Polycarbazoles and polytriphenylamines showing aggregation-induced emission (AIE) and intramolecular charge transfer (ICT) behavior for the optical detection of nitroaromatic compounds

Article abstract of DOI:10.1016/j.polymer.2015.08.064

Acceptor-substituted polycarbazoles (PCzTPAN) and polytriphenylamines (PTPATPAN) bearing electron-deficient 2,3,3-triphenylacrylonitrile (TPAN) side groups have been successfully synthesized. Both of them are aggregation-induced emission (AIE)-active and show intramolecular charge transfer (ICT) behavior. PCzTPAN and PTPATPAN aggregates in 90% water/THF were used for the detection of 1,3,5-trinitrobenzene (TNB) as prototypical nitroaromatic compound. They show amplified PL quenching upon addition of TNB with a maximum quenching constant of 5.5 × 10⁵ M^-1. As additional application example, the detection of the glass transition temperature of polystyrene (PS) was accomplished for PTPATPAN blended into PS at doping concentrations of 0.1-1.0 wt%.

Full text of DOI:10.1016/j.polymer.2015.08.064

Accepted Manuscript
Polycarbazoles and Polytriphenylamines Showing Aggregation-Induced Emission
(AIE) and Intramolecular Charge Transfer (ICT) Behavior for the Optical Detection of
Nitroaromatic Compounds
Wenyue Dong, Jõao Pina, Yuyu Pan, Eduard Preis, J.Sérgio Seixas de Melo, Ullrich
Scherf
PII:
S0032-3861(15)30203-2
10.1016/j.polymer.2015.08.064
JPOL 18084
DOI:
Reference:
To appear in: Polymer
Received Date: 29 June 2015
Revised Date: 10 August 2015
Accepted Date: 29 August 2015
Please cite this article as: Dong W, Pina J, Pan Y, Preis E, Seixas de Melo JS, Scherf U, Polycarbazoles
and Polytriphenylamines Showing Aggregation-Induced Emission (AIE) and Intramolecular Charge
Transfer (ICT) Behavior for the Optical Detection of Nitroaromatic Compounds, Polymer (2015), doi:
10.1016/j.polymer.2015.08.064.
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ACCEPTED MANUSCRIPT
Graphical abstract
Polycarbazoles and Polytriphenylamines Showing Aggregation-Induced Emission (AIE) and
Intramolecular Charge Transfer (ICT) Behavior for the Optical Detection of Nitroaromatic
Compounds
Wenyue Dong, Jõao Pina, Yuyu Pan, Eduard Preis, J. Sérgio Seixas de Melo, Ullrich Scherf
Polycarbazoles
(PCzTPAN)
or
polytriphenylamines
(PTPATPAN)
decorated
with
2,3,3-triphenylacrylonitrile side groups have been synthesized and characterized for the occurrence of
aggregation-induced emission (AIE) and intramolecular charge transfer (ICT) effects. PCzTPAN and
PTPATPAN dispersions in 90% water/THF were further used for the high sensitivity detection of
1,3,5-trinitrobenzene (TNB) as prototypical nitroaromatic analyte, showing amplified PL quenching with
a maximum quenching constant of 5.5×105 M-1. Moreover, PTPATPAN was used as AIE-active
fluorescent probe for detection of the glass transition temperature of a polystyrene (PS) film, exhibiting a
very reliable response to the glass transition of PS, up to low probe concentration of 0.1 wt%.
1

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Polycarbazoles and Polytriphenylamines Showing Aggregation-Induced Emission (AIE) and
Intramolecular Charge Transfer (ICT) Behavior for the Optical Detection of Nitroaromatic
Compounds
Wenyue Dong1, Jõao Pina2, Yuyu Pan3, Eduard Preis1, J. Sérgio Seixas de Melo2, Ullrich Scherf1,*
1Bergische Universität Wuppertal, Macromolecular Chemistry Group (buwmakro) and Institute for
Polymer Technology, Gauss-Str. 20, D-42097 Wuppertal, Germany.
2Coimbra Chemistry Centre, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535
Coimbra, Portugal.
3State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012,
PR China.
Correspondence to: U. Scherf (E-mail: scherf@uni-wuppertal.de)
Abstract
Acceptor-substituted polycarbazoles (PCzTPAN) and polytriphenylamines (PTPATPAN) bearing
electron-deficient 2,3,3-triphenylacrylonitrile (TPAN) side groups have been successfully synthesized.
Both of them are aggregation-induced emission (AIE)-active and show intramolecular charge transfer
(ICT) behavior. PCzTPAN and PTPATPAN aggregates in 90% water/THF were used for the detection of
1,3,5-trinitrobenzene (TNB) as prototypical nitroaromatic compound. They show amplified PL quenching
upon addition of TNB with a maximum quenching constant of 5.5×105 M-1. As additional application
example, the detection of the glass transition temperature of polystyrene (PS) was utilized for PTPATPAN
blended into PS at doping concentrations of 0.1-1.0 wt%.
