An anthracene-based photochromic macrocycle as a key ring component to switch a frequency of threading motion

Article abstract of DOI:10.1002/chem.200701291

A concept and demonstration of a switching in frequencies of molecular motions are described using a pseudorotaxane system. The setup consists of dibenzylammonium hexafluorophosphate and a photochromic dianthrylethane-based [24]crown-8-type macrocycle, which we designed as a key ring component for the pseudorotaxane system having photocontrollable threading functionality by changing the size of ring component due to the action of light.

Full text of DOI:10.1002/chem.200701291

FULL PAPER
DOI: 10.1002/chem.200701291
An Anthracene-Based Photochromic Macrocycle as a Key Ring Component
To Switch a Frequency of Threading Motion
Keiji Hirose,* Yoshinobu Shiba, Kazuaki Ishibashi, Yasuko Doi, and Yoshito Tobe[a]
Abstract: A concept and demonstration of a switching in frequencies of molecular
motions are described using a pseudorotaxane system.The setup consists of diben-
Keywords: crown compounds · mo-
zylammonium hexafluorophosphate and a photochromic dianthrylethane-based
lecular devices · noncovalent inter-
[24]crown-8-type macrocycle, which we designed as a key ring component for the
actions · photochromism · rotaxanes
pseudorotaxane system having photocontrollable threading functionality by chang-
ing the size of ring component due to the action of light.
Introduction
termediate region between pseudorotaxanes and rotax-
anes,[11] effects of the size of stoppers,[12] a ring shape and a
stopper structure,[13] a length of dumbbell component on
thermodynamic parameters of these motions.[14] In this
paper, we report a new concept and a demonstration of a
switching in the frequency of molecular motions using a
pseudorotaxane system in which frequencies of threading
and dethreading motions is reversibly and quantitatively
changed in response to physical stimuli by changing the size
of ring component.
Interlocked molecules such as catenanes and rotaxanes[1] are
thought to be prime candidates for the implementation and
the development of devices at the nanometer scale,[2] artifi-
cial photosynthesis,[3] construction of ion channels,[4] or the
development of artificial molecular machines.[5] The me-
chanically interlocked components of these molecules can
be induced to switch between different geometries in re-
sponse to either physical or chemical stimuli, since the com-
ponents of catenanes and rotaxanes can be induced to per-
form relative motions, such as circumrotation[6] (rotary
motion) and shuttling[7] (linear motion).Based on such geo-
metrical switching properties, molecular electronics devices
have been developed.[8] On the other hand, a control of the
rate of molecular motion is one way to create new devices
at molecular level.Schalley and co-workers reported a con-
trol mechanism of the rate of shuttling motions in [2]ro-
taxanes by different solvent effects on electrostatic interac-
tions.[9] In order to control the rate of molecular motion,
pseudorotaxanes are the promising candidates for molecular
machines and device components, because pseudorotaxanes
are viewed as prototypes of simple molecular machines and
show characteristic motion, namely slippage and deslippage
motions.[10] Recently, interesting investigations on these mo-
tions have been reported including a description of the in-
Results and Discussion
Design of a switching system: In order to design a switching
system controlled by a frequency of molecular motions, we
chose a pseudorotaxane which consists of dibenzylammoni-
um hexafluorophosphate (DBA) and a photochromic di-
anthrylethane-based macrocycle 1.[15] We designed 1 as a
key ring component of the pseudorotaxane system to in-
clude photocontrollable threading functionality (Fig-
ure 1a).
a
The photodimerization and the thermal reversion of the
anthracene units between open-form molecule 1 and closed-
form molecule 2 would cause substantial change of the
cavity size reversibly.[16] Because the cavity size of 2 should
be similar to that of dibenzo-[24]crown-8, 2 would form a
stable complex with a secondary ammonium salt.[17] In addi-
tion to the stabilization of closed-form crown ether and am-
monium moiety, destabilization at transition state, which is
presumably when the crown ether is placed on the bulky
group at the ends, is also important, because the energy dif-
ference between these strategies correspond to activation
[a] Dr.K.Hirose, Y.Shiba, K.Ishibashi, Y.Doi, Prof.Dr.Y.Tobe
Division of Frontier Materials Science
Graduate School of Engineering Science, Osaka University
1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)
Fax : (+81)6-6850-6229
E-mail: hirose@chem.es.osaka-u.ac.jp
Chem. Eur. J. 2008, 14, 981 – 986
ꢀ 2008 Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim
981

Figure 1.a) A concept of switching between fast and slow threadings in pseudorotaxane by using a photochromic anthracene-based [24]crown-8-type
macrocycle and DBA.b) Ideal non-threadable supramolecules.
