Energy transfer and concentration-dependent conformational modulation: A porphyrin-containing [3]rotaxane

Article abstract of DOI:10.1002/asia.201200443

A zinc porphyrin-containing [3]rotaxane A was synthesized through a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Energy donors and acceptor porphyrin were introduced to dibenzo[24]crown-8 (DB24C8) and dibenzyl ammonium (DBA) units of [

Full text of DOI:10.1002/asia.201200443

DOI: 10.1002/asia.201200443
Energy Transfer and Concentration-Dependent Conformational Modulation:
A Porphyrin-Containing [3]Rotaxane
Xiao-Ye Wang, Ji-Min Han, and Jian Pei*[a]
Abstract: A zinc porphyrin-containing
[3]rotaxane A was synthesized through
a copper(I)-catalyzed azide–alkyne cy-
cloaddition (CuAAC) reaction. Energy
donors and acceptor porphyrin were in-
The fluorescence of energy donors in
the region of 400 to 450 nm was effi-
ciently absorbed by the porphyrin ac-
ceptor under irradiation at 345 nm, and
finally a red light emission at about
600 nm was achieved. Further investi-
gation indicated that the conformation
of [3]rotaxane A was self-modulated by
changing its concentration in CH2Cl2.
The triazole groups on the wheel coor-
dinated or uncoordinated to Zn2+
through intramolecular self-coordina-
tion with the change in the concentra-
tion of [3]rotaxane A in CH2Cl2. There-
fore, this conformational change was
reversible in a non-coordinating sol-
vent such as CH2Cl2 but inhibited in
a coordinating solvent such as THF.
Such interesting behaviors were rarely
observed in porphyrin derivatives. This
self-modulation feature opens up the
possibility of controlling molecular
conformation by varying concentration.
troduced
to
dibenzo[24]crown-8
(DB24C8) and dibenzyl ammonium
(DBA) units of [3]rotaxane A to un-
derstand the intramolecular energy
transfer process. Investigations of the
photophysical properties of [3]rotaxane
A demonstrated that the intramolecu-
lar efficient energy transfer readily oc-
curred from the donors on the wheels
to the porphyrin center on the axis.
Keywords: conformational change ·
cycloaddition · energy transfer ·
porphyrinoids · rotaxanes
Introduction
both artificial photosynthetic models and stimuli-responsive
molecular machines.[9] Most porphyrin-containing MIMs
were developed in relation to energy transfer (ET) and elec-
tron transfer as mimics of photosynthetic systems.[10] Few ex-
amples were reported in host–guest chemistry with porphy-
rin units as receptors.[11] This situation prompts us to explore
new structures of this class of molecules and to investigate
their novel properties and functions.
Herein, we develop a highly functionalized zinc porphy-
rin-containing [3]rotaxane A (Scheme 1), in which the por-
phyrin segment functions not only as the energy acceptor in
an ET process, but also as the coordination center for con-
formational change. The molecule is comprised of two trux-
ene units on the wheels and a porphyrin core on the axis.
Efficient intramolecular ET readily occurs from the wheels
to the porphyrin center due to the mechanical linkage of
energy donors and acceptors. Furthermore, a conformational
change is observed due to the coordination of triazole li-
gands to the zinc(II) porphyrin in dilute solutions, and such
a molecular movement is well controlled by varying concen-
trations. To the best of our knowledge, this is the first report
on concentration-dependent conformational change in por-
phyrin-containing rotaxanes.
Mechanically interlocked molecules (MIMs), such as cate-
nanes and rotaxanes, have attracted substantial research in-
terest for their functional properties and potential applica-
tions in molecular machines.[1] The interlocked components
in MIMs have a large mobility in nature, hence various stim-
uli-responsive molecular movements are realized. A myriad
of molecular machines were constructed and successfully op-
erated by several external stimuli, such as light,[2] redox re-
actions,[3] pH changes,[4] and ions.[5]
Porphyrin and its derivatives have exhibited their unique
applications in organic materials and supramolecular
chemistry.[6,7] Particularly, they were extensively studied in
synthetic models of photosynthesis to mimic the functions of
the light-harvesting antenna complexes and the photosyn-
thetic reaction center in natural systems.[8] The incorporation
of porphyrins into MIMs creates a new family of compounds
which combines the excellent optoelectronic properties of
porphyrins with the flexibility of the mechanically inter-
locked structures, thus providing potential applications in
[a] X.-Y. Wang, J.-M. Han, Prof. J. Pei
Beijing National Laboratory for Molecular Sciences (BNLMS)
Key Laboratory of Bioorganic Chemistry and Molecular Engineering
College of Chemistry and Molecular Engineering
Peking University, Beijing 100871 (P. R. China)
Fax : (+86)10-62751708
Results and Discussion
Design and Synthesis
E-mail: jianpei@pku.edu.cn
The chemical structures of [3]rotaxane A along with models
B, C, and D are shown in Scheme 1. The truxene skeleton
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201200443.