Introduction
Since the first report on the aggregation-induced emission (AIE) phenomenon by Tang et al. in 20011,2, a
lot of attention has been paid on developing novel AIE chromophores that are weakly emissive in dilute
solution but strongly emissive in aggregate state (in dispersion or in the solid state). The main source of
the AIE effect is a restriction of intramolecular motion3-6, as concluded from both theoretical and
experimental studies. The appearance of AIE, as opposite effect to the well-established
aggregation-induced photoluminescence quenching provides a new path for designing luminophores with
high fluorescence quantum yields in the aggregated state for applications in optoelectronic devices7-11
,
bio/chemosensors12-17, bioimaging18-22, etc.
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The detection of nitroaromatic explosives is of high importance for national security and environment
protection23-28, because they are not only explosive but also act as toxic pollutants. Nitroaromatic
compounds with their electron-deficient character can be detected via PL quenching of suited
luminophores induced by excited state charge transfer processes. AIE luminophores are very promising
materials for this purpose. They often show high fluorescence quantum yields in the aggregated state.
Moreover, their bulky 3D structure may facilitate the diffusion of analyte molecules, thus causing
amplified sensing behavior29-34
.
The glass transition is a characteristic and reversible thermal transition of amorphous materials (or the
amorphous domains within semicrystalline materials). The correct detection of the glass transition
temperature (Tg) is very important because pronounced changes of thermal, electric and mechanical
properties are observed when passing Tg. The fluorescence probe technique was introduced as a promising
approach for detecting Tg, expecially of thin films35-38, as often used in optoelectronic devices. Several
fluorescent probe molecules have been tested for this purpose, often with limited sensitivity, since the
ACQ effect occurs. This problem was recently solved by Tang39 et al. They utilized AIE-active TPE and
TPE derivatives for the reliable detection of Tg. Hereby, the sensitivity could be improved by increasing
the probe loading, without occurrence of ACQ effects.
In this manuscript, AIE-active polycarbazoles (PCzTPAN) and polytriphenylamines (PTPATPAN) with
acceptor substituents have been successfully synthesized. The 2,3,3-triphenylacrylonitrile (TPAN) moiety
was chosen as the electron-deficient side group of the polymers. TPAN exhibits so-called
crystallization-induced emission (CIE) and was used for constructing AIE-active luminophores40,41
.
TPAN as electron-deficient moiety was now attached to the backbone of electron-rich polycarbazoles42,43
and polytriphenylamines44,45 thus designing donor-acceptor-type polymers. In this paper, the
aggregation-induced emission (AIE) and the intramolecular charge transfer (ICT) properties of PCzTPAN
and PTPATPAN have been investigated. Furthermore, the novel polymers were used for the detection of
1,3,5-trinitrobenzene (TNB) as prototypical nitroaromatic explosive. In addition, one polymer
(PTPATPAN) was used as fluorescent probe in the detection of the glass transition temperature of
polystyrene (PS).
Experimental
Characterization of Materials
1
13
NMR spectra were recorded on a Bruker AVANCE 400 or AVANCE III 600. H and C NMR spectra
were measured with tetramethylsilane (TMS) as internal standard. Gel permeation chromatography (GPC)
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measurements were carried out on a PSS/Agilent SECurity GPC System equipped with polystyrene gel
columns using chloroform as eluent. GCMS measurements were obtained on a Shimadzu GC-17a with a
Shimadzu GCMS-QP 5050 mass spectrometer (column: FS-OV1-CB-0.25) under helium. Maldi-Tof
mass spectra were recorded on a Bruker Reflex TOF. Elemental analyses were performed on a Vario EL
(CHN) instrument. UV-visible absorption spectra were recorded on a Jasco V-670 spectrometer, and PL
spectra on a HORIBA Scientific FluroMax-4. The PL quantum efficiencies of polymer films were
measured with an integrating sphere. Fluorescence decays were measured using a picosecond
time-correlated single-photon counting (TCSPC) apparatus. The highest occupied molecular orbital
(HOMO) energy levels were estimated on a Surface Analyzer MODEL AC-2 on RIKEN, given as the
threshold where photoelectron emission first occurs. Differential scanning calorimetry (DSC) was
performed on a DSC1 STAR System (Mettler Toledo) at a heating rate of 10 °C min-1 under argon.
Synthesis
All reagents were obtained from commercial suppliers and were used without further purification. All
reactions were carried out under argon atmosphere by standard and Schlenk techniques. The solvents
were used as commercial p.a. quality.
2-(4-Bromophenyl)-3,3-diphenylacrylonitrile40
Into a 250 mL three-necked round bottom flask equipped with a condenser benzophenone (4.65 g,
25.5 mmol), sodium hydride (60% NaH) (5 g, 128 mmol) and toluene (150 mL) were placed under argon.