sodium hydroxide resulted in low yields of the macrocycliza-
tion, partly because of the lability of diol 7.Even though
diol 7 is relatively stable in form of crystals, it decomposes
rapidly in solution.For this reason, high dilution conditions,
which are common for macrocyclization, could not be ap-
plied.Therefore, diol 7 obtained as fine crystals was con-
verted to stable bis(trimethylsilyl)ether 8 using N,O-bis(tri-
methylsilyl)acetamide (BSA) in 74% yield.Then in situ de-
protection and coupling of 8 with ditosylates 9 furnished
macrocycle 1 with considerably improved yield (27%) com-
pared with the previous syntheses of related molecules as
Figure 2.Concept and energy diagram of switching between fast and slow
threading in pseudorotaxane.
shown in Scheme 1.[18]
energy as shown in Figure 2.Because dibenzo-[24]crown-8 is
not able to do deslippage over the 3,5-dimethylphenyl stop-
per, 3,5-dimethylphenyl group is expected to be large
enough to prevent deslippage of the closed-form 2.Then,
we chose the phenyl group as a proper end group of axle-
like component.Consequently, it is expected that the photo-
controllable threading motion would be achieved using
crown ether 1 as the key ring component and DBA as the
proper axle-like component.For comparison, the rotaxanes
Scheme 1.Synthesis of the photochromic ring component 1.
5 and 6 composed of the same crown ether as ring compo-
nent and axle-like component with bulky stopper moieties
at the both ends were also prepared, where the threading/
dethreading motion was completely stopped.
Preparation of rotaxane 5: The synthesis of rotaxane 5 is
summarized in Scheme 2.The closed-form 2 was prepared
from 1 in benzene by irradiation with a 500-W high-pressure
mercury lamp followed by evaporation of the solvent with
cooling.Because the closed-form 2 is stable enough at low
temperature to handle, the freshly prepared 2 and secondary
ammonium phosphate 10 were dissolved in CH2Cl2/CH3CN.
The resulting pseudorotaxane 11 was treated with acid anhy-
dride 12 in the presence of 40 mol% of nBu3P under ice
Preparation of macrocycle 1: The previously reported prepa-
ration of the photocontrollable [18]crown-6- and [12]crown-
4-type compounds[18] containing a dianthrylethane moiety
from 1,2-bis(10-hydroxy-9-anthryl)ethane (7)[19] and corre-
sponding oligoethyleneglycol ditosylates in the presence of
982
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim
Chem. Eur. J. 2008, 14, 981 – 986

Photochromic Macrocycles
FULL PAPER
py: 10 min at 303 K, whereas 148 min at 283 K.Because of
the long half-life at low temperature, the closed-form mole-
cule 2 could be conveniently isolated and then converted re-
versibly at room temperature to the open-form molecule 1.
The photoirradiation and subsequent thermolysis were
performed repeatedly using the sample solution prepared in
quartz cell for absorption spectra in well-degassed CH3CN
(0.1 mm).Photoreaction was carried out using the 500-W
high-pressure mercury lamp through Pyrex filter for 30 s
cooling with water bath, then thermal reversion was carried
at 313 K for 45 min monitoring absorbance at 383 nm by
means of UV/Vis spectrometer.The change of the absorb-
ance is shown in Figure 4.After 10 times repetition, 974. %
durability is obtained based on the difference in absorbance.
Scheme 2.Synthesis of the [2]rotaxanes 5 and 6.
cooling.[20] Thermal reversion of the rotaxane 6 to 5 oc-
curred during the post-treatment.The open-form [2]ro-
taxane 5 was obtained in 57% yield (three steps from 10).
Quantitative interconversion of ring component 1 and 2:
The photoisomerization of ring component 1 to the corre-
sponding closed-form molecule 2 proceeded quantitatively.
The solution of 1 in well-degassed CD3CN was placed in a
Pyrex NMR tube at 285 K and irradiated with the high-pres-
sure mercury lamp for 10 min.After the irradiation, the so-
lution was kept under 273 K in order to avoid significant
thermal reversion of 2.In the 1H NMR spectra, a sharp sin-
glet signal assigned to the benzylic protons (Ha) of 1 at
4.1 ppm disappeared and a singlet signal assigned to the ali-
phatic protons appeared at 2.9 ppm after the irradiation as
shown in Figure 3.In the aromatic region, the characteristic
Figure 4.Ten continuous cyclical changes in relative absorbance at
383 nm during photoreaction and thermal reversion cycles between open-
form 1 and closed-form 2; recorded in CD3CN at 313 K.