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FULL PAPER
Scheme 1. The chemical structures of [3]rotaxane A, its corresponding derivatives A1 and A2, axis B, wheel C, and model D.
functions as the energy donors due to its high fluorescence
quantum efficiency.[12] [3]Rotaxane A was synthesized utiliz-
ing a “threading-followed-by-stoppering” strategy among
various template-directed protocols.[13] The well-known in-
teraction between dibenzo[24]crown-8 (DB24C8) and diben-
zyl ammonium (DBA) was chosen for the mechanical as-
sembly,[14] and the CuI-catalyzed azide–alkyne cycloaddition
(CuAAC) was applied for the stoppering due to its good
functional-group tolerance and high efficiency.[14a,15]
The synthetic route to wheel C is illustrated in Scheme 2.
Compound 1 was synthesized following our previous
report.[16] A Horner–Wadsworth–Emmons (HWE) reaction
between 1 and diethyl benzylphosphonate 2 afforded 3 in
91% yield, which was converted to compound 4 by a Suzuki
cross-coupling reaction with 4-formylphenyl boronic acid.
Reduction of 4 followed by bromonation afforded 6 in 83%
yield for two steps. Subsequently, a nucleophilic substitution
with NaN3 afforded azide-functionalized derivative 7, which
was applied for the CuAAC reaction with ethynyl-substitut-
ed DB24C8 8 to give wheel C as a white solid.
The synthetic approach to [3]rotaxane A is depicted in
Scheme 3. Compound 10 was prepared and converted to
porphyrin 12 according to the literature.[17] The ester group
was reduced by LiAlH4 to produce diol 13, which was fur-
ther oxidized to afford dialdehyde 14. A condensation of
compound 14 and benzylamine 15 in refluxing chloroform
gave imine in quantitative yield, which was used for the sub-
sequent reduction without further purification. Com-
pound 16 was obtained in 91% yield for two steps as a red
solid. Unfortunately, when we tried to acidify benzyl amine
with 6m HCl, trifluoroacetic acid (TFA), or trifluorometha-
nesulfonic acid (TfOH), the nitrogen atoms in the porphyrin
moiety were also protonated.[18] Finally, we succeeded in
solely protonating the amine part with dilute aqueous acetic
acid (HOAc). However, the free-base porphyrin could not
survive from the CuAAC reaction because CuI inserted into
its central cavity.[19] Therefore, we turned the free-base por-
phyrin derivative 16 to its corresponding zinc porphyrin,
which was more stable in acidic conditions and tolerant to
the CuAAC reaction. Subsequent acidification with dilute
aqueous HCl (pH 1) followed by anion exchange with
NH4PF6 afforded DBA 17 in 83% yield. We chose the
“threading-followed-by-stoppering” strategy for the synthe-
Abstract in Chinese:
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Porphyrin-Containing [3]Rotaxane
Scheme 2. The synthetic route to wheel C.
Scheme 3. The synthetic route to [3]rotaxane A. TFA=trifluoroacetic acid, DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone, PCC=pyridinium chloro-
chromate.
sis of [3]rotaxane A. Although the binding constant of
DB24C8 and DBA in CH2Cl2 is quite large, excess of C was
present to ensure complete threading. Such a well-estab-
lished process was very fast, and the threaded assembly was
then subjected to the stoppering reaction. [3]Rotaxane A
was purified by flash chromatography and recycling prepara-
tive GPC and isolated in 45% yield. Model B was also pre-
pared for comparison.
[AÀ2PF6]2+, while no signals of by-product B or mono-
threaded [2]rotaxane was observed, indicating high purity of
[3]rotaxane A. The ESI-HRMS characterization perfectly
matched
with
the
calculated
results
for
[C372H416N18O22Zn]2+, which strongly confirmed the identity
of A.
