Dual-stimulus luminescent lanthanide molecular switch based on an unsymmetrical diarylperfluorocyclopentene

Article abstract of DOI:10.1021/ja4018804

A [2]pseudorotaxane formed from an unsymmetrical diarylperfluorocyclopentene (1) and a Eu³⁺ complex of terpyridinyldibenzo-24-crown-8 (2) revealed excellent reversible lanthanide luminescence switching behavior dual-modulated by host-guest and optical stimuli.

Full text of DOI:10.1021/ja4018804

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Communication
Dual Stimulus Luminescent Lanthanide Molecular Switch
Based on Unsymmetrical Perfluorocyclopentene Diarylethene
Hong-Bo Cheng, Heng-Yi Zhang, and Yu Liu
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja4018804 • Publication Date (Web): 10 May 2013
Downloaded from http://pubs.acs.org on May 12, 2013
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Dual Stimulus Luminescent Lanthanide Molecular Switch Based
on Unsymmetrical Perfluorocyclopentene Diarylethene
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HongꢀBo Cheng, HengꢀYi Zhang and Yu Liu*
Department of Chemistry, State Key Laboratory of ElementoꢀOrganic Chemistry, Nankai University, Tianjin 300071 , Peoꢀ
ple’s Republic of China
Supporting Information Placeholder
tive (1) to a Eu3+ complex of dibenzoꢀ24ꢀcrownꢀ8 (DB24C8)
ABSTRACT: [2]Pseudorotaxane formed from unsymmetrical
derivative bearing a terpyridine moiety (2) through the interaction
perfluorocyclopentenodiarylethene (1) and a Eu3+ complex (2) of
of the dialkylammonium moiety in 1 with the 24C8 ring in 2, to
demonstrate how the Eu3+ luminescence is reversibly modulated
terpyridinyldibenzoꢀ24ꢀcrownꢀ8 revealed excellent reversible
lanthanideꢀluminescence switching behavior dualꢀmodulated by
by the ringꢀclosing and ringꢀopening reactions of 1 caused upon
UV and visible light irradiation. We introduced an indole chroꢀ
mophore to 1 in order to lower the excitation energy for facilitatꢀ
ing the resonant energy transfer (RET) from the excited lanthaꢀ
nide ion to one of the isomers of the photochromic switch.8 We
hostꢀguest and optical stimuli.
Research on optically modulated smart materials has received
also introduced thermally stable thiopheneꢀbased unsymmetrical
much attention for their potential application to optical switches,
diarylethene as a RET acceptor of 1, and a perfluorocyclopentene
optoelectronics, smart surfaces, photoinduced shapeꢀmemory
as the central ethene linker because of its resistance to fatigue.
polymers, functional vesicles, bionanodevices, and molecular
machines.1 Photochromic compounds can be interconverted by
light between two states of different spectroscopic properties,2
which makes them good candidates for realizing smart optical
modulation. Diarylethene derivatives (DTEs) are the most promisꢀ
ing optically responsive compounds, featuring notable thermally
irreversible photochromic behavior, high photoisomerization
quantum yields, and outstanding fatigue resistance.3 On the other
hand, lanthanide luminescenceꢀbased devices4 are also well deꢀ
veloped because of their unique luminescence properties, such as
longꢀlived excited states, visible light emission, large Stokes shift,
and narrow emission bandwidths. The integration of photoꢀ
chromic DTEs with luminescent lanthanide component has disꢀ
Figure 1. Structures of diarylethene 1 and Eu3+ complex 2 and
reference compound without DB24C8 3.