Quantitative interconversion of rotaxane 5 and 6: The pho-
toisomerization of 5 to 6 proceeded also quantitatively.The
1H NMR spectra of 5 at 273 K are shown in Figure 5.In the
Figure 3.Partial 1H NMR spectra (270 MHz) of a) open-form macrocycle
1 and b) closed-form 2; recorded in CD3CN at 243 K.
signals at d 8.12 and 7.55 ppm disappeared after irradiation
and the corresponding aromatic protons (Hb, Hc) appeared
at d 6.8–7.0 ppm.
The thermal reversion of 2 to 1 involved appreciable spec-
tral change observed in UV-visible spectroscopy.The half-
life of 2 in acetonitrile was obtained based on the increase
of absorbance at 383 nm by means of UV-visible spectrosco-
Figure 5.Partial 1H NMR spectra (270 MHz) of a) open-form rotaxane 5
and b) closed-form 6; recorded in CD3CN at 273 K.
Chem. Eur. J. 2008, 14, 981 – 986
ꢀ 2008 Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim
www.chemeurj.org
983

K.Hirose et al.
1H NMR spectra, characteristic changes for the signals of
the ring component protons are observed.A sharp singlet
signal assigned to the benzylic protons (Ha) of 5 at d
4.05 ppm disappeared and corresponding signal of an ali-
phatic proton (Ha) appeared at 2.84 ppm after the irradia-
tion, the aromatic signals (Hb, Hc) at 8.12 and 7.55 ppm
shifted to 6.92–6.75 ppm after irradiation. The signal as-
signed to the benzylic protons of axle-like component (Hd)
of 5 at 4.42 ppm shifted to 5.08 ppm after the irradiation.
The thermal reversion of 5 to 6 was observed by the
1H NMR spectra and the UV-visible spectra.
the half-lives of corresponding rotaxane 6 to 5 are apprecia-
bly longer than those, apparent half-lives of 2 to 1 in the
presence of DBA are slightly longer than those of the ring
components 2 to 1 itself.
In order to characterize the pseudorotaxane formation of
the ring component 1 or 2 with the axle-like ammonium salt
1
component H NMR titration experiments were performed.
Although kinetic and thermodynamic data at high tempera-
tures were not obtainable because of the less thermal stabili-
1
ty of closed-form complex, H NMR spectroscopy at room
temperature gave information both on thermodynamic sta-
bility of pseudorotaxane and kinetic information of thread-
ing and dethreading rate.
The photoirradiation for 30 s and following thermolysis at
313 K for 60 min was performed repeatedly.The change of
the absorbance at 382 nm by means of UV/Vis spectrometer
is shown in Figure 6.After 10 times repetition, 975. % dura-
The addition of DBA to a solution of 1 in CD3CN formed
a crown ether–ammonium cation complex.The complexa-
tion equilibrium was fast on the NMR time scale and gave
signals at weight averaged chemical shifts of the free and
complexed host.The binding constants of this system were
obtained based on the chemical shift change by the titration
experiment followed by non-linear least-square data treat-
ment method.The binding constants are listed in Table 2 in
Table 2.Association constants of crown ethers 1 and 2 with dibenzyl am-
monium hexafluorophosphate in CD3CN, determined by nonlinear least-
squares method and single point measurement, respectively.
T [K]
K [mÀ1
]
1
2
273
263
253
243
233
23
30
42
53
63
67
82
126
184
286
Figure 6.Ten continuous cyclical changes in relative absorbance at
382 nm during photoreaction and thermal reversion cycles between open-
form 5 and closed-form 6; recorded in CD3CN at 313 K.
bility is obtained based on the difference in absorbance.The
half-life of 6 in acetonitrile was determined based on the in-
crease of absorbance at 383 nm by means of UV-visible
spectroscopy: 18 min at 303 K, whereas 222 min at 283 K.
Half-lives of the rotaxanes 6 to 5 are significantly longer
than those of the ring components 1 to 2.It seems very
likely that the presence of the salt will increase the stability
of the crown ether and slow down its retrophotodimeriza-
tion.
a temperature range from 273 to 233 K.In addition to the
binding constants, information on the frequency of molecu-
lar motions was obtained from this experiment.Even at a
low temperature of 233 K, the host–guest complexation
equilibrium has a fast exchange rate compared with the
NMR time scale.
In contrast, the host–guest complexation equilibrium of
the closed-form complex 2 with DBA in CD3CN has a slow
exchange rate compared with the NMR time scale so that
the peaks due to the complexed host and the free host are
observed individually in an NMR spectrum.The 1H NMR
spectrum of a mixture of 2 and DBA is shown in Figure 7
together with those of 2 c) and DBA a).In Figure 7b), the
signals with asterisks (*) are assigned to the pseudorotaxane
and others are due to the free DBA and free 2.