Photophysical Properties
The chemical structure of [3]rotaxane A was verified by
1H and 13C NMR spectroscopy and ESI-HRMS characteriza-
tion (Figure 1). The peak at m/z=2778.0 corresponded to
The absorption spectra of [3]rotaxane A and models B and
C are illustrated in Figure 2a. Compound C showed a broad
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As shown in Figure 2b, for compound B, an emission
maximum at 604 nm with a shoulder peak at 652 nm was ob-
served, featuring fluorescence from the ZnP moiety. Com-
pound C showed an intense emission from 380 to 500 nm,
which had a large overlap with the absorption of B. This
spectral overlap together with the close proximity caused by
the mechanical linkage was crucial for fluorescence reso-
nance energy transfer (FRET).[20] To investigate the FRET
process, we examined the photoluminescence (PL) spectra
of [3]rotaxane A excited at different wavelengths. As shown
in Figure 2c, under excitation at the absorption maximum of
axis B (425 nm), compound A exhibited a typical fluores-
cence from the ZnP moiety as discussed above. When excit-
ed at the absorption lmax of wheel C at 345 nm, compound
A also showed similar emission characteristics, which was
not observed in axis B when it was exited at the same wave-
length, thus indicating efficient intramolecular energy trans-
fer occurred from wheel C to the ZnP unit. To further un-
derstand this ET process, we compared the emission spectra
of A and C. As shown in Figure 2d, the fluorescence feature
of [3]rotaxane A from 380 to 500 nm was split into two
main peaks. Compared to that of free molecule C, the inten-
sity was greatly weakened in the region of 400 to 450 nm,
which corresponded to the absorption of the porphyrin
moiety. Therefore, it was concluded that excitons generated
in the energy donors partially went to the energy-acceptor
chromophore, ZnP unit in this case. The fluorescence quan-
tum yield (FF) of A was measured to be 1.8% under excita-
tion at 345 nm, using tetraphenylporphyrin (TPP) as a stan-
dard.[21]
Figure 1. ESI-MS spectra of [3]rotaxane A. The peak at m/z=2778.0 cor-
responds to [AÀ2PF6]2+. Shown in the inset are the ESI-HRMS spectra
of a) experimental results; b) calculated results.
absorption band with lmax =345 nm, which was assignable to
the p-extended truxene derivatives. Compound B showed
typical absorption features of zinc porphyrin (ZnP) with
a sharp Soret band at 425 nm and Q bands in the region of
500 to 650 nm. The absorption of compound A was con-
structed by weighted addition of that of axis B and two-fold
intensity of wheel C, suggesting a 1:2 molar ratio of B and C
in [3]rotaxane A without ground-state interaction in THF
solution.
Figure 2. a) The absorption spectra of A, B, and C. b) The absorption and emission spectra of B and C. c) The emission spectra of A excited at different
wavelengths. d) The absorption spectrum of B and emission spectra of A and C excited at 345 nm. All the spectra were recorded in THF (1ꢁ10À6 m).
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Porphyrin-Containing [3]Rotaxane
the fact that the Soret band at 425 nm in THF showed
a slight bathochromic shift compared to 420 nm in CH2Cl2.
To further demonstrate this assumption, we carried out
the demetalation of A to afford the free-base porphyrin. Al-
though the obtained [3]rotaxane A1 exhibited identical
peaks at 345 and 420 nm, the Q bands of A1 showed the
four characteristic peaks (517, 547, 590, and 645 nm) of
a free-base porphyrin (Figure S1 in the Supporting Informa-
tion). More importantly, the absorption features of [3]rotax-
ane A1 did not change with concentration and time, suggest-
ing that Zn2+ in the porphyrin core was necessary for such
a process. That means the emerging peak at 435 nm implied
the occurrence of coordination to the ZnII ion in the porphy-
rin.
Since there are two kinds of triazole groups separately at-
tached on the wheels and the thread, we speculate that the
ones on the wheels have more opportunities to coordinate
to ZnP due to their flexible conformation. When we exam-
ined the absorption spectra of model B in CH2Cl2 at differ-
ent concentrations (Figure S2 in the Supporting Informa-
tion), only one sharp peak in the Soret band at 420 nm was
observed, and no peak at 435 nm appeared even after 24 h.
These results strongly supported our speculation that only
the triazole groups on the wheel played a key role in coordi-
nating to ZnP moiety on the thread. However, the confor-
mation of the wheel in [3]rotaxane A is partially fixed by
the hydrogen bonding between DB24C8 and DBA units,
which explains why it takes a long time for their geometry
to adjust to a thermodynamically favored self-coordinated
conformation.[23] In order to confirm our hypothesis on the
above kinetic issues, we managed to break the hydrogen
bonding by treating [3]rotaxane A with Na2CO3 to deproto-
nate the ammonium groups, thus reducing the energy barri-
ers for adjusting conformation of the wheels. The absorption
spectra of the obtained [3]rotaxane A2 in dilute CH2Cl2 sol-
utions were recorded (Figure 4a). The new peak at 435 nm
showed up immediately after dilution, and the peak intensi-
ty at 420 nm decreased gradually. By concentrating the solu-
tion, we confirmed that this process was exactly reversible,
as a reversed tendency could be observed. These results not
only confirm the above-mentioned coordination hypothesis,
but also indicate that such a concentration-dependent con-
formational change shows fast response without the hydro-
gen-bonding fixture between wheels and axis.
