Influence of alkyl length on properties of piezofluorochromic aggregation induced emission compounds derived from 9,10-bis[(N-alkylphenothiazin-3-yl) vinyl]anthracene

Article abstract of DOI:10.1016/j.tet.2013.12.015

Three 9,10-bis[(N-alkylphenothiazin-3-yl)vinyl]anthracene derivatives with different propyl, hexyl, and dodecyl side chains (AnPh₃, AnPh ₆, and AnPh₁₂) were synthesized and confirmed by standard spectroscopic methods. All of the compounds exhibited obvious aggregation induced emission (AIE) and piezofluorochromic (PFC) properties. The PFC behaviors were investigated and showed that proportional alkyl-length dependent relationship existed not only in the ground states of the compounds, but also in the melted states compared with the fumed states of the compounds. The PFC mechanism was explored and ascribed to the crystalline-amorphous phase transformation. More importantly, these derivatives showed reversible significant PFC properties and reproducibility in various states including fumed, ground, annealed, and melted states, making them promising stimuli-responsive and smart luminescent materials for pressure-sensors, information-recording, and light-emitting device applications.

Full text of DOI:10.1016/j.tet.2013.12.015

Tetrahedron 70 (2014) 924e929
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Influence of alkyl length on properties of piezofluorochromic
aggregation induced emission compounds derived from
9,10-bis[(N-alkylphenothiazin-3-yl)vinyl]anthracene
,
b
a
a
c
c
Xiqi Zhang a , Zhiyong Ma , Yang Yang , Xiaoyong Zhang , Zhenguo Chi , Siwei Liu ,
*
Jiarui Xu c, Xinru Jia b, Yen Wei a
,
*
a Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084, China
b Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education, College of
Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
c PCFM Lab, DSAPM Lab and KLGHEI of Environment and Energy Chemistry, FCM Institute, State Key Laboratory of Optoelectronic Materials and
Technologies, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 17 October 2013
Received in revised form 27 November 2013
Accepted 5 December 2013
Available online 13 December 2013
Three 9,10-bis[(N-alkylphenothiazin-3-yl)vinyl]anthracene derivatives with different propyl, hexyl, and
dodecyl side chains (AnPh3, AnPh6, and AnPh12) were synthesized and confirmed by standard spec-
troscopic methods. All of the compounds exhibited obvious aggregation induced emission (AIE) and
piezofluorochromic (PFC) properties. The PFC behaviors were investigated and showed that proportional
alkyl-length dependent relationship existed not only in the ground states of the compounds, but also in
the melted states compared with the fumed states of the compounds. The PFC mechanism was explored
and ascribed to the crystallineeamorphous phase transformation. More importantly, these derivatives
showed reversible significant PFC properties and reproducibility in various states including fumed,
ground, annealed, and melted states, making them promising stimuli-responsive and smart luminescent
materials for pressure-sensors, information-recording, and light-emitting device applications.
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
Aggregation induced emission
Reversible piezofluorochromic property
Alkyl-length dependent
Crystallineeamorphous phase
transformation
Divinylanthracene derivative
Stimuli-responsive luminescent material
1. Introduction
performance have been developed involving various architectural
frameworks,
such
as
siloles,9
tetraphenylethene,10e14
Piezofluorochromic (PFC) materials have attracted great interest
in sensors, security inks, and memory chips applications due to
their advanced luminescent properties that change in response to
external force stimuli with superior high efficiency and re-
producibility.1,2 Molecular assembly structure change is one major
PFC way and believed easier to realize the dynamic control of the
fluorescent process than that of chemical structure change.1 The
first example appeared in 2002, Weder and collaborators reported
on cyano-substituted diphenylethene derivatives as the first two
PFC materials.3 However, rare organic PFC materials had been re-
ported until 2010 due to the notorious problem of aggregation-
caused quenching (ACQ) effect exist in solid state of organic com-
pounds, and eventually cause the lack of propertyestructure re-
lationship established for these kinds of materials.4e8 Aggregation-
induced emission (AIE) materials with advanced anti-ACQ
triphenylethene,15e20 distyrylanthracene,21e23 cyano-substituted
diarylethene derivatives24e30 conjugated molecules, and utilized
for chemosensor, and bioimaging applications.