played a few remarkable potential applications, including a phoꢀ
tochromic Eu3+ complex with the sulfone moiety incorporated in a
DTE for a potential optical memory medium with nondestructive
The syntheses of 1, 2, and reference compound 3 are shown in
Figure S1 in the Supporting Information. Briefly, 1 was syntheꢀ
sized by the condensation of 4ꢀ(3,3,4,4,5,5ꢀhexafluoroꢀ2ꢀ(5ꢀ
readout capability.5a The combination of lanthanideꢀdoped upꢀ
converting nanoparticles (UCNPs) and DTE photoswitches enaꢀ
bles not only the optical memory application5b but also the moduꢀ
methoxyꢀ1,2ꢀdimethylꢀ1Hꢀindolꢀ3ꢀyl)cyclopentꢀ1ꢀenyl)ꢀ5ꢀ
lation with nearꢀinfrared (NIR) light,5c,5d offering new opportuniꢀ
methylthiopheneꢀ2ꢀcarbaldehyde with primary amines, and the
ties in photodynamic therapy. Photoswitching and photoresponꢀ
subsequent protonation and counterion exchange. The electronꢀ
sive modulation of the emission properties of luminescent moleꢀ
withdrawing property of the perfluoro substituents promoted the
cyclization reaction.9 Eu3+ complex 2 was prepared in 83% yield
cules with photochromic units is one of the promising research
areas in molecular photoswitches and photomemory because of
by the reaction of 4ꢀformylꢀDB24C8 with 1ꢀ(pyridinꢀ2ꢀ
yl)ethanone under basic conditions,10a followed by the comlexaꢀ
their high sensitivity, resolution, contrast, and fast response time
which are essential in luminescence technology.6 An interesting
tion of the resulting terpyridineꢀappended DB24C8 derivative
with europium thenoyltrifluoroacetonate [Eu(tta)3ꢁ3H2O] .10b
example was recently reported on the luminescence from lanthaꢀ
nideꢀappended rotaxanes and the nonꢀradiative quenching upon
binding of a halide in the rotaxane cavity.6d However, the reversiꢀ
Compound 1 exhibited reversible and bistable photochromism.
Irradiation of a solution of openꢀform (OF) 1 with UV light at 365
nm led to the generation of a new absorption band at around 614
nm with accompanying isosbestic point at 370 nm. Thus, the colꢀ
or of the solution changed from colorless to dark green (Figure 2).
Upon irradiation with visible light (614 nm), the dark green soluꢀ
tion of closedꢀform (CF) 1 returned to colorless (Figure 2). The
laser flash photolysis of OFꢀ1 in a 1:1 mixture of acetonitrile and
chloroform showed a transient absorption at around 420 nm with
ble optical modulation of the luminescence intensity of lanthanide
complexes remains a challenge. We recently constructed some
interesting
supramolecular
devices,7
in
which
the
tris[2]pseudorotaxane7a and [2]pseudorotaxane7b systems behave
as reversible luminescent lanthanide switches in the presence of
K+ or 18ꢀcrownꢀ6 (18C6).
In this work, we have noncovalently combined unsymmetrical
perfluorocyclopenteneꢀfused photochromic diarylethene derivaꢀ
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a decay lifetime of 650 ꢀs, further confirming the conversion of
diarylethene moiety from the coꢀplanar OF to the twisted CF.9e
CFꢀ1 turned out to maintain its inherently high thermal stability.
At an elevated temperature (60 °C), it did not show any sign of
thermal ringꢀopening in the dark at least for 15 h upon monitoring
at 614, 485 and 425 nm (Figure S39). The photocyclization quanꢀ
tum yields (Φoꢀc) corrected for the active conformer were deterꢀ
mined for compound 1 as 0.38 and for [2]pseudorotaxane 1⊂2 as
0.20 (Figure S31). Moreover, [2]pseudorotaxane 1⊂2 displayed
excellent photochromic performance in poly(methyl methacrylate)
(PMMA), as was the case in solution (Figure S42).
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Figure 3. (a) The crystal structure of 1. (b) Color changes of the
single crystal 1 upon alternate irradiation at 365 nm and 614 nm.