Conformational Change in Dilute Solution
We further investigated the absorption features of [3]rotax-
ane A in dilute CH2Cl2. A new peak at 435 nm in the Soret
band appeared after 24 h, and the intensity of the peak at
420 nm decreased (Figure 3b,c). This phenomenon was
more significant in dilute solutions and turned out to be
concentration-dependent. Such a change was not observed
in our previous study in THF solution. Considering the dif-
ferent solvent effects on coordination between THF and
CH2Cl2, we attributed this emerging peak at longer wave-
length to the coordination of triazole groups to ZnII ion in
the porphyrin nucleus.[22] CH2Cl2 is a non-coordinating sol-
vent, so that triazole groups coordinate to the ZnP moiety
through intramolecular interaction in dilute solutions,
whereas such a complex was disrupted in a coordinating sol-
vent such as THF. This explanation is also consistent with
To give more insight into this process, we synthesized an-
other model D containing a triazole group. By adding com-
pound D to a solution of B in CH2Cl2 (5ꢁ10À6 m), a signifi-
cant bathochromic shift of the Soret band was observed
(Figure 4b). The intensity of the peak at 420 nm decreased
gradually, and a new peak at 432 nm emerged. A clear iso-
sbestic point was observed during the titration, thus indicat-
ing that the transformation happened between two identical
states. The association constant (Ka) was estimated to be 2ꢁ
102 mÀ1, suggesting a quite weak interaction between the tria-
zole groups and ZnP motif in this system. Scheme 4 illus-
trates the concentration-dependent conformational change
in [3]rotaxane A, which is achieved by such a weak interac-
Figure 3. The absorption spectra of [3]rotaxane A monitored at different
times (0 h and 24 h) in CH2Cl2: a) 1ꢁ10À5 m; b) 1ꢁ10À6 m; c) 1ꢁ10À7 m.
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Conclusions
We have synthesized a highly functionalized zinc(II) porphy-
rin-containing [3]rotaxane A through the CuAAC reaction.
The detailed investigation of the photophysical properties of
[3]rotaxane A indicates that the efficient intramolecular ET
process readily occurs from the wheels to the porphyrin
moiety on the axis. Further investigation demonstrates that
a concentration-dependent conformational change is exactly
reversible in the dilute solution of [3]rotaxane A in CH2Cl2.
This is the first example of modulating conformation by
changing concentration of porphyrinic rotaxanes. The inves-
tigation results demonstrate that concentration variations
can be used as a stimulus to trigger the conformational
change in a mechanically interlocked molecule. Such a con-
formational change is reversible in CH2Cl2 and inhibited in
a coordinating solvent such as THF. This work greatly en-
riches the structures and properties of the family of porphy-
rin-containing MIMs, and such a unique concentration-de-
pendent conformational change shows potential in its appli-
cation to magnetic spin switching of molecules in solution.[24]
Experimental Section
Figure 4. The absorption spectra of a) the neutral [3]rotaxane A2 in dif-
ferent concentrations; b) the model compound B in CH2Cl2 (5ꢁ10À6 m)
after adding different amounts of compound D at room temperature.
General Methods
All commercially available chemicals were used without further purifica-
tion unless otherwise noted. Dichloromethane was distilled from CaH2
under a nitrogen atmosphere. Tetrahydrofuran (THF) was freshly dis-
tilled from sodium under a nitrogen atmosphere prior to use. Column
chromatography was performed with silica gel. Analytical thin-layer
chromatography (TLC) was performed on 0.2 mm silica gel coated glass
sheets with F254 indicator. All yields given refer to yields of isolated
products. Nuclear magnetic resonance (NMR) spectra were recorded on
300 or 400 MHz Varian spectrometers. Chemical shifts were reported in
ppm. Coupling constants (J values) were reported in Hertz. 1H NMR
chemical shifts were referenced to TMS (0 ppm) or CHCl3 (7.26 ppm) or
CHD2CN (1.94 ppm) and 13C NMR chemical shifts were referenced to
CDCl3 (77.00 ppm) or CD3CN (118.69 ppm). HRMS (ESI) spectra were
recorded on a Bruker Apex IV FTMS. The recycling preparative GPC
separation was performed by using JAI LC-9201 recycling preparative
HPLC with 1H and 2H GPC column. Absorption spectra were recorded
on PerkinElmer Lambda 750 UV/Vis Spectrometer. Photoluminescence
(PL) spectra were recorded on a PerkinElmer LS 55 Luminescence Spec-
trometer.