In 2010, our group incorporated AIE feature into the PFC mate-
rial, and thus obtained a piezofluorochromic AIE (PAIE) compound
derived from tetraphenylethylene and divinylanthracene.31 Since
then, a number of new PAIE materials had been synthesized in our
lab, and a common structureeproperty relationship had been
established for helping identifying and synthesizing more novel
PFC materials.32e37 Hereafter, a series of novel organic PAIE com-
pounds were synthesized and greatly broadened the field of PFC
materials.38e54 In view of this situation, the very critical thing is to
explore in-depth the structureeproperty relationship of PFC ma-
terials and clearly understand the piezofluorochromism.
It is well known that alkyl chain length has a significant impact
on the PFC property. In the previous work, six multifunctional or-
ganic PFC materials derived from 9,10-distyrylanthracene with
various alkyl endgroups have been reported in our group,
* Corresponding authors. E-mail addresses: sychyzhang@126.com (X. Zhang),
weiyen@tsinghua.edu.cn (Y. Wei).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.12.015

X. Zhang et al. / Tetrahedron 70 (2014) 924e929
925
exhibiting obvious proportional relationship of chain length-
dependent PFC behavior.37 A similar research was investigated
about the alkyl chain length effect of 9,10-bis(p-alkoxystyryl)an-
thracenes by Yang’ group.55 Very recently, they have also explore
the
length-dependent
PFC
behavior
of
9,10-bis[(9,9-
dialkylfluorene-2-yl)vinyl]anthracene and 9,10-bis[(N-alkylcarba-
zol-3-yl)vinyl]-anthracene derivatives, which interestingly showed
apparent different chain length-dependent properties. Among the
former derivatives, proportional relationship of chain length-
dependent PFC behavior was observed, whereas the latter ones
exhibited inverse relationship of alkyl chain length effect, however,
the morphology of solid state before and after grinding didn’t show
conspicuous divergence.39,40
In this contribution, we have designed and facilely synthesized
a series of 9,10-bis[(N-alkylphenothiazin-3-yl)vinyl]anthracene de-
rivatives with various length of alkyl chains (propyl, hexyl, and
dodecyl) (AnPh3, AnPh6, and AnPh12, Scheme 1), which showed
obvious AIE feature and PFC behavior. Then quantum mechanical
computations were conducted to reveal the origin of the AIE effect.
Solid fluorescence spectra and UVevis spectra were studied to ex-
plore their PFC properties. Furthermore, the piezofluorochromism
was investigated by differential scanning calorimetry (DSC), small
and wide-angle X-ray scattering (SWAXS), and time-resolved emis-
sion-decay behaviors. The results demonstrate that synthesized
compounds are not only reversible PFC materials but also display
proportional relationship of chain length-dependent behavior.
Fig. 1. Calculated spatial electron distributions of HOMOs and LUMOs of AnPh3,
AnPh6, and AnPh12
.
Scheme 1. Schematic showing the chemical structures of AnPh3, AnPh6, and AnPh12
.
2. Results and discussion
The fluorogens AnPh3, AnPh6, and AnPh12 were prepared by
the WittigeHorner reaction with extremely high yields of 94e98%
following the synthetic route shown in Scheme S1. Theirs struc-
tures were characterized and confirmed by standard spectroscopic
methods. To gain the lowest energy spatial conformations of the
compounds, we conducted quantum mechanical computations via
Gaussian 03 software. The highest occupied molecular orbitals
(HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) of
AnPh3, AnPh6, and AnPh12 were obtained (Fig. 1) according to the
density functional method at the B3LYP/6-31 G level after the
structural optimization.56
The HOMOs of these compounds exhibited dispersed electron
cloud distributions located at phenothiazine and anthracene
groups on the molecules, whereas the electron clouds of the LUMOs
showed migration from both sides of the phenothiazine groups to
the anthracene core groups. It is noteworthy that all of the com-
pounds adopted twisted spatial conformations from the optimized
structure. The dihedral angles of the anthracene groups and the
adjacent phenothiazine groups were calculated as 64ꢀ for all these
compounds. From these twisted conformations, we can speculate
the AIE properties of these three compounds according to the re-
stricted intramolecular rotation mechanism of AIE materials pro-
posed by Tang et al.57
To determine whether the compounds are AIE-active, the pho-
toluminescence (PL) emission spectra of their diluted mixtures
were investigated using THFewater mixtures with different water
fractions. As shown in Fig. 2A, when the water fraction is lower than
Fig. 2. PL spectra of (A) AnPh3, (B) AnPh6, and (C) AnPh12 in THFewater mixtures with
different water fractions. The insets depict the changes in PL peak intensities under
different water fractions.