When an equimolar amount of compound OFꢀ1 was added to
the solution of 2, the luminescence intensity of the complex was
decreased by about 10% due to the photoinduced electron transfer
(PET) between OFꢀ1 and 2.7a This means that the association with
OFꢀ1 does not significantly alter the luminescent behavior of 2. In
1
the H NMR spectrum of an equimolar mixture of the two comꢀ
ponents (Figure 4), the aromatic protons Hg, Hh and Hi in 2 were
shifted upfield (ꢂδ = –0.50 ppm, –0.02 ppm, and –0.22 ppm,
respectively), while H4 and H5 adjacent to the outer ammonium
site on the axle component in 1 were shifted downfield (ꢂδ = 0.38
ppm and 0.49 ppm, respectively), when compared with free 1 and
2. This observation confirms the interaction of the secondary amꢀ
monium moiety in 1 with the 24C8 ring in 2, leading to the forꢀ
mation of OFꢀ1⊂2 [2]pseudorotaxane.
Figure 2. Absorption spectra of 1 (1.0 × 10−5 M) undergoing phoꢀ
toconversion from the initial openꢀform (OF) to closedꢀform (CF)
upon exposure to 365 nm light; after 2 min, the maximal change
was achieved at 614 nm. Inset: changes in chemical structure and
photographic images of 1 upon alternate irradiation with UV and
visible light in 1:1 CH3CN/CHCl3 solution.
Significantly, we obtained a single crystal of 1ꢁCl by slow
evaporation from a CH3CN/H2O solution. Xꢀray crystallographic
analysis11 revealed a favorable structure for solidꢀstate photoꢀ
chromism; i.e., 1 adopts exclusively the antiparallel conformation
(Figure 3a), which is in sharp contrast to the solutionꢀphase beꢀ
havior, where both antiparallel and parallel conformer coexist, as
evidenced by 1H NMR spectroscopy (Figure S27). Moreover,
rightꢀhanded helical chains were formed by the hydrogenꢀbond
interactions threading 1 molecules (Figure S26). The distance
between the photocyclizing carbon atoms (C6ꢁꢁꢁC20) was 3.645
Å, allowing photochromic cyclization reaction in the crystal.12
Like in solution, the bulk crystals of 1ꢁCl readily underwent the
reversible photochromic ringꢀclosure/opening reaction upon irraꢀ
diation at 365 nm/614 nm (Figure 3b).
1
Figure 4. Partial H NMR spectra (400 MHz, CD3CN/CDCl3 =
1:1, 298 K) of (a) free 2, (b) an equimolar mixture of 2 and 1, and
(c) free 1. [1] = 5.0 mM. See Figure 1 for atom labels.
It is well known that the luminescence switching properties
originate from good spectral overlap between the emission band
of the metal complex and the absorption band of the colored phoꢀ
tochromic unit.13 In the present OFꢀ1⊂2 [2]pseudorotaxane sysꢀ
tem, the strongest emission of complex 2 occurs at 619 nm, while
all of the absorption bands of OFꢀ1 occur at less than 400 nm.
Therefore, no intermolecular RET process from the Eu3+ moiety
of 2 to diheteroaryl ethene of OFꢀ1 is expected to happen. Howꢀ
ever, when the OFꢀ1⊂2 [2]pseudorotaxane was exposed to UV
light at 365 nm, approximately 80 % of the fluorescence intensity
at 619 nm was quenched, with accompanying decrease of the
quantum yield from 0.128 to 0.020 (Figure 5). In addition to the
decrease of steadyꢀstate fluorescence, the fluorescence lifetime of
Eu3+ in OFꢀ1⊂2 [2]pseudorotaxane (τ = 638 ꢃs (88.68%); 321 ꢃs
(11.32 %), Figure S32, top) was dramatically decreased in CFꢀ
1⊂2 [2]pseudorotaxane (τ = 216 ꢃs (90.01%); 371 ꢃs (9.9 %) in
Figure S32, bottom). These observations jointly indicate the ocꢀ
currence of the intermolecular RET from the Eu3+ (donor) in 2 to
Benefiting from the excellent luminescence property of Eu3+,
complex 2 displayed satisfactory luminescence in solution. When
excited at 390 nm, the complex showed five emission peaks at
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580 nm (5D0 → F0), 594 nm (5D0 → F1), 619 nm (5D0 → F2),
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656 nm (5D0 → F3), and 700 nm (5D0 → F4) (Figure S30). The
strong fluorescence of complex 2 may be attributed to the intraꢀ
molecular energy transfer (ET)13a,b from the excited terpyridine
moiety to Eu3+.
