. From this

observation, it could be argued that this newly synthesized

Shift bases could be optimized and investigated further to

obtain an emission with different white light color

temperature or single emission bands from blue to near

infrared region of the spectrum. By introducing different

transition metals or rare-earth materials to main matrix

structure, the studies could be extended more for further

investigations.

CONCLUSIONS

Four novel substituted carbazole derivatives referred as S1,

S2, S3 and S4 were successfully synthesized using

condensation reaction between carbazole amines and

aromatic aldehydes. All synthesized carbazole Schiff bases

were purified by crystallizing from chloroform. They were

characterized structurally by means of FT-IR, NMR and

microanalysis and confirmed their formations. The

temperature and excitation power density dependent PL

measurements were also carried out for optical

characterization. The broad and complex bands centered at

about ~2.16 and ~1.76 eV are observed in PL spectra for all

samples compared to reference carbazole host material,

which indicate an efficient charge transfer to π-conjugated

systems. Their relative intensities depend on functional

groups associated with the carbazole. These newly

synthesized Schiff bases could be considered as an active

emissive or electron/hole transport layer for organic light

emitting diodes. Further systematic investigations are needed

to identify the origin of emission bands and optimize the

structure for designated purposes.

ACKNOWLEDGEMENTS

This study was supported financially by Balıkesir

University Projects Unit; project no: BAP.2015.0001 and

BAP.2017/181.

SUPPLEMENTARY MATERIAL

All FT-IR, H-NMR, C-NMR, LC-MS spectra (Figure

1-4) for S1-S4 are given in supportive/supplementary

material.

Figure 5. The relative integrated intensities of decomposed

emission peaks deduced by Gaussian fittings for sample S1,

S2, S3 and S4. The peaks for each sample are placed

vertically. The dashed line is drawn for eye-guide.

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REFERENCES

enamines as charge transport materials for

electrophotography. Synth. Met., 2008, 158, 462-467.

[

1] Mullen, K., Scherf, U. Organic Light-Emitting

Devices, Synthesis, Properties, and Applications;

Eds.; Wiley-VCH: Weinheim, 2006.

[14] Lygaitis, R.; Getautis, V.; Grazulevicius, J. V. Hole-

transporting hydrazones. Chem. Soc. Rev., 2008, 37,

70-788.

2] Sun, S. S., Sariciftci, N. S. Organic Photovoltaics,

Mechanisms, Materials and Devices, Eds.; CRC:

New York, NY, 2005.

[15] Bubniene, G.; Malinauskas, T.; Stanisauskaite, A.;

Jankauskas, V.; Getautis, V. Synthesis of new hole-

transporting molecular glasses with pendant

carbazolyl-based hydrazone moieties. Synth. Met.,

3] Mas-Torrent, M.; Rovira, C. Tetrathiafulvalene

derivatives for organic field effect transistors. J.

Mater. Chem., 2006, 16, 433-436.

009, 159, 1695-1700.

[

16] Getautis, V.; Daskeviciene, M.; Malinauskas, T.;

Stanisauskaite, A.; Stumbraite, J. An Efficient

4] Forrest, S. R. The path to ubiquitous and low-cost

organic electronic appliances on plastic. Nature,

Scalable

Synthesis

2,3-Epoxypropyl

2004, 428, 911-918.

Phenylhydrazones. Molecules, 2006, 11, 64-71.

5] Grazulevicius, J. V.; Strohriegl, P. Charge-

17] Shirota, Y.; Kageyama, H. Charge Carrier

Transporting Molecular Materials and Their

Applications in Devices. Chem. Rev., 2007, 107, 953-

1010.

Transporting Molecular Glasses. Adv. Mater., 2002,

14, 1439-1452.

6] Liu, Y.; Nishiura, M.; Wang, Y.; Hou, Z. π-

Conjugated Aromatic Enynes as a Single-Emitting

Component for White Electroluminescence. J. Am.

Chem. Soc., 2006, 128(17), 5592-5593.

18] Bubniene, G.; Malinauskas, T.; Daskeviciene, M.;

Jankauskas, V.; Getautis, V. Easily Functionalizable

Carbazole Based Building Blocks with Extended

Conjugated Systems for Optoelectronic Applications.

Tetrahedron, 2010, 66, 3199–3206.

[

7] Tsai, M.-H.; Hong, Y.-H.; Chang, C.-H.; Su, H.-C.;

Wu, C.-C.; Matoliukstyte, A.; Simokaitiene, J.;

Grigalevicius, S.; Grazulevicius, J. V.; Hsu, C.-P. 3-

[

19] Ates, M.; Özyılmaz, A.T. The Application of

(

9-Carbazolyl)carbazoles

and

3,6-Di(9-

Polycarbazole,

Polycarbazole/nanoclay

and

carbazolyl)carbazoles as Effective Host Materials for

Efficient Blue Organic Electrophosphorescence. Adv.