926
X. Zhang et al. / Tetrahedron 70 (2014) 924e929
50%, the PL intensity of AnPh3 is indeed very weak. However, when
the water fraction reaches 60%, a significant increase of PL intensity
is observed from 9.0 to 940 a.u., which showed approximately 104
times higher than that in the pure THF, demonstrating the ex-
traordinary AIE feature of AnPh3. Similar phenomena can be ob-
served in the other two compounds (Fig. 2B and C). It is worth
mentioning that the PL intensities exhibit a zig-zag pattern as the
water fractions increase. This may be due to the affect of different
types of nanoparticle suspensions including crystal or amorphous
morphology existed in the solution.36
The twisted conformations bring about AIE features to the
compounds, meanwhile, may generate PFC properties for them.
Therefore, the compound AnPh3 was ground in a mortar with
a pestle directly, the fluorescent color of the compound changed
from yellow to orange immediately (Fig. 3A), which revealed con-
spicuous PFC behavior. After the ground AnPh3 was conducted with
annealing or fuming treatment, the fluorescent color returned to its
original appearance, demonstrating good reversibility in the fluo-
rescent emission. The ground, fumed or annealed sample were
further carried out for melting treatment. An interesting phe-
nomenon could be observed that the fluorescent color changed to
orange-red with even longer wavelength emission. More impor-
tantly, the melted sample could recover its very original state just
via recrystallized procedure. Similar diverse phenomena appeared
in the other two synthesized compounds (Fig. 3B and C).
Fig. 3. Fluorescent images of (A) AnPh3, (B) AnPh6, and (C) AnPh12 with different
treatments (ground, fumed, annealed, melted, and recrystallized) when taken at room
temperature under 365 nm UV light.
Fig. 4. (A) Normalized solid-state fluorescent spectra of AnPh3 in fumed, ground, and
melted states; (B) Normalized solid-state fluorescent spectra of AnPh3 in ground and
annealed states; (C) Normalized solid-state UVevis spectra of AnPh3 in fumed, ground,
annealed, and melted states.
To quantitatively measure the fluorescent wavelength changes
of the three compounds among the different states, solid-state
fluorescent spectra were carried out. As shown in Fig. 4A, the
fluorescent emission wavelength of the fumed AnPh3 sample lo-
cated at 566 nm. When ground, the wavelength red-shifted to
599 nm with a 33 nm wavelength shift. While the fumed or ground
sample was heated to obtain a melted state sample, the emission
even red-shifted to a longer emission wavelength at 620 nm, which
exhibited a 54 nm red-shift compared with the fumed one. The
resulted ground sample can easily return to the original state with
short-wavelength by fuming with an organic vapor like dichloro-
methane or via annealing on a hot plate at 150 ꢀC for 5 min (Fig. 4B),
demonstrating excellent reversibility of the obtained PFC material.
The fluorescent wavelength of the fumed AnPh6 sample was
563 nm (Fig. S1A), while its ground sample red-shifted to 603 nm
with a 40 nm wavelength shift. The melted state of AnPh6 derived
from its fumed or ground state showed a 619 nm for the emission
wavelength, which emerged a 56 nm red-shift than that of the
fumed AnPh6. Compared with the previous two compounds, the
fluorescent wavelength of the fumed AnPh12 sample exhibited
a shorter emission wavelength at 551 nm (Fig. S2A), when ground
in a mortar, the resulting wavelength moved to 596 nm with a red-
shift of 45 nm. The emission of the melted sample of AnPh12
reached 629 nm with a 78 nm red-shift compared with its fumed
state. The above result indicated that the longer the alkyl chain
length is, the more obvious red-shift not only the ground sample
but also the melted sample is. The solid-state UVevis spectra also
revealed the changes in fumed, ground, annealed, and melted
states (Fig. 4C, Figs. S1C and S2C). The annealed sample showed
similar absorption as the fumed one. When the samples were
ground, the absorption areas ranging from 500 nm to 700 nm

X. Zhang et al. / Tetrahedron 70 (2014) 924e929
927
significantly increased. Whereas the samples were in melted states,
the absorption at 500e700 nm further dramatically increased, even
more obviously than that of the ground ones. These results dem-
onstrate that these compounds are not only PFC materials but also
piezochromic materials (color change under external force) as well.
As shown in Fig. S3, the melted samples can easily recover to the
original state by recrystallization. These reversible color change
features make them promising candidates for optical recording and
temperature- or pressure-sensing systems.
