Tetraphenylethene modified [n]rotaxanes: Synthesis, characterization and aggregation-induced emission behavior

Article abstract of DOI:10.1039/c5ob00068h

A series of novel [n]rotaxanes based on a tetraphenylethene (TPE) backbone were constructed by a template-directed clipping approach and their structures were well-characterized. Investigation of their optical properties showed that these rotaxanes and th

Full text of DOI:10.1039/c5ob00068h

View Article Online
View Journal
Organic &
Biomolecular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Yin, G. Liu, D.
Wu, J. Liang, X. han and S. Liu, Org. Biomol. Chem., 2015, DOI: 10.1039/C5OB00068H.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/obc

Page 1 of 10
Organic & Biomolecular Chemistry
Journal Name
RSCPublishing
View Article Online
DOI: 10.1039/C5OB00068H
ARTICLE
Tetraphenylethene Modified [n]Rotaxanes: Synthesis,
Characterization and Aggregation-Induced Emission
Behaviors
Cite this: DOI: 10.1039/x0xx00000x
Guoxing Liu,† Di Wu,† Jinhua Liang, Xie Han, Sheng Hua Liu, Jun Yin*
Received 00th January 2012,
Accepted 00th January 2012
A series of novel [n]rotaxanes based on tetraphenylethene (TPE) backbone were constructed
by a template-directed clipping approach and their structures were well-characterized.
Investigation on optical properties showed that these rotaxanes and their corresponding
ammoniums had aggregation-induced emission (AIE) behaviors. However, there were obvious
differences as following: 1) rotaxanes occurred the aggregation state under the amount of less
water compared with the corresponding ammonium; 2) the rotaxanes with long alkoxyl chain
on the pyridine unit of crown ether formed the aggregation state under the amount of less water
than that of no alkoxyl-substituted rotaxanes and 3) nearer distance between TPE unit and N-
hetero crown ether component resulted in the aggregation state more easily than that of farther
distance. The result suggested that the mechanically interlocked structures can adjust the
aggregate state of AIE molecules.
DOI: 10.1039/x0xx00000x
www.rsc.org/
shielding host-guest complex. As a consequence, the AIE
property will be influenced by mechanical interaction. Herein,
Introduction
we design and synthesize three TPE molecules with an
ammonium moiety, in which the ammonium is employed as a
template to efficiently generate the mechanically interlocked
rotaxanes. Their photophysical properties indicated that the
target rotaxanes exhibited excellent aggregation-induced
emission effect, which make them act promising candidates as
AIE supermolecule materials with potential technological
applications. While this work was in progress, a closely-related
paper was published by Tang.14
Studies on the mechanically interlocked molecules (MIMs)
have become one of the popular topics of supramolecular
chemistry.1 Rotaxanes, one of the most important classes of
mechanically interlocked molecules, have deserved increasing
interest owing to their beautiful architectures, topological
importance and great applications in the fields of materials
science, nanotechnology, and biological science.2 Recently,
functional [n]rotaxanes possessing fluorescence have attracted
considerable attention.3
Since Tang’s group observed a novel phenomenon of
aggregation-induced emission (AIE) in 2001 4 and elaborated
the cause for the AIE phenomenon that was restriction of
intramolecular rotation (RIR).5 Lately, some fluorogens with an
AIE effect have attracted increasing interest ascribing to the
unique emission characterization.6 As a classic backbone,
tetraphenylethylene (TPE) is a typical AIE-active material.
Over the past several years, an abundant amount of researches
have been contributed to design and synthesize functional TPE-
based molecules with attractive optical properties. The unique
luminescence behaviour of TPE has been harnessed for the
development of solid state lighting materials,7 biological
sensors,8 chemosensors,9 explosive detection,10 latent finger
print11 and luminescent polymers.12
Results and discussion
To study impact of N-hetero crown ring on AIE behavior of
dialkylammonium salts based tetraphenylethene (TPE),
[2]rotaxanes 11a and 11b with N-hetero crown ether ring
adjacent to TPE stopper were designed and synthesized. The
synthetic protocol for rotaxanes 11 is outlined in Scheme 1.
Firstly, diphenylmethane
1
as starting material was reacted with
n
-BuLi in anhydrous THF at 0 °C for 1 h, then 4-
bromobenzophenone
2
was added and further stirred for 6 h to
. Subsequently, was refluxed in toluene
in the presence of p-toluene sulphonic acid to give the desired
15 Compound
was reacted with -BuLi in anhydrous THF at
-78 °C for 2 h, and then N-formylpiperidine was added to
obtain the corresponding aldehyde 5 16
Then, condensation of
with (3,5-dimethoxyphenyl)methanamine
obtain the alcohol
3
3
4
.
4
n
In our recent works, we have confirmed the mechanical
interaction can be used as an efficient strategy to adjust the
properties of photochromic materials owing to the formation of
pseudorotaxanes.13 For the TPE derivatives, we also want to
know if such mechanical interaction can modify the AIE
behavior. It is well known that TPE can induce the AIE
property due to the inhibition of bonds rotation of benzene rings.
.
aldehyde
5
6
produced the corresponding reversible dynamic imine, which
was reduced by NaBH4 in the solution of THF and MeOH, to
give the kinetically stable amine
7 in 82% yield. Protonation of
the free amine with excess trifluoroacetic acid (TFA) and
7-12
Exactly, rotaxane with mechanical interaction can form a
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 1

Organic & Biomolecular Chemistry
Page 2 of 10
Journal Name
ARTICLE
subsequent counter-ion exchange with saturated NH4PF6
solution afforded the dialkylammonium salt
8
in 95% yields for
View Article Online
DOI: 10.1039/C5OB00068H
Scheme 1. Synthesis of Rotaxanes 11.
Scheme 2. Synthesis of the macrocycles 13.
the two steps. Afterwards, the dynamic covalent chemistry such as NMR, mass spectrometry and elemental analyses (see
approach was adopted to bring about three-component self- Supporting Information).
assembly processes to afford [2]rotaxane 11. Compounds 9a
Following introduction of AIE-active tetraphenylethylene
and substituted dialdehyde 9b had been utilized to construct (TPE) units, the photoluminescence (PL) spectra and UV
[2]catenanes,17 hetero[n]rotaxanes,18 dendritic rotaxanes,19 spectra were studied in acetonitrile / water mixtures with
rotacatenanes,20 and others 13, 21 in our previous works. Herein, various water contents, to evaluate the AIE behaviors of salt
8
ammonium salt
clipping reaction with
then the mixture was treated with BH3·THF to afford However, when the water fraction exceeds 85%, the PL
[2]rotaxanes 11a-b in 85% and 82% yields, respectively. intensity rapidly increases. dramatic enhancement in
-hetero crown ethers 13a and luminescence is observed when the water fraction reaches 90%.
was synthesized to aid spectroscopic analysis of the As the compound is insoluble in water, increasing the water
8 was also subjected to perform the dynamic and rotaxanes 11a-b. As shown in Figure 2A, the solutions of
22
9
and 10 in anhydrous CH3CN, and salt 8 are not obviously emissive until fw was up to 80%.