Scheme 4. Graphical representation of the concentration-dependent con-
formational change in dilute CH2Cl2 solution. This process is inhibited in
a coordinating solvent such as THF.
Compound 3
A mixture of compound 1 (4.02 g, 3.54 mmol) and diethyl benzylphosph-
onate 2 (2.02 g, 8.86 mmol) was dissolved in anhydrous THF (50 mL)
under a nitrogen atmosphere. After the mixture was cooled to À788C,
a solution of tBuOK (1.00 g, 8.91 mmol) in THF (15 mL) was added
dropwise. The mixture was stirred for 3 h and then warmed to room tem-
perature for another 12 h. Aqueous HCl (10 mL, 3m) was added and the
aqueous layer was extracted with CH2Cl2. The organic extraction was
washed with water and dried over anhydrous Na2SO4. After removal of
the solvent under reduced pressure, the residue was purified by column
chromatography over silica gel (petroleum ether/CH2Cl2 =15:1) to afford
4.05 g (91%) of 3 as a white solid. 1H NMR (400 MHz, CDCl3, 298 K):
d=8.46–8.37 (m, 2H), 8.25 (d, J=8.6 Hz, 1H), 7.77 (d, J=8.2 Hz, 4H),
7.73–7.65 (m, 8H), 7.60–7.52 (m, 6H), 7.38 (t, J=7.4 Hz, 4H), 7.28 (t, J=
7.4 Hz, 2H), 7.21 (s, 4H), 3.04–2.88 (m, 6H), 2.19–2.04 (m, 6H), 0.95–
0.82 (m, 36H), 0.64–0.54 ppm (m, 30H); 13C NMR (100 MHz, CDCl3,
298 K): d=156.0, 154.3, 154.2, 145.6, 145.2, 144.5, 140.3, 139.5, 139.4,
tion. In extremely dilute solutions, the complex favored
a self-coordinated conformation between the triazole groups
on the wheel and the ZnP unit on the thread; whereas by in-
creasing the concentration, such a weak interaction was
easily disrupted by intermolecular van der Waals interac-
tions and the [3]rotaxane adopted an extended conforma-
tion. Such a low Ka value ensures the sensitivity of the [3]ro-
taxane to concentration and makes the concentration-de-
pendent conformational change possible.
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Porphyrin-Containing [3]Rotaxane
139.3, 138.6, 138.2, 138.0, 137.4, 137.3, 136.3, 129.2, 128.7, 128.6, 128.2,
127.7, 127.3, 127.0, 126.5, 125.9, 125.4, 125.0, 124.9, 124.8, 120.7, 120.3,
56.0, 55.8, 55.7, 37.1, 36.9, 31.5, 29.5, 29.4, 23.9, 22.3, 13.9 ppm; HRMS
(ESI, m/z): Calcd for C91H109Br: 1280.7707; found: 1280.7709 [M]+.
(m, 6H), 2.19–2.04 (m, 6H), 0.95–0.82 (m, 36H), 0.64–0.54 ppm (m,
30H); 13C NMR (100 MHz, CDCl3, 298 K): d=154.3, 145.3, 145.2, 141.4,
140.4, 139.9, 139.7, 138.5, 138.3, 138.0, 137.9, 137.3, 136.2, 134.1, 128.8,
128.7, 128.6, 128.2, 127.6, 127.5, 127.2, 127.0, 126.5, 125.1, 124.9, 120.5,
120.3, 55.8, 54.5, 37.1, 31.5, 29.5, 23.9, 22.3, 13.9 ppm; HRMS (ESI, m/z):
Calcd for C98H115N3: 1333.9086; found: 1333.9068 [M]+.
