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DOI: 10.1039/C5CC04720J

Cite this: DOI: 10.1039/c0xx00000x

COMMUNICATION

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Rener Chen,1 Huajiang Jiang,1 Haining Gu,2 Qizhong Zhou*,1 Jiashou Wu,1 Dingben Chen1 and Jie Zhang1
5

Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/c0xx00000x
A pH-responsive fluorescent [5]Pseudorotaxane formed by
self-assembly of cationic water-soluble pillar[5]arenes and a
tetraphenylethene derivative was reported.

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The design and preparation of interlocked threaded structures,1

such
as
pseudorotaxanes,
rotaxanes,
catenanes,
polypseudorotaxanes, polyrotaxanes, and polycatenanes, are hot
topics in chemistry due to not only their topological importance
but also their potential applications including molecular machines
and drug delivery materials. Chemists have paid attention to
making interlocked threaded structures for more than 50 years,
not only because of their aesthetic beauty but also due to their
unique applications.1 As one type of threaded structures, the
pseudorotaxanes architecture is considered as a versatile platform
to construct functional artificial nanomachines. Up to now, the
main hostguest recognition motifs used for fabrication of the
threaded structures are crown ether/paraquat,2 crown
ether/secondary
ammonium
salts,3
cryptand/paraquat,4
cyclodextrins/hydrophobic compounds,5 calixarene/paraquat,6
and cucurbituril/paraquat or secondary ammonium salts.7 These
recognition motifs are mainly based on hydrogen bonding,
stacking, charge transfer, and hydrophilichydrophobic
interactions. Pillararenes are a new generation of macrocyclic
hosts for supramolecular chemistry after crown ethers,
cyclodextrins, calixarenes, and cucurbiturils,8 therefore, the
threaded structures formed by pillararene-based hostguest
recognition motifs are relatively less reported.
Pseudorotaxanes may be viewed as prototypes of molecular
machines because of their reversible assembly/disassembly and
shuttling movement under external stimuli. In some cases, their
photophysical properties are influenced along with the kinetic
process, making them sensitive analytical tools in many areas.9
They can be used as chemical sensors when fluorescent signaling
elements are involved. In 2001, a phenomenon of aggregationinduced emission (AIE) was observed by Tang et al. in some
propeller-like molecules,10 such as tetraphenylethene (TPE) and
hexaphenylsilole. These luminogens are nonemissive in good
solvents, but become highly luminescent in the aggregated state.
Restriction of intramolecular rotation (RIR) in the aggregates has
been identified as the main cause for the AIE effect.10 In solution,
the active intramolecular rotation of the phenyl rings of AIE
molecules consumes energy. However, in the aggregated state,
This journal is The Royal Society of Chemistry [year]

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such motion is restricted, which blocks the nonradiative pathway

and activates radiative decay.10 Hostguest inclusion has attracted
considerable attention in recent years for its wide applications in
nano-machines, smart materials and so on.11 The guest molecules
are accommodated inside the cavity of the host driven by physical
interactions. Hence, the hostguest inclusion can be used to
restrict the motions of AIE molecules, giving birth to fluorescent
pseudorotaxanes.

Self-Assembly

Fluorescent

Nonfluorescent

Scheme 1. Chemical structures of 1, 2 and 3 and cartoon representation of

the pH-controlled complexation between 1 and 3.

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Based on the above knowledge, the utilization of the

recognition of cationic water-soluble pillar[5]arene 1 to TPE
derivatives 2 can be a good method to prepare a fluorescent
pseudorotaxane (Scheme 1). Herein, we report a simple strategy,
based on the hostguest complexation between 1 and a TPE
derivative 2, to tune the emission behaviour of 2 in dilute aqueous
solution. The spontaneously formed [5]pseudorotaxane units
efficiently restricted the intramolecular rotation and the nonradiative relaxation channel, thereby resulting in the strong
emission of 2 in dilute solution.10 Furthermore, due to the pHresponsiveness of the water-soluble pillar[5]arene-based host
guest interactions, the complex can be disassembled by adding
acid, releasing the captured TPE derivative and decreasing the
fluorescence intensity. The complex can reassembled through the
addition of base, recapturing TPE derivative and increasing the
fluorescence intensity.

[journal], [year], [vol], 0000 | 1

ChemComm Accepted Manuscript

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A pH-responsive fluorescent [5]Pseudorotaxane formed by self-assembly

of cationic water-soluble pillar[5]arenes and a tetraphenylethene
derivative

ChemComm

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DOI: 10.1039/C5CC04720J

in D2O at 298 K provides further evidence for the formation of

the threaded structure (Figure 3). It is evident from the spectrum
that all the peaks correlated to the signals in the chemical shift
dimensions are in a horizontal line. Thus, all proton signals due to
the 1 and 2 displayed the same diffusion co-efficient, supporting
their participation in a common aggregate.

Fig. 1 Partial 1H NMR spectra (500 MHz, D2O, 298 K): a) 3.00 mM 2; (b)
12.0 mM 1 and 3.00 mM 2; (c) 12.0 mM 1.

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1 and 2 were prepared according to the previous work.12 Firstly,

H NMR experiments were carried out to investigate the host
guest complexation between 1 and 2 (Fig. 1). The proton NMR
spectra of 1, 2, and a mixture of 12.0 mM 1 and 3.00 mM 2
showed that this complexation system is fast exchanged on the
proton NMR time scale. Significant chemical shift changes were
observed for some protons on 1 and 2 after complexation (Fig. 1).
Upfield shifts were observed for H6H8 of 2. Downfield shifts of
the protons H3 of 1 were observed. From the 2D NOESY
spectrum (Fig. 2) of a mixture of 12.0 mM 1 and 3.0 mM 2 in
D2O, correlations were observed between protons H5 of 1 and
protons H6 and H7 of 2, suggesting the hostguest complexation
between 1 and 2. Therefore, we concluded the formation of the
inclusion complex between 1 and 2 in water.
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Fig. 3 Partial DOSY spectrum (500 MHz, D2O, 298 K) of a mixture of

12.0 mM 1 and 3.00 mM 2.