A
22
Furthermore, for comparison,
13b
N
17
assembly processes, as outlined in Scheme 2. [2]rotaxane 11a fraction in the mixed solvent might change the form of the
1
was well depicted by 1H NMR spectra. From the H NMR compound from a dissolved or well-dispersed state in pure
(Figure 1), an obvious upfield shift was observed for the acetonitrile to aggregated particles in the mixtures with high
resonance of the protons on the stopper units (H2, H3, H6 and water content. The emission of salt
8 is thus caused by
H1) due to the shielding effect of the encircling crown ethers. aggregation, which is typically AIE active. In the acetonitrile
Furthermore, the resonances for the central methylene (H4 and solution, the multiple phenyls of TPE undergo active twisting
+
H5) shifted downfield. It was notable that protons NH2 in the motions against the 3, 5-dimethoxy phenyl units linked by the
+
template of rotaxane 11a could be detected at 8.85 ppm because dimethylammonium NH2 axis. In the aggregates, the
of the stabilizing effect of the hydrogen bonding interactions of intramolecular rotations are restricted, thus turning on the
the oxygen atoms on N-hetero crown ether 13a with the emission of the dialkylammonium salt 11. It is known that the
ammonium hydrogen atoms. In addition, [2]rotaxane 11b molecular size and effect of steric hindrance influence their
displayed some similar shifts with [2]rotaxane 11a. Further rotation, and a larger molecule should have lower freedom of
proof was proved by MALDI-MS in acetonitrile. The peak at rotation.23 Subsequently, the photolumminescence of
- +
m/z 991.61 and 1203.76 can be assigned to the [M-PF6 ]
[2]rotaxanes 11a and 11b were also investigated. As shown in
species, in which
M
was [2]rotaxanes 11a and 11b
,
Figure 2B and 2C, when the water fraction reaches 80% and
respectively. The chemical structures of all the new compounds 70%, respectively, the fluorescence intensity of 11a-b is found
were confirmed by standard spectroscopic characterizations,
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 3 of 10
Journal Name
Organic & Biomolecular Chemistry
ARTICLE
to rapidly get enhanced, which implies [2]rotaxanes 11a-b arise
aggregation state more easily in acetonitrile in comparison to
View Article Online
DOI: 10.1039/C5OB00068H
Figure 1. 1H NMR spectra (600 MHz in CD3CN at rt) of 13a (A); 11a (B);
8 (C); 11b (D) and 13b (E).
1.2x107
4.0x106
3.5x106
3.0x106
2.5x106
2.0x106
1.5x106
1.0x106
7x106
6x106
5x106
4x106
3x106
2x106
f
(vol%)
f
(vol%)
w
f
(vol%)
w
w
1.0x107
8.0x106
6.0x106
4.0x106
A
0
B
C
0
0
30
50
60
70
75
80
85
90
95
30
50
60
70
75
80
85
90
95
30
50
60
70
75
80
85
90
95
2.0x106
0.0
1x106
0
5.0x105
0.0
375 400 425 450 475 500 525 550 575 600 625
Wavelength(nm)
375 400 425 450 475 500 525 550 575 600 625
Wavelength(nm)
375 400 425 450 475 500 525 550 575 600 625
Wavelength(nm)
Figure 2. PL spectra of 8 (A), 11a (B) and 11b (C) in CH3CN / water mixtures with different water fractions.
Figure 3. Photographs of 8(A), 11a(B) and 11b(C) in CH3CN /
water mixtures with different fractions of water (fw) taken under UV
illumination.
corresponding ammonium. Moreover, rotaxane 11b with long
alkyl chain displays more significant compared with 11a
Further proofs were supplied by UV-vis absorption spectra of
.
,
8
11a and 11b in different water fraction. The level-off tails are
found at the longer wavelength region when water fraction up
to 70%. Such tails are commonly observed in nanoparticle
suspensions and are attributed to the light scattering effect of
the aggregates. (Figure S1) As shown in Figure 3A-C,
photographs of them in different water fraction furnish further
critical evidence to manifest their different levels of AIE
behavior. In view of the effect of molecular structures towards
AIE behavior, we consult a theoretical DFT calculation by
using Gaussian 09 programs at the B3LYP/6-31G* level. As
shown in Figure S2, the host macrocycles have a large overlap
with TPE group in 11a-b. The introduce of long alkyl chain in
11b made the host macrocycles have a larger overlap with TPE
group than that of 11a which result in the AIE phenomena of
11b came early than that of 11a. In all, the AIE phenomena of
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3

Organic & Biomolecular Chemistry
Page 4 of 10
Journal Name
ARTICLE
11a-b came early than that of ammonium salt
introducing of host macrocycles.
8 due to the
To further confirm the results described above,
a
symmetrical [3]rotaxane 17 with similar molecular feature as
View Article Online
[2]rotaxanes 11 that host macrocycle adjacent to TPE unit was
DOI: 10.1039/C5OB00068H
Scheme 3. Synthesis of Rotaxanes 17.
1.0x107
8.0x106
6.0x106
4.0x106
1.2x107
f
(vol%)
f
(vol%)
f
(vol%)
w
w
1.0x107
8.0x106
6.0x106
4.0x106
w
A
B
C
0
0
0
1.0x107
8.0x106
6.0x106
4.0x106
30
50
60
70
75
80
85
90
95
30
50
60
70
75
80
85
90
95
30
50
60
70
75
80
85
90
95
2.0x106
2.0x106
2.0x106
0.0
0.0
0.0
375 400 425 450 475 500 525 550 575 600 625 650
Wavelength(nm)
375 400 425 450 475 500 525 550 575 600 625 650
Wavelength(nm)
375 400 425 450 475 500 525 550 575 600 625 650
Wavelength(nm)
Figure 4. PL spectra of 16 (A), 17a (B) and 17b (C) in CH3CN / water mixtures with different water fractions.
of aldehyde with hexane-1, 6-diamine 14 produced the
5
corresponding reversible dynamic imine, which was reduced by
NaBH4, to afford the kinetically stable amine. In consideration
of convenient purification, the NH of free amines was protected
by the Boc2O before purification. Then, the Boc-protected
alkylamines 15 were obtained in overall yield of 76% for the
two steps. The Boc protective group was removed with excess
trifluoroacetic acid (TFA) in dry dichloromethane, and the
amine generated was simultaneously protonated. Subsequent
counterion exchange with saturated NH4PF6 solution afforded
ammonium salt 16 in 92% yield. Then ammonium salt 16 was
also subjected to perform the dynamic clipping reaction with
9
and 10 in anhydrous CH3CN, and then the mixture was treated
with BH3•THF to afford [3]rotaxanes 17a and 17b were
prepared by using same method in 55% and 48% yields,
respectively. Evidence for the formation of 17a and 17b in this
process came from analysis of their 1H NMR spectrum.
[3]rotaxane 17a is shown in Figure S3-A, and compared with
the spectrum of template 16 (Figure S3-B), the resonance of the
methylene protons (H2') displayed a downfield shift while the
protons on the stopper units (H1') showed an obvious upfield
Figure 5. Photographs of 16(A), 17a(B) and 17b(C) in CH3CN /
water mixtures with different fractions of water (fw) taken under UV
illumination.
+
shift. Moreover notably, the ammonium (NH2 ) is detected at
designed and synthesized. Similarly, the synthesis of
8.66 ppm. These results indicated that the N-hetero crown ether
[3]rotaxanes 17a and 17b is outlined in Scheme 3, condensation
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 5 of 10
Journal Name
Organic & Biomolecular Chemistry
ARTICLE
1
- +
encircled the site of ammonium. The investigation on the H ]+, 1763.98 for [M - HPF6 - PF6 ] and 2188.52 for [M - HPF6 -
- +
NMR indicated that [3]rotaxane 17b had similar shifts in PF6 ] could be detected, which further confirmed the formation
comparison to 17a. Further proof was proved by MALDI-MS
in acetonitrile. For example, the peak at 1909.91 for [M - PF6
View Article Online
DOI: 10.1039/C5OB00068H
-
Scheme 4. Synthesis of Rotaxanes 25.
Figure 6. 1H NMR spectra (600 MHz in CD3CN at rt) of 25a (A); 24 (B) and 25b (C).
7x106
6x106
5x106
4x106
3x106
2x106
f
(vol%)
f
(vol)
5x106
4x106
3x106
2x106
w
w
f
(vol%)
2.0x106
1.5x106
1.0x106
C
B
w
A
0
0
0
30
50
60
70
75
80
85
90
95
30
50
60
70
75
80
85
90
95
30
50
60
70
75
80
85
90
95
5.0x105
0.0
1x106
1x106
0
0
375 400 425 450 475 500 525 550 575 600 625 650
Wavelength(nm)
375 400 425 450 475 500 525 550 575 600 625 650
Wavelength(nm)
400 425 450 475 500 525 550 575 600 625 650
Wavelength(nm)
Figure 7. PL spectra of 24(A), 25a (B) and 25b (C) in CH3CN / water mixtures with different water fractions.