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was gradually recovered (Figure S36), suggesting that the RET
the diheteroarylethene moiety (acceptor) of CFꢀ1 because of the
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process is inhibited due to the disassembling of
[2]pseudorotaxane. When 18C6 was added to this solution, the
lanthanide emission of complex 2 was quenched, due to the RET
from Eu3+ to diheteroarylethene in regenerated CFꢀ1⊂2
[2]pseudorotaxane.
perfect energy matching of the emission of 2 with the absorption
of CFꢀ1 as well as the short donorꢀacceptor distance. The centerꢀ
toꢀcenter distance between CFꢀ1 and Eu3+ of 2, which was estiꢀ
mated as 20.2 Å (Figure S41) from the molecular mechanics
(Dreiding
forcefield)ꢀoptimized
structure
of
CFꢀ1⊂2
[2]pseudorotaxane, is well within the Förster radius (R0 = 30.7
Å),14 facilitating RET. In contrast, reference compound 3, lacking
DB24C8, quenched the fluorescence by only 9 % (Figure S37),
revealing the critical role of the crown ether moiety in facilitating
the RET process in CFꢀ1⊂2 [2]pseudorotaxane.
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The fluorescence modulation of the 1⊂2 [2]pseudorotaxane
system upon alternate exposure to UV and visible light is illusꢀ
trated in Figure 6. After irradiating the complex solution with UV
light at 365 nm for five minutes, the solution was immediately
moved into the fluorescence spectrometer to perform the emission
measurements (with excitation at 390 nm). The characteristic
fluorescence emission of Eu3+ was significantly quenched. Howꢀ
ever, after illumination with visible light at 614 nm for ten
minutes, the fluorescence intensity was totally recovered.
Figure 6. Fluorescence spectra and intensity changes at 619 nm
(inset) of the 1⊂2 system (in CH3CN/CHCl3 1:1, v/v) observed
upon alternate UV/vis irradiation cycles at 390 nm and 619 nm.
PSS represents photostationary state.
Upon irradiation of the aboveꢀmentioned solution containing
OFꢀ1, 2, and KPF6 at 365 nm for five minutes, the fluorescence
intensity was only slightly decreased (Figure S35), revealing that
the RET was suppressed when the pseudorotaxane structure was
destroyed by the addition of K+ even if OFꢀ1 was converted to
CFꢀ1. The schematic representation of the switch modes for the
1⊂2 system is illustrated in Scheme 1, which reveals the expected
luminescent lanthanide switch behavior.
Scheme 1. Schematic illustration of the light- modulated mo-
lecular switch.
Figure 5. Emission spectra of the 1⊂2 system (1.0 × 10ꢀ5 M) and
the emission intensity changes at 619 nm upon UV irradiation
(inset) in CH3CN/CHCl3 solution (1:1), λex = 390 nm. Photograph
shows the emission color change upon UV irradiation.