Characterization of pseudorotaxanes: The apparent half-life
of 2 in the presence of DBA in acetonitrile was obtained
based on the increase of absorbance at 383 nm by means of
UV-visible spectroscopy: apparent half-life is 11 min at
303 K, whereas it is 160 min at 283 K (Table 1).Although
1
Based on the H NMR spectra, the binding constants of 2
with DBA were obtained by the integration of the com-
plexed and free host signals.The results are listed in Table 2
together with those of 1 with DBA.The binding constants
of 2 are two to four times larger than those of the open-
form 1.The stable binding between 2 and DBA may explain
the elongation of apparent half-lives of 2 and slow exchange
in the presence of DBA.
Table 1.Apparent half-lives of the thermal reversion of 2, 6 and pseudo-
A
spectral changes.
T [K]
t1/2 [min]
2
2 with DBA
6
283
303
148
10
160
11
222
18
984
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim
Chem. Eur. J. 2008, 14, 981 – 986

Photochromic Macrocycles
FULL PAPER
fication for 30 min, was added through the dropping funnel.The solution
was added dropwise into the flask during 22.5 h under reflux. After an
additional 1 h stirring at 558C, the reaction mixture was cooled to room
temperature.The resulting reddish suspension was neutralized with 6 n
HCl.The mixture was extracted with Et 2O and CH2Cl2, washed with
brine, and dried over anhydrous MgSO4.The solvent was removed under
reduced pressure, which was followed chromatography (hexane/AcOEt
1:1) gave 1 (685 mg, 27%) as yellow foam. 1H NMR (300 MHz, CD3CN,
308C): d=8.12 (d, J=8.6 Hz, 4H), 7.53 (d, J=8.7 Hz, 4H), 7.21 (ddd, J=
1.0, 8.7, 8.6 Hz, 4H), 6.98–6.87 (m, 8H), 4.20 (t, J=4.8 Hz, 4H), 4.14 (s,
4H), 4.11 (t, J=4.8 Hz, 4H), 3.86 (t, J=6.8 Hz, 4H), 3.75 (t, J=2.8 Hz,
4H), 3.70–3.64 ppm (m, 8H); 13C NMR (100 MHz, CDCl3): d=150.6,
149.9, 131.7, 130.0, 125.6, 125.1, 125.0, 124.9, 123.4, 122.4, 115.5, 80.0,
71.7, 71.5, 70.9, 70.8, 69.9, 27.7 ppm; IR (KBr): n˜ = 3064, 3048, 2921,
2869, 1618, 1592, 1559, 1503, 1348, 1255, 1093, 771, 753 cmÀ1; HR-MS
(FAB): m/z: calcd for C48H48O8: 752.3349; found: 752.3346 [M+].
Closed crown ether 2: A solution of crown ether 1 (14.6 mg, 19.4 mmol)
in CD3CN (1.0 mL) was placed in a Pyrex NMR tube and was well de-
gassed by a bubbling of dry argon for 30 min.Then, the solution was irra-
diated using a 500-W high-pressure mercury lamp for 10 min.After irra-
diation, the reaction mixture was immediately chilled to 08C to avoid
thermal reversion reaction. 1H NMR (270 MHz, CD3CN, À308C): d=
7.29 (t, J=4.5 Hz, 4H), 7.10 (m, 4H), 7.02–6.84 (m, 12H), 4.18 (br, 4H),
3.94–3.88 (m, 12H), 3.77 (br, 4H), 3.39 (br, 4H), 2.94 ppm (s, 4H).
Figure 7. 1H NMR spectra (270 MHz, CD3CN, 243 K) of a 1:1 mixture
(20 mm) of open-form macrocycle 1 and DBA.The descriptors “*” refer
to signals representing protons of pseudorotaxane.
Conclusion
Rotaxane 5: A solution of crown ether 1 (100 mg, 133 mmol) in benzene
(10 mL) was placed in a Pyrex tube and was well degassed by a bubbling
of dry argon.Then, the solution was irradiated using a 500 W high-pres-
sure mercury lamp for 15 min in an ice bath.After irradiation, the sol-
vent was evaporated off with cooling.Freshly prepared 2 in CH2Cl2
(600 mL) was mixed with secondary ammonium phosphate 10 (49.0 mg,
121 mmol) in CH3CN (100 mL) and acid anhydride 12 (226 mg,
226 mmol) in CH2Cl2 (400 mL) in an ice-salt bath.Then, 40 mol% of
nBu3P (12 mmol) was added to the mixture solution under N2 atmos-
phere and the reaction solution was stirred for 3 h in the ice-salt bath.