Then, [3]rotaxanes 17a-b and the corresponding ammonium 16
of [3]rotaxanes 17a-b successfully. (see supporting
were also studied in the photoluminescence spectra and UV
information).
spectra. As shown in Figure 4A-C, the emission from the
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 5

Organic & Biomolecular Chemistry
Page 6 of 10
Journal Name
ARTICLE
acetonitrile solution of the ammonium 16 was so weak that rotaxane 25a could be observed at 8.83 ppm due to the same
almost no photoluminescence signal was observed. However, a reason as [2]rotaxanes 11a and 11b. Moreover the similar
dramatic enhancement of luminescence could be observed chemical shift changes for characteristicDpOroI:t1o0n.1s03o9Vn/ieC[w25AO]rrtBoic0tle0aO0x6nal8ninHee
when the water fraction in the acetonitrile solution exceeded 25b were detected. These results described above were in good
17-20, 25
85%. Meanwhile, with regard to [3]rotaxanes 17a-b, the PL agreement with a wealth of published literature.13,
intensity of them was observed to get significantly enhanced, Additional evidence supporting this conclusion comes from
when water fraction reached 75% and 70%, respectively. analysis of the MALDI mass spectrum, which contains peaks at
Further, we found that [3]rotaxanes 17a-b arise aggregation m/z 1328.58 and 1395.92 that correspond to - PF6 salts of
state more easily by a comparison of salt 16.( Figure 5A-C). [2]rotaxanes 25a and 25b, respectively.
Similar to [2]rotaxanes 11a-b
,
these [n]rotaxanes with
Subsequently, we studied the AIE behaviors of salt 24 and
molecular feature that N-hetero crown ether ring adjacent to [2]rotaxanes 25a-b. As could be observed in Figure 7A-C, the
TPE stopper arise aggregation state more easily than three compounds arise aggregation state nearly simultaneously
corresponding ammonium salts. Accordingly, it is concluded that the PL curves of them are basically flat lines paralleled to
that the non-covalent mechanical interaction can affect the abscissa with water fraction of acetonitrile/water mixture
molecular AIE behavior, despite they possess similar UV/vis increased from 0% to 60% and that notably the PL intensity of
absorption spectra (Figure S1). For ammonium and rotaxanes, them all dramatically jumps with the increase in water fraction
the existence of host macrocycles in rotaxanes will affect the up to 70%. The PL spectra of them all indicate similar AIE
rotation of TPE moiety due to near distance between the behaviors (Figure S4). And they also revealed similar UV-vis
template ammonium and TPE unit. The rotaxanes 11b and 17b absorption (Figure S1). The optimized structures of 25a-b
with long alkoxyl chain on the pyridine unit of crown ether showed that there was no obvious overlap between the host
arise aggregation state more easily than no alkoxyl-substituted macrocycles and TPE groups as shown in Figure S2. These
rotaxanes 11a and 17a, which was possibly attributed to the investigations suggest that the mechanical interaction can
effect of longer alkoxyl chains for TPE moiety. The theoretical change the AIE behavior when the host macrocycle is nearby
DFT calculation results were record (ESI in Figure S2), the the TPE moiety. Moreover, the functional group such as
results were similar to that of
8, 11a-b. According to the alkoxyl group on the pyridine unit of macrocycle component
optimized structures, we find that the crown ether components also has influence on the AIE behavior and this may due to the
of 17a and 17b wrap a benzene ring of TPE moiety, which will hydrophilic character of the alkoxyl group.
affect the rotation of TPE. As a hydrophobic group, the
From the above, [2]rotaxanes 11a-b and [3]rotaxanes 17a-b
introduction of long alkoxyl chain on host crown ether with the molecular feature that N-hetero crown ether ring
component of 17b makes the crown ether components have a adjacent to TPE unit arise aggregation state more easily in
larger shielding than that of 17a, resulting in the aggregation comparison to the corresponding ammonium, respectively.
state more easily.
However, [2]rotaxanes 25a and 25b in which host macrocycle
For confirming the effect of alkoxyl chain on the pyridine, located at the far position of TPE have similar AIE behavior as
we deign and synthesize another ammonium, in which, the template 24. In other words, N-hetero crown ether ring has
ammonium template lies in far position from TPE moiety. The great influence on AIE behavior of the template based on TPE,
stepwise synthesis of rotaxanes 25a-b is depicted in Scheme 4. as the ring is close to TPE; On the contrary, if the ring is far
Firstly,
the
intermediate
1-(4-hydroxyphenyl)-1,2,2- from TPE, there is little influence on AIE behavior of
triphenylethene 20 was prepared by cross-coupling of 4- ammonium salt.
hydroxyl-phenylbenzophenone 18 and benzophenone 19 using
Zn powder as the catalyst.24 Subsequently, the alcohol 20 was
converted to compound 22 upon treatment with 21 in DMF in
Conclusions
In summary, a series of novel AIE-active [n]rotaxanes have
been successfully developed in this work. Owing to
introduction of tetraphenylethene (TPE) units, it endows
the presence of K2CO3 in 75% yield. Similarly, the ammonium
24 was prepared by condensation of aldehyde 22 and
6
followed by reduction, protonation, and counterion exchange.
Afterwards, the similar clipping reaction was further performed
to synthesize [2]rotaxanes 25a and 25b in yields of 78% and
73%, respectively. Evidence for the formation of 25a and 25b
[n]rotaxanes
predominant
photophysical
properties.
Photoluminescence and UV-vis properties of the rotaxanes and
their templates were investigated. To our excitement, these
[n]rotaxanes express perfect aggregation-induce emission (AIE)
effect. Meanwhile, It is noteworthy that [n]rotaxanes with
characteristic of N-hetero crown ether ring adjacent to TPE
stopper arise aggregation state more easily than their
1
in this process came from analysis of their H NMR spectrum.
As shown in Figure 6, an investigation of the 1H NMR
manifested that an obvious downfield shifts for the methylene
protons (H4'' and H5'') and upfield shifts for benzene ring protons
(H2'', H3'', H6'', H7'') on benzene rings of 25a and 25b by a
comparison of the spectra of 24, which indicated that the crown
ether unit encircled the site of ammonium template. Meanwhile,
methyl protons (H1'') on the stopper unit displayed obvious
corresponding ammonium salts;
[n]rotaxanes with host
macrocircle distant to TPE stopper show same AIE behavior as
corresponding ammonium salt. The present results may provide
a novel perspective for the design and construct of AIE-active
mechanically interlocked molecules. Further work will focus on
their functionalization and application, such as preparing
+
upfield shifts. In addition, protons NH2 in the template of
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 7 of 10
Journal Name
Organic & Biomolecular Chemistry
ARTICLE
·THF solution
dynamic AIE-active supramolecular materials, AIE-active atmosphere at room temperature. Then 1M BH3
fluorescent supramolecular biosensor.
(1.6 mL) was added and the mixture was further stirred
View Article Online
overnight. The solvents were removed under vacuum and the
DOI: 10.1039/C5OB00068H
residue was purified by column chromatography (silica gel,
Experimental Section
DCM / MeCN / MeOH = 100 : 0 : 0 ~ 75 : 25 : 1) to give the
General Methods. All manipulations were carried out under an
argon atmosphere by using standard Schlenk techniques, unless
otherwise stated. THF was distilled under argon atmosphere
from sodium-benzophenone. Compound 21 was prepared by
literature methods.26 All other starting materials were obtained
commercially as analytical-grade and used without further
purification. 1H NMR spectra were collected with Varian
Mercury Plus 400 MHz or 600 MHz spectrometer, while 13C
NMR spectra were collected with a 400 MHz spectrometer.