To determine the mechanism of the PFC compounds, SWAXS
measurements and DSC experiments were conducted (Fig. 5, Figs.
S4 and S5). SWAXS measurements were employed to elucidate
the micro-structures of the compounds in fumed, ground,
annealed, and melted states. The sharp scattering peaks were ob-
served for the fumed samples, indicating an ordered crystalline
structure. After grinding, a transition from crystalline structure to
amorphous phase occurred with the above sharp peaks attenuated
or even disappeared. When annealed, the ground samples led to
the recovery of the crystalline structure by accompanying the ap-
pearance of sharp peaks that coincided with the original sample.
Melting treatments of the ground, fumed or annealed sample were
further carried out for the SWAXS measurements, the result
showed that complete transition to amorphous phase occurred
with the diffraction peaks disappeared. The results indicate that the
reversible transition between the ordered and disordered molec-
ular aggregations is crucial for the PFC features. Reproducible
heating DSC result showed that the ground state of AnPh3 had an
endothermic peak located at 135 ꢀC before the melting point with
enthalpy value 3.7 kJ molꢁ1, whereas no endothermic peak
appeared around this temperature for the fumed state. Meanwhile,
it should be mentioned that the up and down peaks around 260 ꢀC
could be observed, which represented the melt-crystallization
transformation process. The ground samples of AnPh6 and
AnPh12 also emerged endothermic peakꢁs1located at 136 ꢀC and
132 ꢀC with enthalpy values 6.6 kJ mol and 1.7 kJ molꢁ1, re-
spectively. The trace of endothermic peaks around the same tem-
perature range still could not be found in the fumed samples. The
DSC results indicated that the ground samples showed significant
changes of the morphologies with respect to the fumed states.
The time-resolved emission-decay behaviors of AnPh3, AnPh6,
and AnPh12 in fumed, ground, annealed, and melted states were
investigated to obtain further information of the PFC materials. The
time-resolved fluorescence curves and the lifetime data are illus-
trated in Fig 6 and Table 1, respectively. Two relaxation pathways
were found in the fluorescence decays, indicating that the time-
resolved PL spectra of the compound included independent emis-
sions from the segments with different
p-conjugation extent
Fig. 5. (A) SWAXS patterns of AnPh3 in fumed, ground, annealed, and melted states;
(B) DSC curves of AnPh3 in fumed and ground states.
Fig. 6. Time-resolved emission-decay curves of (A) AnPh3, (B) AnPh6, and (C) AnPh12
in fumed, ground, annealed, and melted states.

928
X. Zhang et al. / Tetrahedron 70 (2014) 924e929
Table 1
bromododecane purchased from Alfa Aesar were used as received.
All other agents and solvents were purchased from commercial
sources and used directly without further purification. Tetrahy-
drofuran (THF) was distilled from sodium/benzophenone. Ultra-
pure water was used in the experiments.
Solid-state fluorescence lifetime data of AnPh3, AnPh6, and AnPh12 in fumed,
ground, annealed, and melted states
Sample
State
s1 (ns)a
A1
s
2(ns)a
A2
<s
> (ns)c
b
b
AnPh3
Fumed
1.32
1.20
1.43
0.71
1.38
1.25
1.34
0.97
1.57
1.68
1.82
0.99
0.40
0.41
0.52
0.39
0.46
0.38
0.41
0.25
0.52
0.42
0.53
0.17
3.20
3.17
3.43
2.23
3.50
3.44
3.27
2.84
3.57
3.80
3.62
5.06
0.60
0.59
0.48
0.61
0.54
0.62
0.59
0.75
0.48
0.58
0.47
0.83
2.45
2.36
2.39
1.64
2.52
2.61
2.48
2.37
2.53
2.91
2.67
4.37
1H NMR and 13C NMR spectra were measured on a JEOL 400 MHz
spectrometer [CDCl3 as solvent and tetramethylsilane (TMS) as the
internal standard]. HRMS was obtained on Shimadzu LCMS-IT-TOF
high resolution mass spectrometry. Fluorescence spectra and life-
time were measured on FLS 920 lifetime and steady state spec-
trometer. Solid state UVevis spectra were recorded on a Hitachi
U4100 UVeviseNIR spectrophotometer. Differential scanning calo-
rimetry (DSC) curves were performed on TA Instruments DSC
Q2000 at a heating rate of 10 ꢀC minꢁ1 under N2 atmosphere. 1D
small and wide-angle X-ray scattering (SWAXS) experiments were
carried out with a SAXS instrument (SAXSess, Anton Paar) con-
taining Kratky block-collimation system. An image plate was used to
Ground
Annealed
Melted
Fumed
Ground
Annealed
Melted
Fumed
AnPh6
AnPh12
Ground
Annealed
Melted
a
Fluorescence lifetime.