Evaporation of the solvent followed by preparative HPLC separation
The anthracene-based photochromic molecules 1 and 2 are
interconverted reversibly by photoirradiation and thermoly-
sis.The binding constants of 1 and 2 with DBA differ con-
siderably.In addition, considerable differences in half-lives
of thermal reversions of pseudorotaxane 4 and rotaxane 6
are observed.The significant difference in frequencies of
threading motions of DBA with ring components 1 or 2 in
1
pseudorotaxane system is observed by H NMR spectrosco-
py.The rate constant of 1 is higher than the NMR time
scale, however, the rate constant of 2 is smaller within the
temperature range between 233 and 303 K.The switching
frequency of the molecular motion by the structural change
of ring component is possible to produce promising new
switching devices.We are currently investigating the extend-
ed application of this cavity-size changeable ring component
to the syntheses of two-station [2]rotaxanes for the demon-
stration to stop the shuttling process by action of light and
to quantify the shuttling velocity.
(JAIGEL-1H and 2H GPC columns with CHCl3) gave
5 (137 mg,
68.9 mmol, 57%). M.p. 131.0–134.58C; 1H NMR (270 MHz, CD3CN,
08C): d=8.14 (d, J=1.2 Hz, 4H), 7.95 (d, J=8.3 Hz, 4H), 7.95–7.80 (br,
2H), 7.83 (brs, 2H), 7.56 (d, J=8.3 Hz, 4H), 7.44 (d, J=9.0 Hz, 4H),
7.40 (d, J=8.3 Hz, 4H), 6.92–6.89 (m, 4H), 6.78–6.75 (m, 4H), 6.69–6.67
(m, 2H), 6.58–6.55 (m, 2H), 5.28 (s, 4H), 4.42 (brt, J=6.6 Hz, 4H), 4.05
(s, 4H), 3.97–3.95 (m, 4H), 3.86–3.84 (m, 16H), 3.71–3.70 (m, 4H), 1.39
(heptet, J=7.3 Hz, 12H), 1.00 ppm (d, J=7.3 Hz, 72H); 13C NMR
(100 MHz, CDCl3): d=166.9, 148.7, 147.1, 146.41, 146.40, 138.3, 136.4,
134.2, 130.6, 130.4, 129.3, 129.0, 128.1, 128.0, 124.5, 124.1, 123.6, 121.9,
121.8, 112.3, 73.9, 71.2, 70.6, 70.2, 69.6, 68.3, 65.7, 52.7, 26.6, 18.6,
10.8 ppm; IR (KBr): n˜ = 2943, 2866, 1725, 1506, 1459, 1268, 1131, 882,
842 cmÀ1; MS (FAB): m/z: 1843.0 [MÀPF6]+, elemental analysis calcd
(%) for C114H156 F6NO12PSi4: C 68.81, H 7.90, N 0.70; found: C 68.65, H
8.03, N 0.69.
Experimental Section
Closed rotaxane 6: In a manner similar to that described for 2, a solution
of rotaxane 5 (7.0 mg, 3.52 mmol) in CD3CN (700 mL) was irradiated.
After irradiation, the reaction mixture was immediately chilled to 08C to
avoid thermal reversion reaction. 1H NMR (400 MHz, CD3CN, 308C):
d=8.21 (d, J=1.2 Hz, 4H), 7.98 (br, 2H), 7.87 (brt, J=1.2 Hz, 2H), 7.67
(d, J=7.9 Hz, 4H), 7.43 (d, J=8.1 Hz, 4H), 6.95 (d, J=7.2 Hz, 4H), 6.84
(d, J=7.3 Hz, 4H), 6.70–6.57 (m, 12H), 5.31 (s, 4H), 5.08 (br, 4H), 3.98
(br, 8H), 3.73–3.64 (m, 12H), 3.40 (br, 4H), 2.84 (s, 4H), 1.46 (heptet,
J=7.4 Hz, 12H), 1.04 (d, J=7.3 Hz, 72H).