The mixture was stirred at 110 °C for 10 min. A solution of 4-bromobenzylnitrile (5 g, 25.5 mmol) in
toluene (150 mL) was dropwise added into the above mentioned mixture over a period of ~60 min while
maintaining reflux. After 20 h the mixture was cooled to room temperature, and water (100 mL) was
added. The organic layer was collected and washed three times with brine solution. The organic phase
was dried over anhydrous MgSO4 and concentrated under vacuum. The residue was purified by silica gel
chromatography (eluent: dichloromethane/hexane = 3/7) followed by recrystallization from ethanol to
give the desired product as a light yellow solid in 37% yield (3.4 g). 1H NMR (400 MHz, CDCl3)
7.61 - 7.42 (m, 5H), 7.42 - 7.36 (m, 2H), 7.36 - 7.30 (m, 1H), 7.28 - 7.23 (m, 2H), 7.23 - 7.15 (m, 2H),
7.06 (dd, J = 8.4, 1.0 Hz, 2H). 13C NMR (100 MHz, CDCl3)
(ppm) 158.18, 139.96, 138.53, 133.66,
δ (ppm)
δ
131.52, 131.10, 130.49, 129.92, 129.71, 129.11, 128.32, 128.28, 122.39, 119.50, 110.22. MS (GCMS):
m/z calcd 360.2; found 361.0.
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2-[4-(9H-Carbazol-9-yl)phenyl]-3,3-diphenylacrylonitrile
Tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) (48 mg, 0.052 mmol) and tri-tert-butylphosphane
(P(t-Bu)3) (11 mg, 0.052 mmol) were dissolved in dry toluene (12 mL) under argon and stirred for 10 min
at room temperature (preformation of the catalyst). The catalyst solution was then added to a mixture of
9H-carbazole (700 mg, 4.19 mmol), 2-(4-bromophenyl)-3,3-diphenylacrylonitrile (1.81 g, 5.02 mmol)
and sodium-tert-butylate (t-BuONa) (603 mg, 6.28 mmol) in dry toluene (26 mL). The reaction mixture
was stirred at 90 °C overnight. The mixture was cooled down to room temperature, treated with water,
and extracted three times with chloroform. The organic phase was collected, dried over MgSO4 and
concentrated under vacuum. The residue was purified by silica gel chromatography (eluent:
dichloromethane/hexane = 1/1) to give the desired product as a light green solid in 86% yield (1.6 g).
1H NMR (400 MHz, C2D2Cl4)
7.16 - 7.08 (m, 2H). 13C NMR (100 MHz, C2D2Cl4)
δ
(ppm) 8.15 (d, J = 7.7 Hz, 2H), 7.57 - 7.39 (m, 13H), 7.39 - 7.24 (m, 5H),
(ppm) 159.02, 140.60, 140.39, 138.88, 137.68,
δ
133.89, 131.54, 131.06, 130.47, 130.26, 129.77, 128.89, 128.74, 126.89, 126.50, 123.65, 120.67, 120.51,
110.72, 110.08.
2-[4-(Diphenylamino)phenyl]-3,3-diphenylacrylonitrile
The synthetic procedure used was similar to that described for preparation of 2-[4-(9H-carbazol-9-
yl)phenyl]-3,3-diphenylacrylonitrile: reactants are Pd2(dba)3 (53 mg, 0.058 mmol), P(t-Bu)3 (12 mg, 0.058
mmol), diphenylamine (783 mg, 4.63 mmol), 2-(4-bromophenyl)-3,3-diphenylacrylonitrile (2 g,
5.55 mmol) and t-BuONa (667 mg, 6.94 mmol) in toluene (40 mL). The product was purified by silica gel
chromatography (eluent: dichloromethane/hexane = 1/1) to give a yellow crystalline solid in 96% yield
1
(2 g). H NMR (600 MHz, C2D2Cl4)
δ
(ppm) 7.47 - 7.37 (m, 5H), 7.29 - 7.18 (m, 7H), 7.10 - 7.00 (m,
(ppm) 156.47, 148.01, 147.19, 140.85,
13
10H), 6.84 (d, J = 8.8 Hz, 2H). C NMR (150 MHz, C2D2Cl4)
δ
139.47, 130.92, 130.75, 130.19, 129.99, 129.70, 129.24, 128.74, 128.56, 127.86, 125.25, 123.91, 122.11,
13
120.74, 111.44. C NMR (DEPT, 150 MHz, C2D2Cl4)
δ (ppm) 130.93, 130.75, 130.20, 129.99, 129.70,
129.25, 128.75, 128.56, 125.25, 123.92, 122.11.
2-[4-(3,6-Dibromo-9H-carbazol-9-yl)phenyl]-3,3-diphenylacrylonitrile (1)
2-[4-(9H-Carbazol-9-yl)phenyl]-3,3-diphenylacrylonitrile (1.2 g, 2.69 mmol) was dissolved in
dichloromethane (30 mL) under argon and cooled in an ice bath. The solution was stirred under protection
of light. N-Bromosuccinimide (NBS) (1.0 g, 5.64 mmol) was slowly added in three portions. The reaction
mixture was brought to room temperature and stirred overnight. Afterwards, the mixture was treated with
water and extracted three times with chloroform. The organic phase was collected, washed with brine
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solution and dried over MgSO4. The solution was concentrated under vacuum and the resulting product
was purified by silica gel chromatography (eluent: dichloromethane/hexane = 1/1) to give the desired
1
compound as a green solid in 87% yield (1.42 g). H NMR (400 MHz, C2D2Cl4)
δ (ppm) 8.19 (d, J =
1.7 Hz, 2H), 7.60 - 7.45 (m, 9H), 7.37 (dd, J = 14.3, 7.9 Hz, 3H), 7.29 (t, J = 7.4 Hz, 2H), 7.24 (d, J =
13
8.7 Hz, 2H), 7.11 (d, J = 7.1 Hz, 2H). C NMR (100 MHz, C2D2Cl4)
δ (ppm) 159.41, 140.24, 139.68,
138.78, 136.66, 134.70, 131.77, 131.06, 130.58, 130.24, 129.87, 128.90, 128.77, 126.84, 124.29, 123.57,
13
120.39, 113.64, 111.80, 110.43. C NMR (DEPT, 100 MHz, C2D2Cl4)
δ (ppm) 131.77, 131.06, 130.58,
130.25, 129.87, 128.91, 128.77, 126.84, 123.57, 111.80. MS (Maldi-Tof): m/z calcd 604.33; found 604.22.