Mass spectra were all measured with the ultrafleXtreme
MALDI-TOF-TOF. UV−vis spectra were obtained on a
[2]rotaxane 11a, rf=0.67. Yield: 193 mg, 85%. Compound of
11a: 1H NMR (600 MHz, CD3CN). δ 8.85 (s, 2H), 7.80 (t,
J =
7.8 Hz, 1H), 7.37 (d,
- 7.11 (m, 3H), 7.05 - 7.02 (m, 3H), 7.00 - 6.97 (m, 6H), 6.78
(d, = 7.8 Hz, 2H), 6.70 – 6.68 (m, 8H), 6.38 (d, = 4.8 Hz,
2H), 6.21 (s, 1H), 6.01 (s, 2H), 4.46 (s, 4H), 4.34 (s, 2H), 4.12 –
4.10 (m, 2H), 4.03 (d, = 11.4 Hz, 2H), 3.87 – 3.85 (m, 4H),
3.82 (d, = 6.6
J = 7.8 Hz, 2H), 7.15 - 7.14 (m, 2H), 7.12
J
J
J
J
= 3.0 Hz, 1H), 3.70 – 3.67 (m, 6H), 3.64 (d, J
Hz, 3H), 3.36 (s, 6H). 13C NMR (100 MHz, CD3CN) δ 161.5,
159.3, 147.5, 145.1, 144.0, 143.9, 143.9, 137.5, 134.9, 132.0,
131.4, 131.3, 131.2, 129.4, 128.5, 128.4, 127.3, 127.3, 122.7,
121.9, 120.3, 119.2, 113.3, 110.8, 107.1, 101.4, 71.9, 71.6,
71.0, 68.1, 55.5, 53.0, 52.8, 50.4. MALDI MS: m/z = 991.61 [M
Shimadzu UV-3600 UV/Vis/NIR spectrophotometer
,
and
fluorescence spectra were taken on a Hitachi Model F-4500
fluorescent spectrophotometer. The elemental analyses were
-
– PF6 ]; calculated exact mass: 1136.47. Anal. Calcd for
C63H67F6N4O7P: C, 66.54; H, 5.94; N, 4.93. Found: C, 66.65;
H, 5.84; N, 4.88.
obtained on Vario EL
Ⅲ
CHNSO.
Synthesis of 7. A mixture of
5
(0.36 g, 1.0 mmol) and
6 (0.17
Synthesis of [2]rotaxane 11b. A mixture of salt
8 (131 mg,
g, 1.0 mmol) in dry toluene (50 mL) into a 100 mL round-
bottom flask was refluxed for 24 h under argon atmosphere.
The solvent was removed under vacuum and the residue was
dissolved in THF (30 mL) and MeOH (30 mL), and then
NaBH4 (0.38 g, 10.0 mmol) was added in portions. After
stirring for overnight, the solvents were removed under
vacuum, and the residue was extracted by dichloromethane
(DCM). The organic layer was washed by brine till clear, dried
over anhydrous Na2SO4. Removal of solvent under reduced
pressure and purification on a silicagel column using petroleum
ether / ethyl acetate (4 : 1) as the eluent give a kinetically stable
0.20 mmol), tetraethyleneglycol bis(2-aminophenyl)ether 10
(75 mg, 0.20 mmol) and 2,6-pyridinedicarboxaldehyde
derivative 9b (70 mg, 0.20 mmol) were stirred for 48 h in dry
CH3CN (10 mL) under argon atmosphere at room temperature.
Then 1M BH3·THF solution (1.6 mL) was added and the
mixture was further stirred overnight. The solvents were
removed under vacuum and the residue was purified by column
chromatography (silica gel, DCM / MeCN / MeOH = 100 : 0 : 0
~ 75 : 25 : 1) to give the [2]rotaxane 11b, rf=0.48. Yield: 221
mg, 82%
8.90 (s, 2H), 7.15 (d,
7.2 Hz, 3H), 6.99 – 6.97 (m, 6H), 6.89 (s, 2H), 6.77 (d,
Hz, 2H), 6.68 (s, 8H), 6.41(t, = 3.6 Hz, 2H), 6.20 (s, 1H), 6.02
(s, 2H), 4.46 – 4.41 (m, 4H), 4.28 (s, 2H), 4.14 (t, = 6.0 Hz,
2H), 4.09 (br, 2H), 4.02 (d, = 10.8 Hz, 2H), 3.87 (br, 4H),
3.76 (d, = 13.8 Hz, 2H), 3.69 (br, 6H), 3.54 (d, = 16.8 Hz,
2H), 3.37 (s, 6H), 1.84 – 1.82 (m, 2H), 1.52 – 1.48 (m, 2H),
.
Compound of 11b: 1H NMR (600 MHz, CD3CN) δ
J
= 7.2 Hz, 3H), 7.11 (br, 3H), 7.04 (d,
J =
amine
Compound
6.97 (m, 19H), 6.48 (d,
7 as a low yellowish solid, rf=0.54. Yield: 0.42 g, 82%.
1
J
= 7.2
7
: H NMR (400 MHz, CDCl3): δ ppm = 7.09 –
= 2.0 Hz, 2H), 6.36 (t, = 2.0 Hz,
J
J
J
1H), 3.78 (s, 6H), 3.70 (s, 4H). 13C NMR (100 MHz, CDCl3): δ
ppm = 160.8, 143.7, 143.7, 142.4, 140.8, 140.7, 138.0, 131.3,
131.3, 127.6, 127.5, 126.3, 106.0, 99.0, 55.3, 53.0, 52.6.
MALDI MS: m/z = 512.21 [M + H+]; calculated exact mass:
511.25. Anal. Calcd for C36H33NO2: C, 84.51; H, 6.50; N, 2.74.
Found: C, 84.58; H, 6.61; N, 2.68.
J
J
J
J
1.42 – 1.40 (m, 2H), 1.29 (br, 18H), 0.89 (t,
J = 7.2 Hz, 3H).
13C NMR (100 MHz, CD3CN ) δ 167.2, 161.5, 161.1, 147.4,
145.0, 144.0, 143.9, 143.9, 142.5, 140.7, 137.6, 134.9, 131.9,
131.4, 131.3, 131.2, 129.4, 128.5, 128.3, 127.2, 121.9, 120.2,
113.2, 110.8, 108.9, 107.2, 101.4, 71.9, 71.6, 70.9, 68.1, 68.1,
55.5, 53.0, 52.8, 50.4, 32.3, 30.0, 29.7, 29.7, 29.2, 26.3, 23.0,
Synthesis of 8. To a solution of the amine
in dry DCM (20 mL), TFA (0.32 mL, 5.0 mmol) was added at
room temperature. After stirring for under argon
atmosphere, the solvent was removed under vacuum. The
residue was dissolved in MeOH (5.0 mL), and then saturated
NH4PF6 (20.0 mL, aq) was added to yield a off-white
precipitate. After filtering, washing with H2O and dry under
7 (0.51 g, 1.0 mmol)
2
h
-
14.1. MALDI MS: m/z = 1203.76 [M – PF6 ]; calculated exact
mass: 1348.68. Anal. Calcd for C77H95F6N4O8P: C, 68.53; H,
7.10; N, 4.15. Found: C, 68.61; H, 7.19; N, 4.10.
Synthesis of 15. A mixture of
5 (0.72 g, 2.0 mmol) and 14
vacuum, the title compound
solid, rf=0.66. Yield: 0.62 g, 95%. Compound
8
was obtained as an off-white
(0.12 g, 1.0 mmol) in dry toluene (60 mL) into a 100 mL round-
bottom flask was refuxed for 24 h under argon atmosphere. The
solvent was removed under vacuum and the residue was
dissolved in THF (30 mL) and MeOH (30 mL), and then
NaBH4 (0.31 g, 8.0 mmol) was added in portions. After stirring
for overnight, the solvents were removed under vacuum, and
the residue was extracted by dichloromethane (DCM). The
organic layer was washed by brine till clear, dried over
anhydrous Na2SO4 and concentrated in vacuo to give a
kinetically stable amine as a low yellowish oil. The unpurified
amine was dissolved in dry chloroform (20 mL), and then
Boc2O (1.76 g, 8.0 mmol) and triethylamine (0.86 mL) were
added. The mixture was stirred at room temperature for 24 h.