General methods: 1H NMR (270, 300, or 400 MHz) and 13C NMR (67.5,
75.0, or 100 MHz) spectra were recorded on a JEOL JNM-AL-400, a
Varian Mercury 300 or a JEOL JNM-GSX-270 spectrometer.The chemi-
cal shifts of 1H NMR and 13C NMR signals are quoted relative to tetra-
methylsilane.IR spectra were recorded as a KBr disk on a JASCO
FTIR-410 spectrometer.Mass spectral analyses were performed on a
JEOL JMS-DX303HF.Elemental analyses were carried out with
a
Perkin-Elmer 2400II analyzer.UV-visible spectra were recorded on a Hi-
tachi U-3310 spectrometer in acetonitrile.Preparative HPLC separation
was undertaken with
a JAI LC-908 chromatograph using 600 mm”
20 mm JAIGEL-1H and 2H GPC columns with CHCl3 as an eluent.Sol-
vents were dried (drying agent in parentheses) and distilled prior to use:
THF (sodium/benzophenone), CH3CN, CH2Cl2 (CaH2).
Acknowledgements
Crown ether 1: In a 1 L three-necked flask equipped with a reflux con-
denser, a thermometer, a Hershberg dropping funnel, and a magnetic
stirrer bar were placed a saturated aqueous solution (9 mL, 130 mmol) of
KOH and THF (100 mL).A solution of 8 (1.91 g, 3.42 mmol) and ditosy-
late 3 (2.50 g, 3.66 mmol) in THF (500 mL), which was deaerated by soni-
This work was supported by the Izumi Science and Technology Founda-
tion and a Grant-in-Aid for Scientific Research from the Ministry of
Education, Culture, Sports, Science and Technology of Japan.KI..ex-
presses his special thanks to the Global COE (Center of Excellence) Pro-
Chem. Eur. J. 2008, 14, 981 – 986
ꢀ 2008 Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim
www.chemeurj.org
985

K.Hirose et al.
gram “Global Education and Research Center for Bio-Environmental
Chemistry” of Osaka University.
455; u) T.Felder, C.A.Schalley,
In Artificial Rotary Motors Based
on Rotaxanes: Highlights in Bioorganic Chemistry (Eds..: H. Wen-
nemers, C.Schmuck), Wiley-VCH, Weinheim, 2004, p.526; v) E.R.
Kay, D.A. Leigh, F. Zerbetto, Angew. Chem. 2007, 119, 72–196;
Angew. Chem. Int. Ed. 2007, 46, 72–191.
[1] a) G.Schill, Catenanes, Rotaxanes and Knots, Academic Press, New
York, 1971; b) D.M. Walba, Tetrahedron 1985, 41, 3161–3212;
[6] For circumrotation, see: P.L.Anelli, P.R.Ashton, R.Ballardini, V.
Balzani, M. Delgado, M.T. Gandolfi, T.T. Goodnow, A.E. Kaifer,
D.Philp, M.Pietraszkiewicz, L.Prodi, M.V.Reddington, A.M.Z.
Slawin, N.Spencer, J.F.Stoddart, C.Venturi, D.J.Williams,
Chem. Soc. 1992, 114, 193–218.
[7] For shuttling, see: a) P.L. Anelli, N. Spencer, J.F. Stoddart,
c) C.O. Dietrich-Buchecker, J-.P. Sauvage,
Chem. Rev. 1987, 87,
795–810; d) H.W.Gibson, H.Marand, Adv. Mater. 1993, 5, 11–21;
e) D.B.Amabilino, J.F.Stoddart, Chem. Rev. 1995, 95, 2725–2828;
f) R.Jäger, F.Vçgtle, Angew. Chem. 1997, 109, 966–980; Angew.
Chem. Int. Ed. Engl. 1997, 36, 930–944; g) G.A. Breault, C.A.
Hunter, P.C. Mayers, Tetrahedron 1999, 55, 5265–5293; h) Molec-
ular Catenanes, Rotaxanes and Knots (Eds.: J-.P.Sauvage, C.O.Die-
trich-Buchecker), Wiley-VCH, Weinheim, 1999; i) V.Balzani, M.
Venturi, A.Credi, Molecular Devices and Machines, Wiley-VCH,
J. Am.
J. Am.
Chem. Soc. 1991, 113, 5131–5133; b) R.A. Bissell, E. Córdova,
A.E. Kaifer, J.F. Stoddart, Nature 1994, 369, 133–137; c) P.L.
Anelli, M.Asakawa, PR. .Ashton, RA. .Bissell, G.Clavier, R.
Górski, A.E.Kaifer, S.J.Langford, G.Mattersteig, S.Menzer, D.
Philp, A.M.Z.Slawin, N.Spencer, J.F.Stoddart, M.S.Tolley, D.J.
Williams, Chem. Eur. J. 1997, 3, 1113–1135; d) D.A. Leigh, A.
Troisi, F.Zerbetto, Angew. Chem. 2000, 112, 358–361; Angew.
Chem. Int. Ed. 2000, 39, 350–353; e) P.R.Ashton, R.Ballardini, V.