Elemental anal. calcd: C, 65.59%; H, 3.34%; N, 4.64%. Found: C, 65.87%; H, 3.37%; N, 4.44%.
2-(4-[Bis(4-bromophenyl)amino]phenyl)-3,3-diphenylacrylonitrile (2)
The synthesis procedure used was similar to that described for preparation of 2-[4-(3,6-dibromo-9H-
carbazol-9-yl)phenyl]-3,3-diphenylacrylonitrile (1): reactants are 2-[4-(diphenylamino)phenyl]-3,3-
diphenylacrylonitrile (1.22 g, 2.72 mmol) and NBS (1.02 g, 5.71 mmol) in dichloromethane (30 mL). The
product was purified by silica gel chromatography (eluent: dichloromethane/hexane = 1/1) to give desired
compound as a yellow solid in 76% yield (1.26 g). 1H NMR (600 MHz, C2D2Cl4)
δ (ppm) 7.46 - 7.38 (m,
5H), 7.35 (d, J = 8.8 Hz, 4H), 7.26 (t, J = 7.4 Hz, 1H), 7.20 (t, J = 7.5 Hz, 2H), 7.08 (d, J = 8.7 Hz, 2H),
7.02 (d, J = 7.1 Hz, 2H), 6.90 (d, J = 8.8 Hz, 4H), 6.83 (d, J = 8.7 Hz, 2H). 13C NMR (150 MHz, C2D2Cl4)
δ
(ppm) 157.24, 146.98, 146.03, 140.64, 139.28, 132.84, 131.08, 130.90, 130.18, 130.14, 129.39, 129.27,
128.78, 128.58, 126.39, 122.95, 120.59, 116.58, 111.10. 13C NMR (DEPT, 150 MHz, C2D2Cl4)
δ
(ppm)
132.84, 131.08, 130.91, 130.18, 130.15, 129.40, 128.78, 128.58, 126.39, 122.95. MS (Maldi-Tof): m/z
calcd 606.35; found 606.17. Elemental anal. calcd: C, 65.37%; H, 3.66%; N, 4.62%. Found: C, 65.02%;
H, 3.54%; N, 4.64%.
Polymer PCzTPAN
Bis(1,5-cyclooctadiene)nickel(0) (Ni(COD)2) (564 mg, 2.052 mmol) and 2,2’-bipyridine (BPy) (320 mg,
2.052 mmol) were added inside a glove box into a 25 mL Schlenk tube containing monomer 1 (310 mg,
0.513 mmol). 1,5-Cyclooctadiene (COD) (222 mg, 2.052 mmol), toluene (7 mL) and DMF (1.4 mL) were
next added to the mixture with syringes under argon. Polymerization was allowed to proceed for 5 days at
80 °C. The reaction mixture was treated with an aqueous 2 M HCl solution and extracted with chloroform.
The collected organic phase was washed with aqueous NaHCO3 solution, saturated, aqueous EDTA
solution, and brine, and finally dried over MgSO4. Afterwards, the solvents were removed under vacuum.
The resulting solid was dissolved in a small amount of chloroform and precipitated into methanol
(500 mL) to afford the targeted polymer as a yellow powder. Subsequent Soxhlet extractions were carried
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out with methanol, acetone, ethyl acetate and chloroform, respectively. After re-precipitation of the
chloroform-soluble fraction into methanol, the yellow polymer was obtained with 29% yield (65 mg).
1H NMR (600 MHz, C2D2Cl4, 60 °C)
δ (ppm) 8.52 (bs, 2H), 7.82 (bs, 2H), 7.70 - 6.95 (m, 16H). Mn 4700,
Mw 6170, Mw/Mn 1.31 (GPC, PS calibration).
Polymer PTPATPAN
A solution of monomer 2 (300 mg, 0.495 mmol), Ni(COD)2 (544 mg, 1.979 mmol), BPy (309 mg,
1.979 mmol) and COD (214 mg, 1.979 mmol) in THF (8 mL) was reacted under microwave heating46 at
120 °C for 60 min. The workup procedure was similar to that described for the preparation of polymer
1
PCzTPAN. The yellow polymer was obtained with 36% yield (80 mg). H NMR (600 MHz, C2D2Cl4,
60 °C)
δ (ppm) 7.60 - 7.48 (m, 4H), 7.48 - 7.36 (m, 5H), 7.36 - 7.19 (m, 4H), 7.19 - 7.10 (m, 5H), 7.10 -
7.03 (m, 2H), 7.01 - 6.91 (m, 2H). Mn 8460, Mw 12800, Mw/Mn 1.51 (GPC, PS calibration).