Removal of solvent under reduced pressure and purification on
8
: 1H NMR (600
MHz, CD3CN): δ 7.19 (d,
= 7.8 Hz, 2H), 7.05 (d,
J
= 7.8 Hz, 2H), 7.14 (s, 9H), 7.10 (d,
J
J = 6.0 Hz, 6H), 6.55 (s, 2H), 6.52 (s,
1H), 4.01 (s, 2H), 3.96 (s, 2H), 3.78 (s, 6H). 13C NMR (100
MHz, CDCl3) δ 161.3, 145.3, 143.3, 143.1, 142.9, 141.9, 139.8,
133.1, 132.1, 131.1, 128.9, 128.9, 128.8, 127.7, 127.6, 126.6,
107.0, 101.5, 55.4, 50.7, 50.5. MALDI MS: m/z = 512.31[M –
-
PF6 ]; calculated exact mass: 657.22. Anal. Calcd for
C36H34F6NO2P: C, 65.75; H, 5.21; N, 2.13. Found: C, 65.69; H,
5.11; N, 2.22.
Synthesis of [2]rotaxane 11a. A mixture of salt
8 (131 mg, 0.2
mmol), tetraethyleneglycol bis(2-aminophenyl)ether 10 (75 mg,
0.2 mmol) and 2,6-pyridinedicarboxaldehyde 9a (27 mg, 0.2
mmol) were stirred for 48 h in dry CH3CN (10 mL) under argon
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 7

Organic & Biomolecular Chemistry
Page 8 of 10
Journal Name
ARTICLE
a silicagel column using petroleum ether / ethyl acetate (4 : 1) ~ 75 : 25 : 1) to give the [3]rotaxane 2b, rf=0.56. Yield:119 mg,
as the eluent obtained the Boc-protected 15 as a white solid, 48%. Compound of 17b: 1H NMR (600 MHz, CD3CN) δ 8.65
View Article Online
rf=0.76. Yield: 0.76 g, 76%. Compound 15
MHz, CDCl3) δ 7.08 - 7.01 (m, 38H), 4.30 (d,
3.10 (d, = 49.2 Hz, 4H), 1.45 (s, 9H), 1.37 (s, 9H), 1.21 (br, Hz, 2H), 6.78(br, 2), 6.73 (br, 4H), 6.48 (s, 4H), 4.68 (br, 2H),
8H). 13C NMR (100 MHz, CDCl3) δ 143.6, 142.5, 140.9, 140.6, 4.57 (s, 1H), 4.31 (t,
= 6.6 Hz, 3H), 4.21 (br, 15H), 4.07 (s,
: J = 8.4 Hz,
1H NMR (400 (s, 4H), 7.14 - 7.13 (m, 21H), 7.10 (br, 3H), 7.06 (d,
J
= 28.4 Hz, 4H), 5H), 7.02 (br, 8H), 6.99 (br, 5H), 6.91 (br, 4H), 6.85 (d,
DOI: 10.1039/C5OBJ00=0668.H6
J
J
131.3, 127.6, 126.4, 79.4, 28.4, 28.1, 26.6. MALDI MS: m/z
=
2H), 3.91 (br, 9H), 3.73 (s, 1H), 3.64 – 3.58 (m, 12H), 3.43 (br,
1028.01[M + Na+]; calculated exact mass: 1004.55. Anal. Calcd 7H), 1.87 (br, 4H), 1.53 – 1.48 (m, 4H), 1.42 – 1.38 (m, 4H),
for C70H72N2O4: C, 83.63; H, 7.22; N, 2.79. Found: C, 83.71; 1.29 (br, 40H), 0.90 – 0.88 (m, 10H). 13C NMR (100 MHz,
H, 7.26; N, 2.69.
CD3CN) δ 147.6, 145.4, 144.5, 144.2, 144.1, 144.1, 142.6,
141.2, 140.9, 138.2, 133.7, 132.1, 131.6, 131.4, 130.0, 128.7,
128.6, 128.5, 127.4, 122.6, 120.7, 113.9, 105.1, 71.7, 71.3,
71.1, 70.7, 49.2, 32.4, 30.1, 29.8, 29.7, 26.3, 23.2, 14.2.
MALDI MS: m/z = 2188.52 [M - HPF6 - PF6 ]; calculated exact
mass: 2479.30. Anal. Calcd for C142H180F12N8O12P2: C, 68.75;
H, 7.31; N, 4.52. Found: C, 68.71; H, 7.39; N, 4.45.
Synthesis of 16. To a solution of the Boc-protected amine 15
(1.00 g, 1.0 mmol) in dry DCM (20 mL), TFA (0.64 mL, 10.0
mmol) was added at room tempeature. After stirring for 2 h
under argon atmosphere, the solvent was removed under
vacuum. The residue was dissolved in MeOH (5.0 mL), and
then saturated NH4PF6 (30.0 mL, aq) was added to yield a off-
-
white precipitate. After filtering, washing with H2O and dry Synthesis of 22. In a 250 mL two-necked, round-bottom flask
under vacuum, the title compound 16 was obtained as an off- equipped with a magnetic stirrer a mixture of 20 (0.70 g, 2.0
1
white solid, rf=0.65. Yield: 1.01 g, 92%. Compound of 16. H mmol ), 21 (0.57 g, 2.0 mmol) and potassium carbonate (0.55 g,
NMR (600 MHz, CD3CN) δ 7.19 (br, 2H), 7.14 (br, 17H), 7.10 4.0 mmol) was placed, then 150 mL DMF was added. The
(br, 5H), 7.04 (br, 14H), 3.97 (s, 4H), 2.85 (br, 4H), 1.60 (br, reaction was stirred for 24 h at 50 °C under an argon
4H), 1.32 (br, 4H). 13C NMR (100 MHz, CD3CN) δ 145.2, atmosphere. The resulting mixture was allowed to cool to room
144.0, 142.3, 140.8, 131.4, 128.4, 127.2, 51.7, 47.9, 26.3, 25.9. temperature, and filtered. After that, the solvent were removed
-
MALDI MS: m/z = 805.55[M - HPF6 - PF6 ]; calculated exact under vacuum, and the residue was extracted by ethyl acetate,
mass: 1096.39. Anal. Calcd for C60H58F12N2P2: C, 65.69; H, and then dried over anhydrous Na2SO4. Upon removed of
5.33; N, 2.55. Found: C, 65.59; H, 5.25; N, 2.63.
solvent under reduced pressure and purified on a silica gel
column using petroleum ether / ethyl acetate (4 : 1) as the
eluent to obtain the compound 22 as a low yellow oil, rf=0.69.
Yield: 0.83 g, 75%. Compound of 22: 1H NMR (400 MHz,
Synthesis of [3]rotaxane 17a. A mixture of salt 16 (110 mg,
0.1 mmol), tetraethyleneglycol bis(2-aminophenyl)ether 10 (75
mg, 0.2 mmol) and 2,6-pyridinedicarboxaldehyde 9a (27 mg,
0.2 mmol) were stirred for 72 h in dry CH3CN (10 mL) under
CDCl3) δ 9.88 (s, 1H), 7.82 (d,
17H), 6.92 (d, = 8.4 Hz, 2H), 6.62 (d,
2H), 3.89 (s, 2H), 1.81 (d,
= 25.2 Hz, 4H), 1.53 (s, 4H). 13C
J
= 8.4 Hz, 2H), 7.08 – 6.97 (m,
J
J
= 8.0 Hz, 2H), 4.05 (s,
argon atmosphere at room temperature. Then 1M BH3·THF
J
solution (1.6 mL) was added and the mixture was further stirred
overnight. The solvents were removed under vacuum and the
residue was purified by column chromatography (silica gel,
DCM / MeCN / MeOH = 100 : 0 : 0 ~ 75 : 25 : 1) to give the
[3]rotaxane 17a, rf=0.56. Yield: 113 mg, 55%. Compound of
NMR (100 MHz, CDCl3) δ 190.8, 164.1, 157.5, 143.9, 140.5,
140.0, 135.9, 132.5, 132.0, 131.3, 129.7, 127.7, 127.5, 126.3,
126.2, 114.7, 113.5, 68.2, 67.5, 29.2, 29.0, 25.8. MALDI MS:
m/z = 552.31 [M]; calculated exact mass: 552.27. Anal. Calcd
for C39H36O3: C, 84.75; H, 6.57. Found: C, 84.68; H, 6.68.