It is well documented that the assembling/disassembling proꢀ
cesses of [2]pseudorotaxane based on DB24C8 and dialkylammoꢀ
nium salt can be reversibly manipulated by adding K+ and 18C6
in series, which has been proved to be a simple and accessible
strategy for constructing supramolecular switching systems.7,15
The assembling/disassembling processes of [2]pseudorotaxane
1
OFꢀ1⊂2 were examined by H NMR spectroscopy. As shown in
Figure S33, when an excess amount of KPF6 was added to the
solution of OFꢀ1⊂2, the methylene protons H4 and H5 on the axle
component OFꢀ1 shifted upfield relative to the original positions
observed for free OFꢀ1, suggesting that the dialkylammonium ion
of OFꢀ1 is expelled from the ring of DB24C8 by K+. This is reaꢀ
sonable because the association constant of DB24C8 with K+ (Ka
= 7.6 × 103 M−1)16 is larger than that for the formation of OFꢀ1⊂2
(Ka = 1.2 × 103 M−1)17 (Figure S38), leading to the dissociation of
OFꢀ1⊂2 upon addition of K+. When 18C6 was added to the above
system, the proton signals of H4 and H5 were recovered to the
original positions, indicating that [2]pseudorotaxane OFꢀ1⊂2
was regenerated.
In summary, we have designed and synthesized the hostꢀguest
partners 1 and 2 with perfect spectral overlap between the host
emission and the guest absorption. By using terpyridineꢀEu3+
complex with a 24C8 moiety (2) as a host and photochromic DTE
with a dialkylammonium moiety (1) as a guest, [2]pseudorotaxane
1⊂2 was readily constructed through complexation of the ammoꢀ
nium moiety of 1 with 24C8 of 2, facilitating the RET process
upon ringꢀclosing reaction of 1 by UV irradiation. The RET proꢀ
cess controlled by the alternate UV/vis irradiations enabled the
reversible ON/OFF switching of the lanthanoid luminescence.
Furthermore, the reversible luminescence behavior of the
[2]pseudorotaxane system can be manipulated by the successive
addition of K+ as a competitive guest and 18C6 as a competitive
host. This dual stimuliꢀdriven luminescent lanthanide molecular
switch possesses two distinctive features: (1) the combination of
Luminescence spectral experiments were also performed to
confirm the interaction between OFꢀ1⊂2 and KPF6. The fluoresꢀ
cence intensity of complex 2 was slightly enhanced upon addition
of KPF6 (Figure S34), indicating that no RET occurred when OFꢀ
1⊂2 was disassembled. In sharp contrast, when KPF6 was added
to the solution of CFꢀ1⊂2, the lanthanide emission of this system
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Boyer, J.ꢀC.; Carling, C.ꢀJ.; Gates, B. D.; Branda, N. R. J. Am. Chem. Soc.
2010, 132, 15766–15772.
RET with photochromic switching can provide a highly efficient
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luminescence switch, and (2) the selfꢀassembled supramolecular
scaffold can be disassembled and reꢀassembled noncovalently to
function as a molecular switch. The present results may provide a
novel perspective for the design of multistimuliꢀdriven molecular
machines and logic gates.
(6) (a) Chan, J. C.; Lam, W. H.; Wong, H.; Zhu, N.; Wong, W.; Yam,
V. W.ꢀW. J. Am. Chem. Soc. 2011, 133, 12690–12705. (b) Tian, H.;
Wang, S. Chem. Commun. 2007, 781–792. (c) Yildiz, I.; Deniz, E.; Rayꢀ
mo, F. M. Chem. Soc. Rev. 2009, 38, 1859–1867. (d) Allain, C.; Beer, P.
D.; Faulkner, S.; Jones, M. W.; Kenwright, A. M.; Kilah, N. L.; Knighton,
R. C.; Sørensen, T. J.; Tropiano, M. Chem. Sci. 2013, 4, 489–493.
(7) (a) Han, M.; Zhang, H.ꢀY.; Yang, L.ꢀX.; Jiang, Q.; Liu, Y. Org.