Results and Discussion
Synthesis and Characterization
Scheme 1. The synthetic route towards momomers 1/2 and polymers PCzTPAN and PTPATPAN,
respectively.
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The synthetic route towards the monomers 1/2 and polymers PCzTPAN/PTPATPAN is depicted in
Scheme 1. Monobromo-TPAN (2-(4-bromophenyl)-3,3-diphenylacrylonitrile) was obtained by treating a
mixture of benzophenone and 2-(4-bromophenyl)acetonitrile with sodium hydride (NaH). Treatment of
monobromo-TPAN with carbazole or diphenylamine under Buchwald-Hartwig coupling conditions
afforded TPAN-substituted carbazole or triphenylamine in good yields. Dibromo-monomers 1 and 2 were
obtained via bromination of TPAN-substituted carbazole or triphenylamine with NBS. Polymer
PCzTPAN was synthesized by Yamamoto-type homocoupling with Ni(COD)2, COD and Bpy in a solvent
mixture of toluene and DMF under conventional heating at 80 ºC. Polymer PTPATPAN was also
synthesized by Yamamoto-type homocoupling, but in this case under microwave heating to 120 ºC. The
structure elucidation of the monomers was performed by NMR spectroscopy, mass spectrometry and
elemental analysis. The chemical structure of the obtained polymers was finally confirmed by GPC as
well as NMR spectroscopy and optical spectroscopy.
Photophysical Properties
Figure 1. Normalized absorption and PL spectra of (a) PCzTPAN and (b) PTPATPAN in dilute THF
solution (polymer concentration: 10-5 M) and as spin-coated films (measured at room temperature).
Figure 1 shows the UV-vis and PL spectra of polymers PCzTPAN and PTPATPAN in dilute THF
solution and as thin films. The absorption spectra in solution and solid state are quite similar since the
twisted structure of the polymers does not allow significant intermolecular π-π stacking interactions in the
solid state. As thin film, PCzTPAN shows an absorption maximum at 312 nm with a shoulder at 348 nm;
PTPATPAN an absorption maximum at 378 nm, attributed to the π-π transitions of the polymer
backbones. In their PL spectra, the films of PCzTPAN and PTPATPAN show emission maxima at
546 nm and 595 nm, giving rise to a green or orange color of the emitted light, respectively. The
corresponding solutions emitted at 546 nm and 637 nm, with a ~40 nm hypsochromic shift for PCzTPAN
and bathochromic shift in the same order for PTPATPAN, respectively. The shifts are probably caused by
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the different electronic properties of the electron-rich backbones thus resulting in different intramolecular
charge-transfer (ICT) properties.
Intramolecular Charge Transfer Properties
Figure 2. Normalized absorption and PL spectra of (a/b) PCzTPAN and (c/d) PTPATPAN, respectively,
in toluene, THF, DCM and DMF solution (polymer concentration: 10-5 M).
The presence of electron-donating TPA or carbazole in combination with the electron-accepting cyano
groups of the TPAN units should allow the occurrence of ICT processes. To investigate this topic,
absorption and emission spectra of both polymers in varying solvents were recorded. Since the
photophysical properties of such D-A conjugates are strongly dependent on the solvent polarity,
solvatochromic effects of the PL spectra are expected for both polymers (Figure 2). The spectral profiles
of both absorption spectra are very similar (Figure 2a/c), suggesting a solvent polarity-independent
electronic structure of the ground state. However, the emission maxima of both polymers are gradually
bathochromically shifted with increasing solvent polarity, with a 68 or 64 nm red-shift for PCzTPAN and
PTPATPAN (shown in Figure 2b/d), respectively, when going from toluene to DMF. Such a behavior
may reflect an increased dipole moment of the exited state, indicating that the lowest energy excited state
S1 of both polymers involves a strong CT component. The solvatochromic effect can be quantified
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through the slope of a plot of Stokes shift (∆
ν) vs. the orientation polarizability ∆ƒ of the solvents,
according to the Lippert-Mataga equation (see supporting information). In a linear fit of the experimental
data (∆ν
vs. ∆ƒ, Table S1), as shown in Figure 3, both polymers exhibit large slopes of 6904 cm-1 for
PCzTPAN and 6095 cm-1 for PTPATPAN, respectively. The results confirm a substantial charge
redistribution during excitation.
Figure 3. Stokes shift (∆ν) vs. solvent polarity parameter (∆ƒ) plots for PCzTPAN and PTPATPAN, for 8
solvents (toluene, 1,4-dioxane, chlorobenzene, chloroform, o-dichlorobenzene, THF, DCM, DMF).