17a: 1H NMR (600 MHz, CD3CN) δ 8.66 (s, 4H), 7.83 (t,
J =
7.2 Hz, 2H), 7.40 (d,
J = 7.8 Hz, 4H), 7.14 – 7.13 (m, 12H), Synthesis of 23. A mixture of 22 (0.55 g, 1.0 mmol) and 6
7.12 (s, 4H), 7.08 (s, 2H), 7.05 (br, 2H), 7.03 (d,
6H), 7.00 (br, 10H), 6.97 – 6.96 (m, 2H), 6.93 (d,
J
J
= 4.2 Hz, (0.17 g, 1.0 mmol) in dry toluene (50 mL) into a 100 mL round-
= 7.8 Hz, bottom flask was refluxed for 24 h under argon atmosphere.
2H), 6.88 (d,
J
2H), 6.45 (d,
J
= 8.4 Hz, 2H), 6.78 (d,
= 7.8 Hz, 2H), 6.72 (d, = 3.0 Hz, 2H), 6.70 (d,
= 7.8 Hz, 4H), 4.74 (s, 4H), 4.35 – 4.33 (m, 3H), NaBH4 (0.19 g, 5.0 mmol) was added in portions. After stirring
J
= 7.2 Hz, 2H), 6.74 (d, The solvent was removed under vacuum and the residue was
J
J
= 7.2 Hz, dissolved in THF (30 mL) and MeOH (30 mL), and then
J
4.23 (t,
J = 8.4 Hz, 4H), 4.09 – 4.07 (m, 7H), 3.97 – 3.93 (m, for overnight, the solvents were removed under vacuum, and
3H), 3.86 – 3.84 (m, 4H), 3.77 – 3.74 (m, 4H), 3.65 – 3.58 (m, the residue was extracted by dichloromethane (DCM). The
12H), 3.57 – 3.53 (m, 7H), 1.29 (br, 4H), 0.91 – 0.89 (m, 4H). organic layer was washed by brine till clear, dried over
13C NMR (100 MHz, CD3CN) δ 182.3, 159.2, 147.8, 145.0, anhydrous Na2SO4 and concentrated in vacuum to give a
144.1, 144.1, 142.5, 140.9, 138.9, 137.8, 132.0, 131.5, 131.5, kinetically stable amine as low yellowish oil. The unpurified
131.3, 129.6, 128.5, 128.5, 127.3, 122.7, 122.0, 120.6, 120.4, amine was dissolved in dry chloroform (20 mL), and then
113.6, 113.5, 111.1, 111.0, 71.9, 71.5, 70.9, 70.1, 69.4, 68.4, Boc2O (0.88 g, 4.0 mmol) and triethylamine (0.43 mL) were
-
50.8, 26.3. MALDI MS: m/z = 1909.91 [M – PF6 ], 1763.98 [M added. The mixture was stirred at room temperature for 24 h.
-
- HPF6 - PF6 ]; calculated exact mass: 2054.87. Anal. Calcd for Removal of solvent under reduced pressure and purification on
C114H124F12N8O10P2: C, 66.59; H, 6.08; N, 5.45. Found: C, a silica gel column using petroleum ether / ethyl acetate (4 : 1)
66.51; H, 6.00; N, 5.57.
as the eluent obtained the Boc-protected 23 as a low yellowish
oil, rf=0.72. Yield: 0.63 g, 78%. Compound of 23: 1H NMR
Synthesis of [3]rotaxane 17b. A mixture of salt 16 (110 mg,
0.1 mmol), tetraethyleneglycol bis(2-aminophenyl)ether 10 (75
mg, 0.2 mmol) and 2,6-pyridinedicarboxaldehyde derivative 9b
(75 mg, 0.2 mmol) were stirred for 72 h in dry CH3CN (10 mL)
under argon atmosphere at room temperature. Then 1M
(400 MHz, CDCl3) δ 7.12 – 6.99 (m, 15H), 6.92 (d,
J
= 8.8 Hz,
= 8.7 Hz, 2H), 6.43 (s,
= 10.0 Hz, 2H), 4.26
= 6.0 Hz, 2H), 3.89 (t, = 6.4 Hz,
2H), 6.84 (d,
1H), 6.36 (t,
J
J
= 8.4 Hz, 2H), 6.62 (d,
= 11.2 Hz, 4H), 4.34 (d,
J
J
(d,
J
= 7.6 Hz, 2H), 3.95 (t,
J
J
2H), 3.79 – 3.77 (m, 8H), 1.80 – 1.77 (m, 4H), 1.59 (s, 2H),
1.50 (s, 9H), 1.46 (s, 2H). 13C NMR (100 MHz, CDCl3) δ
160.9, 158.3, 157.5, 143.9, 140.5, 139.9, 135.9, 132.5, 131.3,
129.8, 127.6, 127.5, 126.3, 126.1, 114.4, 113.5, 105.7, 105.2,
BH3·THF solution (1.6 mL) was added and the mixture was
further stirred overnight. The solvents were removed under
vacuum and the residue was purified by column
chromatography (silica gel, DCM / MeCN / MeOH = 100 : 0 : 0
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 9 of 10
Journal Name
Organic & Biomolecular Chemistry
ARTICLE
99.0, 79.9, 67.8, 67.5, 55.2, 49.0, 48.7, 29.2, 28.4, 25.9. C89H111F6N4O10P: C, 69.33; H, 7.26; N, 3.63. Found: C, 69.25;
MALDI MS: m/z = 803.29 [M], 826.29 [M + Na+], 842.24 [M H, 7.17; N, 3.60.
+ K+]; calculated exact mass: 803.42. Anal. Calcd for
View Article Online
DOI: 10.1039/C5OB00068H
C53H57NO6: C, 79.17; H, 7.15; N, 1.74. Found: C, 79.24; H,
Acknowledgements
7.26; N, 1.71.
The authors acknowledge financial support from National
Natural Science Foundation of China (21272088, 21472059,
Synthesis of 24. To a solution of the Boc-protected amine 23
(0.80 g, 1.0 mmol) in dry DCM (20 mL), TFA (0.32 mL, 5.0
21402057), the Scientific Research Foundation for the Returned
mmol) was added at room temperature. After stirring for 2 h
Overseas Chinese Scholars, Ministry of Education and the self-
under argon atmosphere, the solvent was removed under
determined research funds of CCNU from the colleges’basic
vacuum. The residue was dissolved in MeOH (5.0 mL), and
research and operation of MOE (CCNU14A05009,
then saturated NH4PF6 (20.0 mL, aq) was added to yield an off-
CCNU14F01003).
white precipitate. After filtering, washing with H2O and dry
under vacuum, the title compound 24 was obtained as an off-
white solid, rf=0.65. Yield: 0.82 g, 96%. Compound of 24: H
1
Notes and references
a
NMR (600 MHz, CD3CN) δ 7.35 (d,
(m, 9H), 7.04 – 7.01 (m, 6H), 6.94-6.90 (m, 4H), 6.65 (d,
8.4 Hz, 2H), 6.59 (s, 2H), 6.52 (s, 1H), 4.06 (s, 2H), 4.03 (s,
J = 8.4 Hz, 2H), 7.15-7.12
Key Laboratory of Pesticide and Chemical Biology, Ministry of
J
=
Education, College of Chemistry, Central China Normal University,
Wuhan 430079, PR China E-mail: yinj@mail.ccnu.edu.cn
b G.L. and D.W. contributed equally to this work.
2H), 3.99 (t,
J = 6.6 Hz, 2H), 3.89 (t, J = 6.6 Hz, 2H), 3.78 (s,
6H), 1.78-1.72 (m, 4H), 1.49 (s, 4H). 13C NMR (100 MHz,
CD3CN) δ 161.8, 160.5, 158.3, 144.6, 141.3, 132.8, 132.2,
131.6, 128.3 , 127.0, 115.3, 114.2, 108.2, 55.8, 51.5, 51.4, 41.5,
† Electronic Supplementary Information (ESI) available: [UV-vis spectra
of
mixtures with different fractions of water
illumination optomized structures, NMR, MS spectra of all the
interminates and AIE-active [n]rotaxanes.]. See DOI: 10.1039/b000000x/
8
,
11
,
16
,
17
,
24 and 25 and Photographs of 24 and 25 in CH3CN/water
(
fw taken under UV
)
；
-
41.2, 29.5, 26.1. MALDI MS: m/z = 704.42 [M – PF6 ];
calculated exact mass: 849.34. Anal. Calcd for C48H50F6NO4P:
C, 67.83; H, 5.93; N, 1.65. Found: C, 67.80; H, 5.85; N, 1.72.