Lett. 2008, 10, 5557–5560. (b) Ding, Z.ꢀJ.; Zhang, Y.ꢀM.; Teng, X.; Liu,
Y. J. Org. Chem. 2011, 76, 1910–1913. (c) Zhang, Z.ꢀJ.; Zhang, H.ꢀY.;
Wang, H.; Liu, Y. Angew. Chem. Int. Ed. 2011, 50, 10834–10838. (d)
Jiang, Q.; Zhang, H. Y.; Han, M.; Ding, Z. J.; Liu, Y. Org. Lett. 2010, 12,
1728–1731.
(8) (a) Zhang, Y.ꢀM.; Han, M.; Chen, H.ꢀZ.; Zhang, Y.; Liu, Y. Org.
Lett. 2013, 15, 124–127. (b) Mizukami, S.; Watanabe, S.; Akimoto, Y.;
Kikuchi, K. J. Am. Chem. Soc. 2012, 134, 1623−1629. (c) Bossi, M.;
Belov, V.; Polyakova, S.; Hell, S. W. Angew. Chem. Int. Ed. 2006, 45,
7462–7465. (d) Díaz, S. A.; Menéndez, G. O.; Etchehon, M. A.; Giordano,
L.; Jovin, T. M.; JaresꢀErijman, E. A. ACS Nano 2011, 5, 2795–2805.
(9) (a) Irie, M. Chem. Rev. 2000, 100, 1685ꢀ1716. (b) Roberts, M. N.;
Carling, C. J.; Nagle, J. K.; Branda, N. R.; Wolf, M. O. J. Am. Chem. Soc.
2009, 131, 16644–16645. (c) Lim, S. J.; Seo, J. W.; Park, S. Y. J. Am.
Chem. Soc. 2006, 128, 14542–14547. (d) Perrier, A.; Maurel, F. O.;
Jacquemin, D. Acc Chem Res. 2012, 45, 1173–1182. (e) Brayshaw, S. K.;
Schiffers, S.; Stevenson, A. J.; Teat, S. J.; Warren, M. R.; Bennett, R. D.;
Sazanovich, I. V.; Buckley, A. R.; Weinstein, J. A.; Raithby, P. R. Chem.
Eur. J. 2011, 17, 4385–4395.
ASSOCIATED CONTENT
Supporting Information
9
General experimental procedures and characterization data for 1,
2 and 3, as well as the fluorescence titrations in control experiꢀ
ments and the crystal data (CCDC 886318) of the complex. This
material is available free of charge via the Internet at
http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
Eꢀmail: yuliu@nankai.edu.cn
ACKNOWLEDGMENT
We thank the 973 Program (2011CB932500), and the NNSFC
(Nos. 20932004 and 20972077) for financial support. We would
like to thank the reviewers for their valuable comments and sugꢀ
gestions regarding the revision. We also thank Prof. Yoshihisa
Inoue at Osaka University (Japan) for assistance in the preparaꢀ
tion of this manuscript.
(10) (a) Zhou, X.; Jin, X. ꢀJ.; Li, D. ꢀH.; Wu, X. Chem. Commun. 2011,
47, 3921–3923. (b) Yang, C.; Fu, L.ꢀM.; Wang, Y.; Zhang, J.ꢀP.; Wong,
W.ꢀT.; Ai, X.ꢀC.; Qiao, Y.ꢀF.; Zou, B.ꢀS.; Gui, L.ꢀL. Angew. Chem. Int.
Ed. 2004, 43, 5010–5013.
(11) Crystallographic data for 1: C29H27ClF6N2OS, Mr = 601.04,
Orthorhombic, space group P212121, a = 6.7922(9) Å, b = 20.030(3) Å, c
= 20.030(3) Å, α = β = γ = 90o, V = 2788.9(7) Å3, Z = 4, ρcalcd = 1.431
gꢁcm3, T = 113(2) K, 29302 measured reflections, 6613 unique reflections
(Rint = 0.0468), R1 = 0.0309, wR2 = 0.0589 (I ≥ 2σ(I)), GOF = 1.010.