Aggregation Induced Emission
The PL quantum yields of PCzTPAN and PPTPATPAN in dilute THF solution, estimated by using
quinine sulfate as standard, have been determined as ca. 4% for both of them. Thin films of the polymers
exhibited much higher PLQYs of 10% and 19% for PCzTPAN and PTPATPAN, respectively. Evidently,
the transition into the condensed state enhances the PL of the polymers due to the presence of the TPAN
side chains. The AIE phenomenon of PCzTPAN and PTPATPAN was further investigated in THF/water
solvent mixtures. THF is a good solvent for both polymers; water serves as non-solvent. Figure 4 shows
PL spectra as well as plots of relative PL intensities and the position of the PL maxima for different
THF/water mixtures for both polymers. For PCzTPAN (Figure 4a/b), the relative PL intensity first
decreases with increasing water content till 50%, accompanied by a bathochromic shift of the PL
maximum, from 505 nm for pure THF to 555 nm for 50% water. The PL quenching as well as the
bathochromic shift may result from an increased solvent polarity as typical ICT-related behavior. From 50%
to 90% water, the PL intensity of PCzTPAN gradually increases without significant PL shift, a behavior
that is characteristic for AIE chromophores that form nanoaggregates at high non-solvent contents, thus
activating the RIR process. For PTPATPAN (Figure 4c/d), up to a water fraction of 10%, the PL intensity
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decreases; from 10% to 90% water, ongoing aggregation causes a 7-fold increase of the PL intensity.
PTPATPAN displays, in contrast to PCzTPAN, a slight blue-shift during water addition. The blue-shift
maybe caused by an introduction of geometrical disorder (increasing distortion) during aggregation. In
comparison, the PCz backbone of PCzTPAN is more rigid and should be more resilient against torsional
disorder. PL decay experiments support the discussion of our steady state PL data (Table S2): The mean
PL lifetime of PCzTPAN decreases from 563 ps in THF to 392 ps in 50% water/THF and increases to 644
ps in 90% water/THF. For PTPATPAN, it decreases from 487 ps in THF to 295 ps in 10% water/THF
and increases to 1174 ps in 90% water/THF. Generally, PL quenching is accompanied by a decrease of
PL lifetimes. Oppositely, increased PL lifetimes indicate an increase of radiative excited state
deactivation process, thus leading to enhanced PL intensity. The observed changes of PL maxima, PL
intensity and PL lifetimes in different solvent mixtures illustrate the competition between ICT and AIE
behavior, occurring in our polymers.
Figure 4. PL spectra of (a) PCzTPAN and (c) PTPATPAN in THF/water mixtures with different water
content; PL intensity and PL maxima with increasing water content for (b) PCzTPAN and (d)
PTPATPAN, respectively (polymer concentration: 10-6 M).
Theoretical calculations were carried out for further understanding of the electronic properties of both
polymers by density functional theory (DFT) using B3LYP functional and 6-31g* basic sets, as
implemented in the Gaussian 09 program. The optimized structures and orbital distributions of the highest
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occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) of PCzTPAN
and PTPATPAN are depicted in Figure 5, in both cases two repeat units are shown. The TPAN side
chains in both polymers adopt a highly twisted conformation, which is a prerequisite for the occurrence of
AIE effects. In this way π-π stacking causing PL quenching in the aggregated state can be prevented. It is
worthy to note that the HOMOs of both polymers are predominantly located at the electron-rich
polycarbazole and polytriphenylamine backbones. In contrast, the LUMOs are mainly located at
electron-poor TPAN side groups. Generally, this type of electron distribution allows for the occurrence of
ICT effects what is consistent with our experimental results.
Figure 5. Calculated molecular orbital amplitude plots for HOMO and LUMO of PCzTPAN and
PTPATPAN.
Explosive Detection
Presence of the electron-rich polycarbazole and polytriphenylamine backbones in combination with the
AIE-based high solid state PL efficiencies, our polymers seem well-suited for the detection of
electron-deficient nitroaromatic compounds. To explore the potential, we selected 1,3,5-trinitrobenzene
(TNB) as prototypical nitroaromatic compound. The tests were carried out with dispersions of
nanoaggregates of both polymers in 90% water/THF mixtures (polymer concentration: 1 µM). Figure 6a/c
show the PL spectra of those PCzTPAN and PTPATPAN dispersions treated with different amounts of
TNB. Hereby, the PL intensity decreases progressively with increased concentration of TNB for both
polymers, without any significant spectral change. The quenching mechanism is based on an electron
transfer between the excited state of the host (PCzTPAN or PTPATPAN) and TNB23. Please notice that
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there is no spectral overlap between absorption of TNB and PL of PCzTPAN and PTPATPAN (Figure
S1), as prerequisite for Förster-type excitation energy transfer. The electron transfer is driven by the
LUMO-LUMO offset between TNB and PCzTPAN/PTPATPAN (see Table S3). The LUMO levels of
PCzTPAN and PTPATPAN (-2.53 eV and -2.58 eV, respectively) allow for this excited state charge
transfer to the energetically lower-lying LUMO level of TNB (-3.1 eV)29, with a LUMO-LUMO offsets
of ca. 0.57 and 0.52 eV, respectively. For the PCzTPAN dispersion, 95% of the PL emission are
quenched at a TNB concentration of 57 µM; for PTPATPAN 85% of the PL are quenched for a
concentration of 143 µM. Stern-Volmer plots of relative PL intensity (I0/I-1) vs. TNB concentration
reflect the very promising sensing performance. The plots display upward-bent curves for both polymers
(Figure 6b/d), indicating a more efficient quenching process, that means so-called amplified quenching,
for higher quencher concentrations. Here, we split each curve into 3 subparts, each of them was linearly
fitted. For PCzTPAN the obtained quenching constants are: 1.2×105 M-1 for a TNB concentration <19 µM,
3.4×105 M-1 for TNB concentrations between 19 µM and 40 µM, and 5.5×105 M-1 for TNB concentrations
between 42 µM and 57 µM. For PTPATPAN somewhat lower quenching constants: 2.5×104 M-1 for a
TNB concentration <46 µM, 4.0×104 M-1 for TNB concentrations between 48 µM and 83 µM, and
5.2×104 M-1 for TNB concentrations between 85 µM and 143 µM. These quenching constants belong to
the top values within the published PL quenching schemes for the detection of nitroaromatic analytes47.