Balzani, A.Credi, KR. .Dress, E.Ishow, CJ..Kleverlaan, O.
Kocian, J.A. Preece, N. Spencer, J.F. Stoddart, M. Venturi, S.
Wenger, Chem. Eur. J. 2000, 6, 3558–3574; f) Q.-C. Wang, D.-H. Qu,
Weinheim, 2003; j) H.Tian, Q-.C.Wang,
Chem. Soc. Rev. 2006, 35,
361–374.
[2] a) A.P.de Silva, H.Q.N.Gunaratne, C.P.McCoy,
Nature 1993, 364,
J. Am.
42–44; b) P.Ghosh, PK. .Bharadwaj, J.Roy, S.Ghosh,
Chem. Soc. 1997, 119, 11903–11909; c) D.L. Feldheim, C.D. Keat-
ing, Chem. Soc. Rev. 1998, 27, 1–12; d) C.P. Collier, E.W. Wong,
M.Belohradsky, F.M.Raymo, J.F.Stoddart, J.P.Kuekes, R.S.Wil-
liams, J.R. Heath, Science 1999, 285, 391–394; e) M.Asakawa, M.
Higuchi, G.Mattersteig, T.Nakamura, A.R.Pease, F.M.Raymo, T.
Shimizu, J.F. Stoddart, Adv. Mater. 2000, 12, 1099–1102; f) C.P.
Collier, G.F.Mattersteig, E.W.Wong, Y.Lou, K.Beverly, J.Sam-
J.Ren, K.Chen, H.Tian,
Angew. Chem. 2004, 116, 2715–2719;
Angew. Chem. Int. Ed. 2004, 43, 2661–2665.
[8] For molecular electronic devices see; A.R. Pease, J.O. Jeppesen,
J.F.Stoddart, Y.Luo, CP. .Collier, JR. .Heath,
Acc. Chem. Res.
2001, 34, 433–444.
[9] P.Ghosh, G.Federwisch, M.Kogej, C.A.Schalley, D.Haase, W.
Saak, A.Lützen, RM. .Gschwind,
2691–2700.
[10] a) V.Balzani, M.Venturi, A.Credi,
paio, F.M. Raymo, J.F. Stoddart, J.R. Heath,
1172–1175; g) E.W. Wong, C.P. Collier, M. Belohradsky, F.M.
Raymo, J.F. Stoddart, J.R. Heath, J. Am. Chem. Soc. 2000, 122,
5831–5840; h) F.Barigelletti, L.Flamigni, Chem. Soc. Rev. 2000, 29,
1–12; i) E.M. Perez, D.T.F. Dryden, D.A. Leigh, G. Teobaldi, F.
Zerbetto, J. Am. Chem. Soc. 2004, 126, 12210–12211; j) D.-H. Qu,
F.-Y. Ji, Q.-C. Wang, H. Tian, Adv. Mater. 2006, 18, 2035–2038.
Science 2000, 289,
Org. Biomol. Chem. 2005, 3,
Molecular Devices and Ma-
chines, Wiley-VCH, Weinheim, 2003, pp.348–386; b) I. Yoon, M.
Narita, T.Shimizu, M.Asakawa,
16740–16741.
J. Am. Chem. Soc. 2004, 126,
[3] a) H.Kurreck, M.Hüber,
Angew. Chem. 1995, 107, 929–947;
[11] For a description of the intermediate region between pseudorotax-
ane and rotaxanes see; A. Affeld, G.M. Hübner, C. Seel, C.A.
Schalley, Eur. J. Org. Chem. 2001, 2877–2890.
Angew. Chem. Int. Ed. Engl. 1995, 34, 849–866; b) G.Steinberg-
Yfrach, P.A. Liddell, S.C. Hung, A.L. Moore, D. Gust, T.A.
Moore, Nature 1997, 385, 239–241; c) G.Steinberg-Yfrach, J-L. .
[12] For effects of the size of stoppers, see: T.Felder, C.A.Schalley,
Angew. Chem. 2003, 115, 2360–2363; Angew. Chem. Int. Ed. 2003,
42, 2258–2260.
Rigaud, E.N.Durantini, A.L.Moore, D.Gust, T.A.Moore,
1998, 392, 479–482.
[4] a) S.Fernandez-Lopez, HS. .Kim, EC. .Choi, M.Delgado, JR. .
Nature
[13] For a ring shape and a stopper structure, see: P.Linnartz, S.Bitter,
C.A.Schalley, Eur. J. Org. Chem. 2003, 4819–4829.
Granja, A.Khasanov, K.Kraehenbuehl, G.Long, D.A.Weinberger,
K.M. Wilcoxen, M.R. Ghadiri, Nature 2001, 412, 452–455; b) N.