Mater., 2007, 19, 862-866.

polycarbazole/Zn-Nanoparticles as

Corrosion

Inhibition for SS304 in Saltwater. Prog. Org.

Coatings, 2015, 84, 50–58.

8] Cells, L.; Zeng, X.; Tavasli, M.; Perepichka, I. F.;

Batsanov, A. S.; Bryce, M. R.; Chiang, C.; Rothe, C.;

Monkman, A. P. Cationic Bis-Cyclometallated

Iridium(III) Phenanthroline Complexes with Pendant

20] Dutta, K.; Deka, R.C.; Das, D.K. A New Fluorescent

and Electrochemical Zn Ion Sensor Based on Schiff

Base Derived from Benzil and L-Tryptophan.

Spectrochim. Acta. A. Mol. Biomol. Spectrosc., 2014,

Fluorenyl

Substituents:

Synthesis,

Redox,

24, 124–129.

Photophysical Properties and Light-Emitting Cells.

Chem. A Eur. J., 2008, 14, 933–943.

[21] Yang, L.; Zhu, W.; Fang, M.; Zhang, Q.; Li, C. A

New Carbazole-Based Schiff-Base as Fluorescent

9] Bettington, S.; Tavasli, M.; Bryce, M. R.; Beeby, A.;

Al-attar, H.; Monkman, A. P. Tris-Cyclometalated

Chemosensor for Selective Detection of Fe and

Cu . Spectrochim. Acta. A. Mol. Biomol. Spectrosc.,

Iridium(III)

Carbazole(fluorenyl)pyridine Ligands: Synthesis,

Redoxand Photophysical Properties, and

Complexes

013, 109, 186–192.

[22] Zhu, W.; Yang, L.; Fang, M.; Wu, Z.; Zhang, Q.; Yin,

F.; Huang, Q.; Li, C. New Carbazole-Based Schiff

Electrophosphorescent Light-Emitting Diodes. Chem.

A Eur. J., 2007, 13, 1423–1431.

Base: Colorimetric Chemosensor for ₃₊Fe

and

Fluorescent Turn-on Chemosensor for Fe and Cr .

[

10] Koyuncu, S.; Usluer, O.; Can, M.; Demic, S.; İcli, S.;

J. Lumin., 2015, 158, 38–43.

Sariciftci,

Electrochromic

and

Electroluminescent Devices Based on a Novel

Branched Quasi-Dendric Fluorene-Carbazole-2,5-

bis(2-Thienyl)-1H-Pyrrole System. J. Mater. Chem.,

[23] Bu, J.; Duan, H.; Wang, X.; Xu, T.; Meng, X.; Qin,

D. New Turn-on Fluorescence Sensors for Co

Based on Conjugated Carbazole Schiff Base. Res.

Chem. Intermed., 2015, 41(5), 2767–2774.

2011, 21, 2684–2693.

11] Sonntag, M.; Strohriegl, P. Novel 2,7-Linked

Carbazole Trimers as Model Compounds for

Conjugated Carbazole Polymers. Chem. Mater., 2004,

[24] Guo, D.; Wu, P.; Tan, H.; Xia, L.; Zhou, W.

Synthesis and Luminescence Properties of Novel 4-

(N-Carbazole Methyl) Benzoyl Hydrazone Schiff

Bases. J. Lumin., 2011, 131(7), 1272–1276.

16, 4736-4742.

[

12] Morin, J.-F.; Leclerc, M.; Ade` s, D.; Siove, A.

Polycarbazoles: 25 Years of Progress. Macromol.

Rapid Commun., 2005, 26, 761-778.

[25] Grigoras, M.; Antonoaia, N.-C. Synthesis and

Characterization of Some Carbazole-Based Imine

Polymers. Eur. Polym. J., 2005, 41, 1079–1089.

13] Matoliukstyte, A.; Burbulis, E.; Grazulevicius, J. V.;

Gaidelis, V.; Jankauskas, V. Carbazole-containing

[26] Mudadu, M.S.; Singh, A.N.; Thummel, R. P.

Preparation

and

Study of

1,8-Di(Pyrid-2′-

ACCEPTED MANUSCRIPT

Short Running Title of the Article

Journal Name, 2014, Vol. 0, No. 0 7

Yl)Carbazoles. J. Org. Chem., 2008, 73(4), 6513–

520.

Microgel-Based Cu (II) Chemosensors via Thermo-

Induced Volume Phase Transitions. Chem. Mater.,

009, 21, 3439–3446.

[

27] Liu, T.; Hu, J.; Yin, J.; Zhang, Y.; Li, C.; Liu, S.

Enhancing Detection Sensitivity of Responsive