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Figure 6. PL spectra of (a) PCzTPAN and (c) PTPATPAN, respectively, in THF/water 1/9 containing
different amounts of TNB (polymer concentration: 10-6 M). (b) Stern-Volmer plots of relative PL
intensity I0/I-1 of (b) PCzTPAN and (d) PTPATPAN, respectively, vs. TNB concentration (I = PL
intensity, I0 = PL intensity at a TNB concentration of 0 M).
Detection of the Glass Transition Temprature of Polystyrene by Doping with an AIE-active
Fluorescent Probe (PTPATPAN)
Based on the initial report of the Tang group39 on the use of AIE-active probes for the determination of
the glass transition temperature (Tg) of polymers, we tested the use of our AIE polymer PTPATPAN as
fluorescent probe. For Tg detection, an AIE-active probe is needed that does not electronically interact
with the host polymer. For this purpose, a polystyrene (PS) sample with a narrow molecular weight
distribution (Mn = 8010, Mw = 8210, PDI = 1.03) was selected as model polymer. First, the glass
transition of the sample was independently measured by differential scanning calorimetry (DSC) to be ca.
89 ºC (Figure S2). Next, PTPATPAN was used as fluorescence probe in a concentration of 1 wt%
PTPATPAN. Increasing the temperature decreases the PL intensity of the sample, a plot of PL intensity vs.
temperature (Figure 7) shows a clear kink of the curve at Tg (88 ºC). Reason for this is a stronger
restriction of intramolecular motions of the probe in the frozen, glassy state. After reaching Tg the free
volume increases thus allowing segmental movements of the PS chains and increased intramolecular
motions within the AIE-active probe.
Figure 7. Integrated PL intensity of a PS sample doped with 1 wt% PTPATPAN as a function of
temperature.
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We also tested lower PTPATPAN doping (0.1 wt%). Also for the lowered dopant loading the Tg is
detectable at 88 ºC, with an decreased contrast of the slopes above and below Tg (Figure 8a). The
repeatability of the measurement was checked for a probe loading of 0.1 wt%, as shown in Figure 8b, for
the PL intensity at 50 ºC (glassy state) and 110 ºC (softened state). The method seems especially suited
for Tg measurements of thin polymer films, e.g. by following corrections between film thickness and Tg.
Figure 8. (a) PL intensity of PS doped with 0.1 wt% PTPATPAN as a function of temperature, and
(b) repeatability of the measurements shown for the PL intensities at 50 °C and 110 °C.
Conclusions
Polycarbazole and polytriphenylamine derivatives with 2,3,3-triphenylacrylonitrile (TPAN) as side
groups have been successfully synthesized via Yamamoto-type coupling procedures. The polymers
exhibit both AIE as well as ICT properties, the latter caused by the interplay of electro-poor TPAN
substituents and electron-rich polycarbazole/polytriphenylamine backbones. The strategy of combining an
electron-rich, conjugated backbone with AIE-active side groups is unique and introduces a couple of
advantages, as mentioned in the introduction, related to e.g.: (1) the good processing properties of
polymers, (2) the occurrence of strong interactions of the electron-rich backbone and electron-poor
analytes, and (3) high exciton diffusion ability provided by the conjugated polymer backbone thus leading
to an amplification in sensitivity towards suited analytes. The occurring ICT effects cause a distinct
solvatochromism. PCzTPAN or PTPATPAN dispersions in 90% water/THF mixtures were used for the
optical detection of nitroaromatic analytes (TNB). Both dispersions show a high sensitivity and amplified
PL quenching upon TNB addition. The maximum quenching constant was determined to be 5.5×105 M-1.
PTPATPAN was also used as PL probe for the optical detection of the glass transition temperature (Tg) of
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polystyrene (PS). Doping PS with our AIE probe allows for a reliable Tg measurement. The method is
especially promising for Tg determination of thin films.
Acknowledgement
W. D. would like to thank for financial support from the fellowship program of the China Scholarship
Council (CSC). Thanks to Anke Helfer for performing GPC analyse and to Sylwia Adamczyk for AC-2
measurements. The research leading to these results has received funding from Laserlab-Europe (grant
agreement no. 284464, EC's Seventh Framework Programme).
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Polycarbazoles and Polytriphenylamines Showing Aggregation-Induced Emission (AIE) and
Intramolecular Charge Transfer (ICT) Behavior for the Optical Detection of Nitroaromatic
Compound
Wenyue Dong, Jõao Pina, Yuyu Pan, Eduard Preis, J. Sérgio Seixas de Melo, Ullrich Scherf
Highlights:
Acceptor-substituted polycarbazoles and polytriphenylamines showing AIE as well as ICT behavior have
been synthesized.