Compound 4
To a solution of 4-formylbenzeneboronic acid (226 mg, 1.56 mmol), com-
pound 3 (1.0 g, 0.78 mmol), and [PdACHTNUGTRNEUNG(PPh3)4] (45 mg, 0.04 mmol) in THF
Compound C
(100 mL) was added aqueous Na2CO3 (331 mg, 3.12 mmol) under nitro-
gen. The mixture was heated at reflux for 12 h under a nitrogen atmos-
phere. The organic layer was separated and washed with saturated aque-
ous NH4Cl and then dried over anhydrous Na2SO4. After removal of the
solvent under reduced pressure, the residue was purified by column chro-
matography over silica gel (petroleum ether/CH2Cl2 =8:1 to 1:1) to
afford 0.97 g (95%) of 4 as a white solid. 1H NMR (400 MHz, CDCl3,
298 K): d=10.10 (s, 1H), 8.52–8.43 (m, 3H), 8.03 (d, J=8.3 Hz, 2H), 7.94
(d, J=8.3 Hz, 2H), 7.80 (d, J=8.3 Hz, 4H), 7.78–7.70 (m, 6H), 7.68 (d,
J=8.4 Hz, 4H), 7.58 (d, J=7.3 Hz, 4H), 7.39 (t, J=7.6 Hz, 4H), 7.28 (m,
2H), 7.21 (s, 4H), 3.04–2.88 (m, 6H), 2.19–2.04 (m, 6H), 0.95–0.82 (m,
36H), 0.64–0.54 ppm (m, 30H); 13C NMR (100 MHz, CDCl3, 298 K): d=
191.9, 154.5, 154.3, 154.2, 147.3, 145.6, 145.5, 145.2, 140.9, 140.3, 139.6,
139.5, 138.6, 138.2, 138.1, 137.7, 137.4, 137.3, 136.3, 135.0, 130.3, 128.7,
128.6, 128.2, 127.6, 127.5, 127.3, 127.0, 126.5, 125.5, 125.0 124.9, 120.8,
120.3, 55.9, 55.8, 37.1, 31.5, 29.5, 23.9, 22.3, 13.9 ppm; HRMS (ESI, m/z):
Calcd for C98H114O: 1306.8864; found: 1306.8858 [M]+.
A mixture of 7 (700 mg, 0.524 mmol), 8 (495 mg, 1.05 mmol), and [Cu-
AHCTUNGTERN(GNUN MeCN)4]PF6 (174 mg, 0.524 mmol) was heated at reflux in dry CH2Cl2
overnight. The mixture was washed with dilute aqueous HCl and water.
The organic layer was dried over anhydrous Na2SO4. After removal of
the solvents under reduced pressure, the residue was purified by column
chromatography (eluent: CH2Cl2 to EtOAc) to afford the crude product.
Preparative GPC (eluent: CHCl3) was used to obtain 892 mg (94%) of
product C as a yellow solid. 1H NMR (400 MHz, CDCl3, 298 K, ppm):
d=8.56–8.32 (m, 3H), 7.86–7.77 (m, 6H), 7.76–7.62 (m, 10H), 7.58 (d,
J=7.6 Hz, 4H), 7.47 (d, J=7.4 Hz, 3H), 7.39 (t, J=7.6 Hz, 4H), 7.34–
7.23 (m, 5H), 7.21 (s, 4H), 6.89 (s, 4H), 5.65 (s, 2H), 4.31–4.12 (m, 8H),
4.01–3.87 (m, 8H), 3.83 (s, 8H), 3.04–2.88 (m, 6H), 2.19–2.04 (m, 6H),
0.95–0.82 (m, 36H), 0.64–0.54 ppm (m, 30H); 13C NMR (100 MHz,
CDCl3, 298 K): d=154.4, 154.3, 148.8, 145.3, 145.1, 141.9, 140.4, 140.0,
139.6, 138.5, 138.1, 138.0, 137.9, 137.3, 136.3, 133.5, 129.0, 128.9, 128.7,
128.6, 128.3, 128.2, 127.7, 127.6, 127.2, 127.0, 126.5, 125.3, 125.1, 124.9,
121.4, 120.5, 120.3, 114.0, 71.2, 69.8, 69.4, 69.3, 55.8, 54.0, 37.1, 31.5, 29.5,
23.9, 22.2, 13.9 ppm; HRMS (ESI, m/z): Calcd for C124H148N3O8:
1807.1261; found: 1807.1239 [M+H]+; calcd for C124H151N4O8: 1824.1526;
found: 1824.1556 [M+NH4]+.
Compound 5
LiAlH4 (52 mg, 1.38 mmol) was added slowly to a solution of compound
4 (900 mg, 0.69 mmol) in anhydrous THF (30 mL) at 08C. The mixture
was warmed to room temperature and stirred overnight. Then the mix-
ture was quenched with aqueous Na2SO4. After filtration, the filtrate was
concentrated under reduced pressure to afford 5 in quantitative yield as
a white solid. 1H NMR (400 MHz, CDCl3, 298 K): d=8.45 (d, J=8.2 Hz,
3H), 7.77–7.80 (m, 6H), 7.67–7.74 (m, 10H), 7.58 (d, J=7.3 Hz, 4H),
7.52 (d, J=7.9 Hz, 2H), 7.39 (t, J=7.6 Hz, 4H), 7.31–7.28 (m, 2H), 7.21
(s, 4H), 4.79 (d, J=5.0 Hz, 2H), 3.04–2.88 (m, 6H), 2.19–2.04 (m, 6H),
0.95–0.82 (m, 36H), 0.64–0.54 ppm (m, 30H); 13C NMR (100 MHz,
CDCl3, 298 K): d=154.3, 145.2, 140.8, 140.4, 139.8, 139.7, 139.6, 138.6,
138.4, 138.0, 137.3, 136.2, 128.7, 128.6, 128.2, 127.6, 127.5, 127.2, 127.0,
126.5, 125.1, 124.9, 120.5, 120.3, 65.2, 55.8, 37.1, 31.5, 29.5, 23.9, 22.3,
13.9 ppm; HRMS (ESI, m/z): Calcd for C98H116O: 1308.9021; found:
1308.8989 [M]+.