Fractional contribution.
Weighted mean lifetime.
b
c
record the scattering patterns form from 0.06 to 29 nmꢁ1
.
according to the detected multiple lifetimes. The weighted mean
lifetimes < > of the fumed, annealed, and ground samples didn’t
exhibit obvious differences, although the fluorescent emission
wavelength of them showed significant divergences. Interestingly,
The THFewater mixtures with different water fractions were
prepared by slowly adding distilled water into the THF solution of
samples under ultrasound at room temperature. The ground sam-
ples were prepared by grinding using a mortar and pestle. The
fumed samples were prepared by treating the ground samples with
CH2Cl2 vapors for 5 min. The annealing experiments were done on
a hot-stage with an automatic temperature control system for
5 min with the annealing temperatures at 150 ꢀC. The recrystallized
samples were obtained via recrystallized treatment with THF/EtOH
mixed solvents.
s
the <
pared with the other states. While the melted AnPh3 showed the
shortest < > among the various states, and the melted AnPh6
sample showed similar < > with its other states, whereas the
melted AnPh12 compound exhibited the longest < > than that of
s> of melted sample emerged stupendous discrepancy com-
s
s
s
the other three states. The reason of these divergences is still not
clear, but the changes of the conjugation extent in the solid-state
aggregates may be the major cause for the PFC mechanism. From
the HOMOs and LUMOs of three derivatives via quantum me-
chanical computations, the conjugation extent didn’t seem any
difference in the molecules with various alkyl chain lengths. The
various alkyl chain lengths mainly affect the crystalline structure
and melting point, which can be observed from the SWAXS pat-
terns and DSC curves of these compounds. This result indicated that
the aggregation state of the derivatives could be altered with dif-
ferent alkyl chain lengths, thus affecting the macroscopic proper-
ties including fluorescent spectra and fluorescence decay times.
4.1.2. Synthesis of AnPh3, AnPh6, and AnPh12. Synthetic route of
the compounds AnPh3, AnPh6, and AnPh12 was showed in Scheme
S1. The intermediate 1 was synthesized according to the litera-
ture.37 The phenothiazine-3-carbaldehyde intermediates (2) with
different alkyl chain length (R¼n-C3H7, n-C6H13, n-C12H25) were
synthesized according to the literature.35,58,59
Synthesis of 9,10-bis[(N-propylphenothiazin-3-yl)vinyl]anthra-
cene (AnPh3). Tetraethyl anthracene-9,10-diylbis(methylene)
diphosphonate (1) (0.24 g, 0.50 mmol) and 10-propyl-10H-pheno-
thiazine-3-carbaldehyde (2) (0.32 g,1.2 mmol) were dissolved inTHF
(20 mL), and then t-BuOK (0.3 g) was added under N2 gas. The so-
lution was stirred at room temperature overnight. After removing
the solvent under reduced pressure, the residue was recrystallized
with THF/EtOH to give AnPh3 (0.16 g, 97% yield). 1H NMR (400 MHz,
3. Conclusions
In summary, we have reported new alkyl length-dependent
solid-state PFC characteristics of AIE-active 9,10-bis[(N-alkylphe-
nothiazin-3-yl)vinyl]anthracene derivatives with different propyl,
hexyl, and dodecyl side chains (AnPh3, AnPh6, and AnPh12). The
PFC behaviors were investigated and found that red-shifted extent
of the ground samples would increased as the length of alkyl chain
increased. The melted samples of the synthesized derivatives also
exhibited proportional alkyl length-dependent features with re-
spect to their fumed states. The derivatives showed reversible
significant PFC properties and reproducibility in various states in-
cluding fumed, ground, annealed, and melted states. These excel-
lent properties make the compounds promising stimuli-responsive
and smart luminescent materials for pressure-sensors, in-
formation-recording, and light-emitting device applications. The
alkyl length-dependent relationship established in this contribu-
tion should be helpful in guiding researchers to synthesize PFC
materials and in-depth understand the PFC mechanism.