CCDC 886318 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif
(12) (a) Kobatake, S.; Uchida, K.; Tsuchida, E.; Irie, M. Chem. Comꢀ
mun. 2002, 2804–2805. (b) Morimoto, M.; Kobatake, S.; Irie, M. Chem.
Eur. J. 2003, 9, 621–627. (c) Zhu, W.; Yang, Y. H.; Métivier, R.; Zhang,
Q.; Guillot, R.; Xie, Y. S.; Tian, H.; Nakatani, K. Angew. Chem. Int. Ed.
2011, 50, 10986–10990.
(13) (a) Kotova, O.; Daly, R.; dos Santos, C. M.; Boese, M.; Kruger, P.
E.; Boland, J. J.; Gunnlaugsson, T. Angew. Chem. Int. Ed. 2012, 51,
7208–7212. (b) Bozoklu, G.; Gateau, C.; Imbert, D.; Pécaut, J.; Robeyns,
K.; Filinchuk, Y.; Farah, M.; Gilles, M.; Mazzanti, M. J. Am. Chem. Soc.
2012, 134, 8372−8375. (c) Giordano, L.; Jovin, T. M.; Irie, M.; Jaresꢀ
Erijman, E. A. J. Am. Chem. Soc. 2002, 124, 7481ꢀ7489.
(14) (a) Zhang, P.; Rogelj, S.; Nguyen, K.; Wheeler, D. J. Am. Chem.
Soc. 2006, 128, 12410–12411. (b) Kuningas, K.; Rantanen, T.; Ukonaho,
T.; Lovgen, T.; Soukka, T. Anal. Chem. 2005, 77, 7348–7355. (c)
Kuningas, K.; Ukonaho, T.; Pakkila, H.; Rantanen, T.; Rpsenberg, J.;
Lovgen, T.; Soukka, T. Anal. Chem. 2006, 78, 4690–4696.
(15) (a) Liu, Y.; Yu, Y.; Gao, J.; Wang, Z.; Zhang, X. Angew. Chem.,
Int. Ed. 2010, 49, 6576–6579. (b) Wang, C.; Chen, Q.; Xu, H.; Wang, Z.;
Zhang, X. Adv. Mater. 2010, 22, 2553–2555. (c) Chiang, P.ꢀT.; Cheng,
P.ꢀN.; Lin, C.ꢀF.; Liu, Y.ꢀH.; Lai, C.ꢀC.; Peng, S.ꢀM.; Chiu, S.ꢀH. Chem.
Eur. J. 2006, 12, 865–876.
REFERENCES
(1) (a) Ma, X.; Tian, H. Chem. Soc. Rev. 2010, 39, 70–80. (b) Leigh,
D. A.; Serreli, V.; Lee, C. F.; Kay, E. R. Nature 2007, 445, 523–527. (c)
Venkataramani, S.; Jana, U.; Dommaschk, M.; Sönnichsen, F. D.;
Tuczek, F.; Herges, R. Science 2011, 331, 445–448. (d) Natali, M.;
Giordani, S. Chem. Soc. Rev. 2012, 41, 4010–4029. (e) Avellini, T.; Li,
H.; Coskun, A.; Barin, G.; Trabolsi, A.; Basuray, A. N.; Dey, S. K.; Credi,
A.; Silvi, S.; Stoddart, J. F.; Venturi, M. Angew. Chem. Int. Ed. 2012, 51,
1–6. (f) Hosono, N.; Kajitani, T.; Fukushima, T.; Ito, K.; Sasaki, S.;
Takata, M.; Aida, T. Science 2004, 303, 1845–1849. (g) Yu, G.; Han, C.;
Zhang, Z.; Chen, J.; Yan, X.; Zheng, B.; Liu, S.; Huang, F. J. Am. Chem.
Soc. 2012, 134, 8711–8717. (h) Fukaminato, T.; Doi, T.; Tamaoki, N.;
Okuno, K.; Ishibashi, Y.; Miyasaka, H. M.; Irie, M. J. Am. Chem. Soc.