1
S. F. M. V. Dongen, S. Cantekin, J. A. A. W. Elemans, A. E. Rowan
and R. J. M. Nolte, Chem. Soc. Rev., 2014, 43, 99 122; (b) A. C.
Fahrenbach, C. J. Bruns, H. Li, A. Trabolsi, A. Coskun and J. F.
Stoddart, Acc. Chem. Res., 2014, 47, 482 493; (c) A. C.
Fahrenbach, C. J. Bruns, D. Cao and J. F. Stoddart, Acc. Chem. Res.
2012, 45, 1581 1592; (d) J. E. Beves, B. A. Blight, C. J. Campbell,
D. A. Leigh and R. T. McBurney, Angew. Chem. Int. Ed., 2011, 50
9260 9327; (e) J.-P. Collin, C. Dietrich-Buchecker, P. Gaviña, M.
C. Jimenez-Molero and J.-P. Sauvage, Acc. Chem. Res., 2001, 34
477 487; (f) F. M. Raymo and J. F. Stoddart, Chem. Rev., 1999,
99 1643 1664; (g) Z. Niu and H. W. Gibson, Chem. Rev., 2009
109 6024 6046; (h) B. Zheng, F. Wang, S. Dong and F. Huang,
Chem. Soc. Rev., 2012, 41, 1621 1636; (i) V. N. Vukotic and S. J.
Loeb, Chem. Soc. Rev., 2012, 41, 5896 5906.
Synthesis of [2]rotaxane 25a. The synthesis procedure of 25a
was similar to the synthesis of 11a. Yield: 155 mg, 78%.
Compound of 25a: 1H NMR (600 MHz, CD3CN) δ 8.83 (s,
－
－
2H), 7.78 (t,
7.10 (m, 9H), 7.04 – 7.01 (m, 6H), 6.91 (d,
6.77 (d, = 8.4 Hz, 2H), 6.71 – 6.99 (m 6H), 6.65 – 6.63 (m,
J
= 7.8 Hz, 1H), 7.34 (d,
J
= 7.8 Hz, 2H), 7.13 –
,
J
= 9.0 Hz, 2H),
－
J
,
2H), 6.52 (d,
1H), 6.09 (d,
J
J
= 8.4 Hz, 2H), 6.39 (t,
= 2.4 Hz, 2H), 4.55 (t,
J
J
= 4.8 Hz, 2H), 6.26 (s,
= 7.2 Hz, 2H), 4.47 –
－
4.44 (m, 4H), 4.11 – 4.08 (m, 4H), 3.93 (br, 3H), 3.89 – 3.87
(m, 2H), 3.79 – 3.78 (m, 2H), 3.75 - 3.74 (m, 5H), 3.72 (br,
,
－
4H), 3.64 (t,
J = 4.8 Hz, 2H), 3.37 (s, 6H), 1.73 – 1.70 (m, 4H),
,
－
,
1.46 (br, 4H). 13C NMR (100 MHz, CD3CN) δ 161.6, 160.1,
159.4, 158.3, 147.4, 144.6, 141.3, 140.8, 138.8, 137.6, 136.4,
135.3, 132.8, 131.6, 131.3, 128.4, 128.3, 127.1, 127.0, 124.2,
122.7, 121.9, 120.2, 115.2, 114.2, 113.1, 110.8, 107.0, 101.4,
71.9, 71.6, 71.0, 68.2, 68.1, 55.6, 52.8, 50.2, 29.5, 29.3, 26.1.
,
－
－
－
2
(a) J. E. Green, J. W. Choi, A. Boukai, Y. Bunimovich, E. Johnston-
Halperin, E. DeIonno, Y. Luo, B. A. Sheriff, K. Xu, Y. S. Shin, H.-
-
MALDI MS: m/z = 1183.75 [M – PF6 ]; calculated exact mass:
1328.58. Anal. Calcd for C75H83F6N4O9P: C, 67.76; H, 6.29; N,
4.21. Found: C, 67.82; H, 6.21; N, 4.10.
R. Tseng, J. F. Stoddart and J. R. Heath, Nature 2007, 445, 414
－
417; (b) B. Lewandowski, G. D. Bo, J. W. Ward, M. Papmeyer, S.
Kuschel, M. J. Aldegunde, P. M. E. Gramlich, D. Heckmann, S. M.
Goldup, D. M. D’Souza, A. E. Fernandes and D. A. Leigh, Science
Synthesis of [2]rotaxane 25b. The synthesis procedure of 25b
was similar to the synthesis of 11b. Yield: 169 mg, 73%.
Compound of 25b: 1H NMR (600 MHz, CD3CN) δ 8.85 (s,
2013, 339, 189
H. Tian, J. Org. Chem., 2013, 78, 2091
Matsumura, T. Yui, O. Ishitani and T. Takata, Org. Lett., 2013, 15
4686 4689; (e) H.-B. Cheng, H.-Y. Zhang and Y. Liu, J. Am.
Chem. Soc., 2013, 135, 10190 10193.
X. Ma and H. Tian, Chem. Soc. Rev., 2010, 39, 70
J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, H. S. Kwok,
X. Zhan, Y. Liu, D. Zhu and B. Z. Tang, Chem. Commun., 2001, 37
1740 1741.
J. Chen, C. C. W. Law, J. W. Y. Lam, Y. Dong, S. M. F. Lo, I. D.
－
193; (c) H. Zhang, B. Zhou,; H. Li, D.-H. Qu and
2H), 7.14 – 7.11 (m, 10H), 7.04 – 7.01 (m, 5H), 6.90 (d,
Hz, 2H), 6.87 (s, 2H), 6.76 (d, = 8.4 Hz, 2H), 6.72 – 6.69 (m,
4H), 6.68 – 6.66 (m, 2H), 6.64 (d, = 9.0 Hz, 2H), 6.51 (d,
8.4 Hz, 2H), 6.43 (d, = 7.2 Hz, 2H), 6.26 (s, 1H), 6.11 (s, 2H),
4.53 (br, 2H), 4.40 (br, 4H), 4.10 – 4.08 (m, 4H), 3.93 (s, 4H),
3.90 – 3.86 (m, 4H), 3.74 (d, = 3.0 Hz, 5H), 3.72 (br, 5H),
3.64 (d, = 15.6 Hz, 2H), 3.39 (s, 6H), 1.81 – 1.78 (m, 2H),
1.72 – 1.71 (m, 4H), 1.46 (br, 6H), 1.38 (br, 2H), 1.29 (br,
18H), 0.88 (t,
= 7.2 Hz, 3H). 13C NMR (100 MHz, CD3CN) δ
J = 8.4
－
2098; (d) Y. Koyama, T.
J
,
J
J =
J
－
－
J
3
4
－80.
J
,
J
－
167.3, 161.7, 161.3, 160.2, 158.5, 147.5, 144.8, 144.7, 141.5,
141.0, 137.8, 136.5, 135.4, 132.9, 131.7, 131.7, 131.4, 128.5,
128.4, 127.1, 127.1, 124.4, 122.0, 120.2, 115.3, 114.3, 113.2,
110.9, 109.0, 107.3, 101.5, 72.1, 71.8, 71.1, 69.1, 68.4, 68.2,
55.7, 52.9, 50.5, 32.4, 30.2, 30.2, 30.1, 30.1, 29.9, 29.8, 29.6,
29.4, 29.4, 26.4, 26.2, 23.2, 14.3. MALDI MS: m/z = 1395.92
5
6
Williams, D. Zhu and B. Z. Tang, Chem. Mater., 2003, 15, 1535
－
1546.