CDCl3)
d
: 1.05 (t, 6H, J¼7.2 Hz), 1.83e1.93 (m, 4H), 3.87 (t, 4H,
J¼7.2 Hz), 6.77 (s, 1H), 6.82 (s, 1H), 6.85e6.98 (m, 6H), 7.11e7.21 (m,
4H), 7.34e7.53 (m, 8H), 7.74 (s,1H), 7.79 (s,1H), 8.35 (q, 4H, J¼3.2 Hz).
13C NMR (100 MHz, CDCl3)
d (ppm): 145.08, 145.06, 132.73, 131.98,
129.70, 126.55, 125.51, 125.25, 115.54, 115.51, 49.41, 20.27, 11.42.
HRMS calcd for C48H40N2S2, [MþH]þ: 709.2706, found 709.2712.
The syntheses of 9,10-bis[(N-hexylphenothiazin-3-yl)vinyl]an-
thracene (AnPh6) and 9,10-bis[(N-dodecylphenothiazin-3-yl)vinyl]
anthracene (AnPh12) were similar to that of AnPh3.
AnPh6 (94% yield). 1H NMR (400 MHz, CDCl3)
d: 0.90 (t, 6H,
J¼3.2 Hz), 1.28e1.52 (m, 12H), 1.85 (quint, 4H, J¼6.8 Hz), 3.90 (t, 4H,
J¼7.6 Hz), 6.78 (s, 1H), 6.82 (s, 1H), 6.85e6.97 (m, 6H), 7.12e7.20 (m,
4H), 7.37e7.51 (m, 8H), 7.75 (s, 1H), 7.79 (s, 1H), 8.36 (q, 4H,
J¼3.2 Hz). 13C NMR (100 MHz, CDCl3)
d (ppm): 145.09, 145.06,
132.73, 131.95, 129.70, 126.56, 125.25, 124.43, 115.48, 115.46, 47.70,
31.58, 27.00, 26.76, 22.71, 14.10. HRMS calcd for C54H52N2S2,
[MþH]þ: 793.3645, found 793.3636.
4. Experimental procedure
4.1. General
AnPh12 (98% yield). 1H NMR (400 MHz, CDCl3)
d: 0.88 (t, 6H,
J¼3.2 Hz),1.23e1.38 (m, 32H),1.46 (quint, 4H, J¼3.2 Hz), 1.85 (quint,
4H, J¼7.2 Hz), 3.89 (t, 4H, J¼7.2 Hz), 6.78 (s, 1H), 6.82 (s, 1H),
6.86e6.97 (m, 6H), 7.13e7.20 (m, 4H), 7.37e7.53 (m, 8H), 7.75 (s,
1H), 7.79 (s, 1H), 8.36 (q, 4H, J¼3.2 Hz). 13C NMR (100 MHz, CDCl3)
4.1.1. Materials and characterization. 9,10-Bis(chloromethyl)an-
thracene, phenothiazine, 1-bromopropane, 1-bromohexane, and 1-
d (ppm): 145.08, 145.06, 132.73, 131.95, 129.70, 125.43, 125.25,

X. Zhang et al. / Tetrahedron 70 (2014) 924e929
929
24. An, B.-K.; Kwon, S.-K.; Jung, S.-D.; Park, S. Y. J. Am. Chem. Soc. 2002, 124,
14410e14415.
25. Zhang, X.; Liu, M.; Yang, B.; Zhang, X.; Chi, Z.; Liu, S.; Xu, J.; Wei, Y. Polym. Chem.
124.43, 115.48, 115.46, 47.69, 32.00, 29.72, 29.66, 29.63, 29.43,
29.36, 27.05, 27.01, 22.77, 14.20. HRMS calcd for C66H76N2S2,
[MþNa]þ: 983.5342, found 983.5392.
2013, 4, 5060e5064.
26. Zhang, X.; Zhang, X.; Yang, B.; Hui, J.; Liu, M.; Chi, Z.; Liu, S.; Xu, J.; Wei, Y. Polym.
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Acknowledgements
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This research was supported by the National Science Foundation
of China (Nos. 21134004, 21201108), and the National 973 Project
(No. 2011CB935700), China Postdoctoral Science Foundation
(2013T60100, 2012M520243).
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Detailed information about synthetic route, normalized fluo-
rescent spectra, UVevis spectra, SWAXS patterns, and DSC curves of
AnPh6 and AnPh12 in different states were provided. Supplemen-
tary data related to this article can be found at http://dx.doi.org/
10.1016/j.tet.2013.12.015.
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