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Fig. 2 Partial NOESY spectrum (500 MHz, D2O, 298 K) of a mixture of

12.0 mM 1 and 3.00 mM 2.

The proton NMR spectrum of an equimolar (3.00 mM) D2O

solution of 1 with 3 was also investigated and similar
complexation-induced chemical shift changes were observed (Fig.
S1, ESI). The ability of 1 to form a 1 : 1 complex with 3 was
assessed by 1H NMR titration of 3 into 1 in water and the
association constant (Ka) of 13 was calculated to be in water
using a nonlinear curve-fitting analysis (Fig. S2S3, ESI).
The DOSY NMR spectrum of an equimolar mixture of 1 and 2
2 | Journal Name, [year], [vol], 0000

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Furthermore, we envisioned that 2 might exhibit very strong

emission upon addition of 1, because the intramolecular rotation
of the phenyl rings of 2 will be inhibited by the formation of the
pseudorotaxane units. The fluorescence properties of 2.00 M 2
in the absence or presence of 1 in water were investigated (Fig.
4a). The intramolecular rotation of phenyl rings of 2 may induce
the efficient nonradiative annihilation process and thus 2 is nearly
nonemissive in water. However, upon the addition of 1, the
rotation of phenyl rings of 2 is restricted. Therefore, the
fluorescence intensity increased remarkably. The change of the
emission intensities nearly became constant when 32.0 M 1 was
added, and an approximate 15-fold fluorescence enhancement
was observed. In addition, when 2 was excited at 365 nm using a
UV lamp in the presence of 32.0 M 1, a strong cyan
fluorescence appeared, further supporting the proposed
mechanism (Fig. 4a).
It is well-known that anionic carboxylate groups and neutral
carboxylic groups can be interconverted by changing the
solution pH; thus the assembly and disassembly of the
complex 12 can be controlled by acid/base treatment. The
carboxylate groups of 2 can be changed to carboxylic groups
by adding aqueous HCl solution, making 2 precipitate in
water and leading to the disassembly of the complex 12.
This was easily observed by naked eyes since white
precipitate appeared after aqueous HCl solution was added
(Fig. 4b). Moreover, the fluorescence of the aqueous solution
vanished, and the precipitate showed strong fluorescence due
to the aggregation of neutralized 2 (Fig. 4b). However, after
the addition of NaOH, the white precipitate disappeared (Fig.
4b), indicating the recovery of the complex. Under this
condition, the rotation of phenyl rings of 2 was restricted
This journal is The Royal Society of Chemistry [year]

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Published on 22 June 2015. Downloaded by University of Louisville on 22/06/2015 20:11:52.

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Department of Chemistry, Taizhou University, Taizhou 318000, P. R.

China. 2Depatment of Chemistry, Zhejiang University, Hangzhou
310027, P. R. China.
E-mail: qizhongchou@tzc.edu.cn (Q. Zhou)
Fax: +86-576-8866-0177; Tel: +86-576-8866-0177
Electronic Supplementary Information (ESI) available: Synthetic
procedures, characterizations, Job plot, and UV-vis data. See DOI:
10.1039/c0xx00000x.
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Fig. 4 a) Fluorescence spectral changes of 2 (2.00 M) upon addition of 1

(0.0016.0 equiv.) in water (ex = 330 nm, em = 490 nm; slits, 5 nm/5
nm). b) Fluorescence spectral changes of the mixture of 2.00 M 2 and
32.0 M 1 upon the addition of aqueous HCl solution (60.0 M) and
subsequent addition of NaOH (60.0 M). The inset photographs show the
corresponding fluorescence changes upon excitation at 365 nm using a
UV lamp at 298 K.

In summary, we prepared a fluorescent pseudorotaxane formed

by self-assembly of cationic water-soluble pillar[5]arenes and a
tetraphenylethene derivative. The intramolecular rotation of the
phenyl rings of 2 was hampered upon the addition of 1, so the
complex emits strong fluorescence in dilute solution. Because of
the pH-responsiveness of the pillararene-based hostguest
interactions in water, the fluorescence of the pseudorotaxane can
be tuned by changing the solution pH, making it sensitive
analytical tool in many areas. We will also employ this strategy
of hostguest complexation induced emission in the construction
of responsive fluorescent materials in the future.
This work was supported by the Natural Science
Foundation of China (21172166, 21402137 and 21302135),
Natural Science Foundation of Zhejiang Province
(LY14B020012 and LQ13B010001), China Postdoctoral
Science Foundation (No. 2013M541456).

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Notes and references

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Journal Name, [year], [vol], 0000 | 3

ChemComm Accepted Manuscript

again, and the solution showed strong fluorescence (Fig. 4b).

This process was also evidenced by the chemical shift changes
in the proton NMR spectra (Fig. S4, ESI).

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455.

Colour Graphic

Fluorescent
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ChemComm Accepted Manuscript

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Self-Assembly

Nonfluorescent

Text:
A pH-responsive fluorescent [5]Pseudorotaxane formed by selfassembly of cationic water-soluble pillar[5]arenes and a
tetraphenylethene derivative was reported.

4 | Journal Name, [year], [vol], 0000

This journal is The Royal Society of Chemistry [year]