(a) Y. Hong, J. W. Y. Lam and B. Z. Tang, Chem. Commun., 2009,
45, 4332 4353; (b) M. Wang, G. Zhang, D. Zhang, D. Zhu and B.
Z. Tang, J. Mater. Chem., 2010, 20, 1858 1867; (c) Y. Hong, J. W.
-
－
[M – PF6 ]; calculated exact mass: 1540.79. Anal. Calcd for
－
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 9

Organic & Biomolecular Chemistry
Page 10 of 10
Journal Name
ARTICLE
Y. Lam and B. Z. Tang, Chem. Soc. Rev., 2011, 40, 5361
－5388; (d) 21 J. Yin, S. Dasgupta and J. Wu, Org. Lett., 2010, 12, 1712－1715.
N. B. Shustova, B. D. McCarthy and M. Dincǎ, J. Am. Chem. Soc., 22 F. Aricó, T. Chang, S. J. Cantrill, S. I. Khan and J. F. Stoddart,
View Article Online
2011, 133, 20126
Cozzolino, V. K. Michaelis, R. G. Griffin and M. Dincǎ, J. Am. 23 X. Zhang, Z. Chi, B. Xu, H. Li, Z. Yang, X. Li, S. Liu, Y. Zhang and
Chem. Soc., 2012, 134, 15061 15070; (f) Y. T. Wu, M. Y. Kuo, Y. J. Xu, Dyes. Pigm., 2011, 89, 56 62.
T. Chang, C. C. Shin, T. C. Wu, C. C. Tai, T. H. Cheng and W. S. 24 Q. Zhao, K. Li, S. Chen, A. Qin, D. Ding, S. Zhang, Y. Liu, B. Liu, J.
Liu, Angew. Chem. Int. Ed., 2008, 47, 9891 9894; (g) P. P. Z. Sun and B. Z. Tang, J. Mater. Chem., 2012, 22, 15128 15135.
Kapadia, L. R. Ditzler, J. Baltrusaitis, D. C. Swenson, A. V. 25 (a) P. T. Glink, A. I. Oliva, J. F. Stoddart, A. J. P. White and D. J.
Tivanski and F. C. Pigge, J. Am. Chem. Soc., 2011, 133, 8490 Williams, Angew. Chem. Int. Ed., 2001, 40, 1870 1875; (b) M.
8493; (h) B.-K. An, J. Gierschner and S. Y. Park, Acc. Chem. Res., Horn, J. Ihringer, P. T. Glink and J. F. Stoddart, Chem.-Eur. J., 2003,
2012, 45, 544 554. , 4046 4054; (c) M. E. Belowich, C. Valente and J. F. Stoddart,
Angew. Chem. Int. Ed., 2010, 49, 7208 7212; (d) M. E. Belowich,
－
20129; (e) N. B. Shustova, T. C. Ong, A. F.
Chem.-Eur. J., 2005, 11, 4655－4666.
DOI: 10.1039/C5OB00068H
－
－
－
－
－
－
－
9
－
－
7
(a) J. Wang, J. Mei, R. Hu, J. Z. Sun, A. Qin and B. Z. Tang, J. Am.
Chem. Soc., 2012, 134, 9956 9966; (b) M. P. Aldred, C. Li, G.-F.
－
C. Valente, R. A. Smaldone, D. C. Friedman, J. Thiel, L. Cronin and
J. F. Stoddart, J. Am. Chem. Soc., 2012, 134, 5243 5261; (e) J. Wu,
－
Zhang, W.-L. Gong, A. D. Q. Li, Y. Dai, D. Ma and M.-Q. Zhu, J.
Mater. Chem., 2012, 22, 7515 7528; (c) J. Li, Y. Duan and Q. Li,
－
K. C.-F. Leung and J. F. Stoddart, Proc. Natl. Acad. Sci. U.S.A.,
Dyes. Pigm., 2013, 96, 391 396; (d) J. Huang, N. Sun, J. Yang, R. 2007, 104, 17266 17271; (f) J. Yin, C. Chi and J. Wu, Org. Biomol.
Chem., 2010, , 2594 2599.
－
－
8
－
Tang, Q. Li, D. Ma, J. Qin and Z. Li, J. Mater. Chem., 2012, 22
,
12001 12007; (e) N. B. Shustova, B. D. McCarthy and M. Dincă, J.
－
26 S. Jiang, M. Liu, Y. Cui, D. Zou and Y. Wu, Eur. J. Org. Chem.,
Am. Chem. Soc., 2011, 133, 20126 20129; (f) P. P. Kapadia, L. R. 2013, 13, 2591 2596.
Ditzler, J. Baltrusaitis, D. C. Swenson, A. V. Tivanski and F. C.
Pigge, J. Am. Chem. Soc., 2011, 133, 8490 8493.
(a) X. Gu, G. Zhang, Z. Wang, W. Liu, L. Xiao and D. Zhang,
Analyst 2013, 138, 2427 2431; (b) X. Chen, X. Y. Shen, E. Guan,
Y. Liu, A. Qin, J. Z. Sun and B. Z. Tang, Chem. Commun., 2013, 49
1503 1505; (c) S. Song and Y.-S. Zheng, Org. Lett., 2013, 15, 820
823; (d) J.-X. Wang, Q. Chen, N. Bian, F. Yang, J. Sun, A.-D. Qi,
C.-G. Yan and B.-H. Han, Org. Biomol. Chem., 2011, , 2219
2226; (e) K. Shiraishi, T. Sanji and M. Tanaka, Tetrahedron Lett.,
2010, 51, 6331 6333.
(a) X. Wang, J. Hu, T. Liu, G. Zhang and S. Liu, J. Mater. Chem.,
2012, 22, 8622 8628; (b) N.-N. Liu, S. Song, D.-M. Li and Y.-S.
Zheng, Chem. Commun., 2012, 48, 4908 4910.
10 B. Xu, X. Wu, H. Li, H. Tong and L. Wang, Macromolecules 2011,
44, 5089 5092.
11 Y. Li, L. Xu and B. Su, Chem. Commun., 2012, 48, 4109
12 W. Z. Yuan, Z.-Q. Yu, Y. Tang, J. W. Y. Lam, N. Xie, P. Lu, E.-Q.
Chen and B. Z. Tang, Macromolecules 2011, 44, 9618 9628.
13 (a) Z. Li, F. Hu, G. Liu, W. Xue, X. Chen, S. H. Liu and J. Yin, Org.
Biomol. Chem., 2014, 12, 7702 7711; (b) F. Hu, J. Huang, M. Cao,
Z. Chen, Y.-W. Yang, S. H. Liu and J. Yin, Org. Biomol. Chem.,
2014, 12, 7712 7720.
14 W. Bai, Z. Wang, J. Tong, J. Mei, A. Qin, J. Z. Sun, B. Z. Tang,
Chem. Commun., 2015, 51, 1089 1091.
15 M. Banerjee, S. J. Emond, S. V. Lindeman and R. Rathore, J. Org.
Chem., 2007, 72, 8054 8061.
－
－
－
8
－
,
－
－
9
－
－
9
－
－
－
－
4111.
－
－
－
－
－
16 R. Hu, J. L. Maldonado, M. Rodriguez, C. Deng, C. K. W. Jim, J. W.
Y. Lam, M. M. F. Yuen, G. Ramos-Ortiz and B. Z. Tang, J. Mater.
Chem., 2012, 22, 232
17 Z. Li, W. Liu, J. Wu, S. H. Liu and J. Yin, J. Org. Chem., 2012, 77
7129 7135.
18 Z. Li, G. Liu, W. Xue, D. Wu, Y.-W. Yang, J. Wu, S. H. Liu, J. Yoon
and J. Yin, J. Org. Chem., 2013, 78, 11560 11570
19 G. Liu, Z. Li, D. Wu, W. Xue, T. Li, S. H. Liu and J. Yin, J. Org.
Chem., 2014, 79, 643 652.
20 W. Xue, Z. Li, G. Liu, X. Chen, T. Li, S. H. Liu and J. Yin, Org.
－240.
,
－
－
－
Biomol. Chem., 2014, 12, 4862
－4871.
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012