2011, 133, 4984–4990.
(2) (a) Kim, S.; Yoon, S. J.; Park, S. Y. J. Am. Chem. Soc. 2012, 134,
12091−12097. (b) Xie, X.ꢀJ; Mistlberger, G.; Bakker, E. J. Am. Chem.
Soc. 2012, 134, 16929−16932. (c) Bossi, M.; Belov, V.; Polyakova, S.;
Hell, S.W. Angew. Chem. Int. Ed. 2006, 45, 7462−7465. (d) Yildiz, I.;
Impellizzeri, S.; Deniz, E.; McCaughan, B.; Callan, J. F.; Raymo, F. M. J.
Am. Chem. Soc. 2011, 133, 871–879. (e) Zhang, J.; Zou, Q.; Tian, H. Adv.
Mater. 2013, 25, 378–399.
(3) (a) Kobatake1, S.; Takami, S.; Muto, H.; Ishikawa, T.; Irie, M. Naꢀ
ture 2007, 446, 778–781. (b) Han, M.; Michel, R.; He, B.; Chen, Y.ꢀS.;
Stalke, D.; John, M.; Clever, G. H. Angew. Chem. Int. Ed. 2013, 52, 1319
–1323. (c) Uno, K.; Niikura, H.; Morimoto, M.; Ishibashi, Y.; Miyasaka,
H.; Irie, M. J. Am. Chem. Soc. 2011, 133, 13558–13564. (d) Lee, S.; You,
Y.; Ohkubo, K.; Fukuzumi, S.; Nam, W. Angew. Chem. Int. Ed. 2012, 51,
13154 –13158. (e) Zhang, H.; Kou, X.ꢀX.; Zhang, Q.; Qu, D.ꢀH.; Tian, T.
Org. Biomol. Chem. 2011, 9, 4051–4056.
(4) (a) Tropiano, M.; Kilah, N. L.; Morten, M.; Rahman, H.; Davis, J.
J.; Beer, P. D.; Faulkner, S. J. Am. Chem. Soc. 2011, 133, 11847–11849.
(b) de BettencourtꢀDias, A.; Barber, P. S.; Bauer, S. J. Am. Chem. Soc.
2012, 134, 6987−6994. (c) McMahon, B. K.; Gunnlaugsson, T. J. Am.
Chem. Soc. 2012, 134, 10725−10728. (d) Lemonnier, J. F.; Babel, L.;
Guénée, L.; Mukherjee, P.; Waldeck, D. H.; Eliseeva, S. V.; Petoud, S.;
Piguet, C. Angew. Chem. Int. Ed. 2012, 51, 11302−11305.
(16) (a) Takeda, Y. Bull. Chem. Soc. Jpn. 1983, 56, 3600–3602. (b)
Takeda, Y.; Kudo, Y.; Fujiwara, S. Bull. Chem. Soc. Jpn. 1985, 58,
1315–1316. (c) Tawarah, K. M.; Mizyed, S. A. J. Solution Chem. 1989,
18, 387–401.
(17) The association constant (Ka) of the OFꢀ1⊂2 [2]pseudorotaxane
was determined by using the 1H NMR spectroscopy with the singleꢀpoint
method; see Frensdorff, H. K. J. Am. Chem. Soc. 1971, 93, 600–606.
(5) (a) Nakagawa, T.; Hasegawa, Y.; Kawai, T. Chem. Commun. 2009,
5630–5632. (b) Zhou, Z.; Hu, H.; Yang, H.; Yi, T.; Huang, K.; Yu, M.; Li,
F.; Huang, C. Chem. Commun. 2008, 4786–4788. (c) Carling, C.ꢀJ.; Boyꢀ
er, J.ꢀC.; Branda, N. R. J. Am. Chem. Soc. 2009, 131, 10838–10839. (d)
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