[14] For a length of dumbbell component on thermodynamic parameters
Sakai, S.Matile, Chem. Commun. 2003, 2514–2523.
of these motions see; P.Linnartz, C.A.Schalley,
2004, 16, 263–267.
Supramol. Chem.
[5] a) J.A. Preece, J.F.Stoddart, Nanobiology 1994, 3, 149–166; b) M.
Gómez-López, J.A. Preece, J.F. Stoddart, Nanotechnology 1996, 7,
183–192; c) M.D. Ward, Chem. Ind. 1997, 640–645; d) V.Balzani,
M.Gómez-López, J.F.Stoddart, Acc. Chem. Res. 1998, 31, 405–414;
e) J.-P. Sauvage, Acc. Chem. Res. 1998, 31, 616–619; f) J.K. Gim-
zewski, C.Joachim, R.R.Schlittler, V.Langlais, H.Tang, I.Johann-
[15] R.Livington, K.S.Wei, J. Am. Chem. Soc. 1967, 89, 3098–3100.
[16] For the anthracene-based photochromic host molecules of crown
ether derivatives see; H.B. -Laurent, A. Castellan, J.-P. Desvergne,
Pure Appl. Chem. 1980, 52, 2633–2648; for cyclodextrin derivatives:
F.Moriwaki, A.Ueno, T.Osa, Chem. Lett. 1986, 1865–1868; for cal-
sen, Science 1998, 281, 531–5333; g) A.Niemz, V.M.Rotello,
Chem. Res. 1999, 32, 42–52; h) A.E.Kaifer, Acc. Chem. Res. 1999,
32, 62–71; i) L.Fabbrizzi, M.Licchelli, P.Pallavicini, Acc. Chem.
Acc.
ixarene derivative: G.Deng, T.Sakai, Y.Kawahara, S.Shinkai,
Su-
pramol. Chem. 1993, 2, 71–76; for cryptand derivative: J.H.R.
Tucker, HB. .-Laurent, P.Marsau, SW. .Riley, -JP. .Desvergne,
Chem. Commun. 1997, 1165–1166.
Res. 1999, 32, 846–853; j) D.A.Leigh, A.Murphy, Chem. Ind. 1999,
178–183; k) N.R. Koumura, W.J. Zijlstra, R.A. van Delden, N.
Harada, B.L.Feringa, Nature 1999, 401, 152–155; l) T.R.Kelly, H.
De Silva, R.A. Silva, Nature 1999, 401, 150–152; m) M.D. Ward,
Chem. Ind. 2000, 22–26; n) V.Balzani, A.Credi, F.M.Raymo, J.F.
Stoddart, Angew. Chem. 2000, 112, 3484–3530; Angew. Chem. Int.
Ed. 2000, 39, 3348–3391; o) B.L. Feringa, R.A. van Delden, N.
Koumura, E.M. Geertsema, Chem. Rev. 2000, 100, 1789–1816;
[17] PT..Glink, C.Schiavo, JF..Stoddart, DJ.Williams,
Chem.
Commun. 1996, 1483–1490.
[18] For [18]crown-6-type compounds see; I.Yamashita, M.Fujii, T.
Kaneda, S.Misumi, Tetrahedron Lett. 1980, 21, 541–544; for
[12]crown-4-type compounds: J.P.Desvergne, J.Lauret, H.B-.Lau-
rent, Recl. Trav. Chim. Pays-Bas 1995, 114, 504–513.
[19] H.D. Becker, D. Sanchez, A. Arvidsson,
4247–4251.
[20] H.Kawasaki, N.Kihara, T.Takata, Chem. Lett. 1999, 1015–1016.
J. Org. Chem. 1979, 44,
p) T.R.Kelly, R.A.Silva, H.De Silva, S.Jasmin, Y.Zhao,
J. Am.
Chem. Soc. 2000, 122, 6935–6949; q) C.A. Schalley, K. Beizai, F.
Vçgtle, Acc. Chem. Res. 2001, 34, 465–476; r) J-.P.Collin, C.Die-
trich-Buchecker, P.GaviÇa, MC. .Jimenez-Molero, JP..Sauvage,
Acc. Chem. Res. 2001, 34, 477–487; s) A.N. Shipway, I. Willner,
Acc. Chem. Res. 2001, 34, 421–432; t) R.Ballardini, V.Balzani, A.
Credi, M.T. Gandolfi, M. Venturi, Acc. Chem. Res. 2001, 34, 445–
Received: August 21, 2007
Published online: November 12, 2007
986
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim
Chem. Eur. J. 2008, 14, 981 – 986