Dispersions containing polymer aggregates have been used for the optical detection of
1,3,5-trinitrobenzene.
Amplified PL quenching was observed with a maximum PL quenching constant of 5.5×105 M-1.
Moreover, one polymer (PTPATPAN) was used as PL-sensitive dopant in the Tg detection of polystyrene
at doping concentrations of 0.1-1.0 wt%.

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Supporting information
Polycarbazoles and Polytriphenylamines Showing Aggregation-Induced Emission (AIE) and
Intramolecular Charge Transfer (ICT) Behavior for the Optical Detection of Nitroaromatic
Compounds
Wenyue Dong, Jõao Pina, Yuyu Pan, Eduard Preis, J. Sérgio Seixas de Melo, Ullrich Scherf
Lippert-Mataga equation1,2:
The solvatochromic behaviors of the polymers can be quantitatively described from the slope of a plot of
the Stokes shift (∆ν) against the orientation polarizability
∆ƒ of the solvents, according to the
Lippert-Mataga equation:
2∆ꢄ
ℎꢅꢆꢇ
ꢈ
ꢌꢍ
ꢉꢊ − ꢉꢋ + ꢅꢎꢏꢐꢑꢆꢏꢑ
ꢀꢁ = ꢁꢂ − ꢁꢃ =
where ∆ƒ is the orientational polarizability of the solvent, νa – νe corresponds to the Stokes shifts, µE and
µG are the excited state and ground-state dipole moment, respectively, h and c are the Planck constant and
the speed of light, respectively, a is the Onsager solvent cavity radius.
Orientational polarizability
∆
ƒ can be calculated as follow:
ɛ − 1
2ɛ + 1 2ꢏꢍ + 1
ꢏꢍ − 1
ꢈ
ꢌ
∆ꢄ ɛ, ꢏ =
−
where
ε and n are the static dielectric and optical refractive index of the solvent, respectively.

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Table S1. Absorption and emission maxima of PCzTPAN and PTPATPAN, as well as Stokes shifts (∆ν),
dielectric constant of the solvents (
ƒ) of the solvents.
ε), refractive index of the solvents (n) and orientation polarizability
(∆
solvent
λUV (nm)
λPL (nm) ∆ν (cm-1)
ε
n
∆ƒ
toluene
302
308
307
308
308
307
479
525
507
547
502
502
515
482
595
659
637
655
637
640
644
604
12236
13420
12849
14186
12547
12653
12945
11933
9303
2.38
8.93
7.58
36.7
5.62
4.81
9.93
2.25
2.38
8.93
7.58
36.7
5.62
4.81
9.93
2.25
1.4969
1.4241
1.4072
1.4305
1.5248
1.4458
1.5514
1.4224
1.4969
1.4241
1.4072
1.4305
1.5248
1.4458
1.5514
1.4224
0.013
0.217
0.210
0.274
0.143
0.148
0.186
0.025
0.013
0.217
0.210
0.274
0.143
0.148
0.186
0.025
PCzTPAN
DCM
THF
DMF
chlorobenzene
chloroform
o-dichlorobenzene 309
1,4-dioxane
toluene
306
383
382
381
383
387
384
PTPATPAN
DCM
11004
10548
11842
10141
10417
10312
9553
THF
DMF
chlorobenzene
chloroform
o-dichlorobenzene 387
1,4-dioxane 383
Table S2. Photoluminescence lifetime data of PCzTPAN and PTPATPAN in different THF/water
mixtures, including decay times (τ), their percentage values (a) as well as the mean PL lifetimes (<τ>).
polymer solvent
THF
a1
a2
a3
τ1 (ps)
70
τ2(ps)
430
τ3 (ps)
1740
2190
2710
940
<τ> (ps)
563
0.453
0.595
0.517
0.308
0.408
0.321
0.285
0.299
0.339
0.499
0.226
0.12
PCzTPAN 50%water
90%water
50
350
392
50
400
0.184
0.353
0.092
644
THF
40
420
487
PTPATPA 10%water
N
50
270
1520
295
90%water
140
630
2520
0.287
0.351
0.362
1174

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Figure S1. Normalized absorption spectrum of TNB and PL spectra of PCzTPAN and PTPATPAN
dispersions in THF/water 1:9, respectively.
Table S3. HOMO and LUMO energies of PCzTPAN and PTPATPAN, as well as the optical bandgap
energies.
Bandgapa
eV
HOMOb
eV
LUMOc
eV
2.88
-5.41
-5.35
-2.53
-2.58
PCzTPAN
2.77
PTPATPAN
a, the optical bandgap (Eg) was calculated from the onsets of the UV/vis absorption bands; b, the HOMO
energies were measured by atmospheric photoelectron spectroscopy (AC-2 method); c, the LUMO
energies were calculated based on the bandgap and HOMO energies.

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Figure S2. DSC measurement of the used PS sample (heating rate: 10 K/min).
Reference:
1. V. E. Z. Lippert, Electrochemistry, 1957, 61, 962-975.
2. N. Mataga, Y. Kaifu, M. Koizumi, Bull. Chem. Soc. Jpn., 1956, 29, 465-470.