Compound 13
LiAlH4 (77 mg, 2.04 mmol) was added slowly to a solution of compound
12 (195 mg, 0.204 mmol) in anhydrous THF (30 mL) at 08C. The mixture
was warmed to room temperature and stirred overnight, and then
quenched with aqueous Na2SO4. After filtration, the filtrate was concen-
trated under reduced pressure to afford 13 in nearly quantitative yield as
a purple-red solid. 1H NMR (400 MHz, CDCl3, 298 K): d=8.90 (d, J=
4.9 Hz, 4H), 8.84 (d, J=4.9 Hz, 4H), 8.22 (d, J=8.0 Hz, 4H), 8.09 (d, J=
1.8 Hz, 4H), 7.80 (t, J=1.8 Hz, 2H), 7.74 (d, J=8.0 Hz, 4H), 5.05 (s,
4H), 1.53 (s, 36H), À2.73 ppm (s, 2H); 13C NMR (100 MHz, CDCl3,
298 K): d=148.7, 141.8, 141.1, 140.1, 134.6, 130.0, 125.2, 121.5, 121.0,
119.5, 65.4, 35.0, 31.7, 29.7 ppm; HRMS (ESI, m/z): Calcd for
C62H67N4O2: 899.5258; found: 899.5246 [M+H]+.
Compound 6
Compound 14
PBr3 (373 mg, 1.38 mmol) was added slowly to a solution of compound 5
(900 mg, 0.69 mmol) in anhydrous CH2Cl2 at 08C. The mixture was
warmed to room temperature and stirred overnight and then quenched
with MeOH in an ice bath. After evaporation of the solvents, the residue
was purified by column chromatography over silica gel (petroleum ether/
CH2Cl2 =10:1) to afford 780 mg (83%) of 6 as a white solid. 1H NMR
(400 MHz, CDCl3, 298 K): d=8.45 (d, J=8.4 Hz, 3H), 7.79 (d, J=8.3 Hz,
4H), 7.77–7.62 (m, 12H), 7.57 (d, J=7.3 Hz, 4H), 7.54 (d, J=8.3 Hz,
2H), 7.39 (t, J=7.6 Hz, 4H), 7.34–7.24 (m, 2H), 7.21 (s, 4H), 4.60 (s,
2H), 3.04–2.88 (m, 6H), 2.19–2.04 (m, 6H), 0.95–0.82 (m, 36H), 0.64–
0.54 ppm (m, 30H); 13C NMR (100 MHz, CDCl3, 298 K): d=154.3, 145.3,
145.2, 141.5, 140.4, 139.9, 139.7, 138.5, 138.2, 138.1, 137.9, 137.3, 136.6,
136.3, 129.6, 128.7, 128.6, 128.3, 127.6, 127.5, 127.3, 127.0, 126.5, 125.1,
124.9, 120.6, 120.3, 55.8, 37.1, 33.5, 31.5, 29.5, 23.9, 22.3, 13.9 ppm; HRMS
(ESI, m/z): Calcd for C98H116Br: 1371.8255; found: 1371.8272 [M+H]+.
A mixture of PCC (88 mg, 0.407 mmol) and compound 13 (183 mg,
0.203 mmol) in anhydrous CH2Cl2 was stirred overnight. The mixture was
concentrated under reduced pressure and the residue was purified by
column chromatography over silica gel (petroleum ether/EtOAc=10:1).
The crude product was washed with MeOH to afford 169 mg (92%) of
14 as a purple solid. 1H NMR (300 MHz, CDCl3, 298 K): d=10.39 (s,
2H), 8.94 (d, J=4.9 Hz, 4H), 8.79 (d, J=4.9 Hz, 4H), 8.42 (d, J=8.0 Hz,
4H), 8.29 (d, J=8.0 Hz, 4H), 8.08 (d, J=1.8 Hz, 4H), 7.81 (t, J=1.8 Hz,
2H), 1.53 (s, 36H), À2.74 ppm (s, 2H); 13C NMR (100 MHz, CDCl3,
298 K): d=192.1, 149.1, 148.9, 141.0, 135.9, 135.1, 131.9, 130.5, 129.9,
127.9, 122.3, 121.3, 118.4, 35.1, 31.8 ppm; HRMS (ESI, m/z): Calcd for
C62H63N4O2: 895.4945; found: 899.4926 [M+H]+.
Compound 16
A solution of 14 (125 mg, 0.140 mmol) and 15 (67 mg, 0.560 mmol) in
CHCl3 was heated at reflux for 5 h. After removal of the solvents under
reduced pressure, the red solid was dissolved in anhydrous THF. LiAlH4
(56 mg, 1.40 mmol) was added slowly to the solution at 08C. The mixture
was stirred for 5 h and then quenched with aqueous Na2SO4. After filtra-
tion, the solution was concentrated under reduced pressure. The crude
product was washed with MeOH to afford 150 mg (91% for two steps)
of 16 as a purple solid. 1H NMR (300 MHz, CDCl3, 298 K): d=8.90 (d,
J=4.9 Hz, 4H), 8.85 (d, J=4.9 Hz, 4H), 8.18 (d, J=8.0 Hz, 4H), 8.09 (d,
J=1.7 Hz, 4H), 7.79 (t, J=1.7 Hz, 2H), 7.70 (d, J=8.0 Hz, 4H), 7.44 (d,
Compound 7
NaN3 (74 mg, 1.14 mmol) was added to
a solution of compound 6
(780 mg, 0.57 mmol) in acetone and the mixture was heated at reflux for
6 h. After filtration, the mixture was concentrated under reduced pres-
sure to afford 750 mg (99%) of 7 as a white solid. 1H NMR (400 MHz,
CDCl3, 298 K): d=8.46 (d, J=8.0 Hz, 3H), 7.80 (d, J=8.0 Hz, 6H), 7.77–
7.63 (m, 10H), 7.58 (d, J=7.4 Hz, 4H), 7.47 (d, J=8.1 Hz, 2H), 7.39 (t,
J=7.6 Hz, 4H), 7.33–7.24 (m, 2H), 7.21 (s, 4H), 4.42 (s, 2H), 3.04–2.88
Chem. Asian J. 2012, 00, 0 – 0
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Jian Pei et al.
FULL PAPER
J=8.5 Hz, 4H), 7.03 (d, J=8.5 Hz, 4H), 4.73 (d, J=2.4 Hz, 4H), 4.14 (s,
4H), 4.00 (s, 4H), 2.54 (t, J=2.4 Hz, 2H), 1.53 (s, 36H), À2.73 ppm (s,
2H); 13C NMR (75 MHz, CDCl3, 298 K): d=206.9, 156.6, 148.7, 141.2,
141.0, 139.7, 134.5, 133.5, 131.1, 129.9, 129.4, 126.4, 121.4, 120.9, 119.7,
114.9, 78.7, 75.5, 55.8, 53.1, 52.9, 35.0, 31.7, 30.9 ppm; HRMS (ESI, m/z):
Calcd for C82H85N6O2: 1185.6729; found: 1185.6706 [M+H]+.
Compound A
A mixture of 17 (100 mg, 0.065 mmol), 18 (90 mg, 0.26 mmol), C (1.17 g,
0.65 mmol), and [Cu(MeCN)4]PF6 (96 mg, 0.26 mmol) was dissolved in
ACHTUNGTRENNUNG
dry CH2Cl2 (4 mL) and heated at reflux for 48 h. Aqueous NH4Cl
(10 mL) was added. The organic layer was washed with water and dried
over anhydrous Na2SO4. After removal of the solvent under reduced
pressure, the residue was first purified by column chromatography over
silica gel (CH2Cl2/MeOH=20:1) and then by preparative GPC (eluent:
CHCl3) to afford 171 mg (45%) of A as a red solid. 1H NMR (400 MHz,
Compound 17
To a solution of 16 (50 mg, 0.0422 mmol) in a mixture of CHCl3 and
MeOH
(10 mL/10 mL)
was
added
Zn
G
(19 mg,
CDCl3, 298 K): d=8.98 (s, 4H), 8.77ACTHNUTRGENUGN(s, 4H), 8.42 (s, 10H), 8.20 (s, 4H),
0.0844 mmol). The mixture was stirred at room temperature for 3 h, and
the solvent was removed under reduced pressure. The residue was dis-
solved in acetone (1 mL), then dilute aqueous HCl (50 mL, pH 1) was
added. After 5 min, NH4PF6 (28 mg, 0.169 mmol) was added to the aque-
ous mixture, and purple precipitate appeared immediately. The solid was
filtrated and washed with water sufficiently to afford 48 mg (83%) of 17.
The 13C NMR spectrum was not obtained due to the poor solubility of 17
in common organic solvents. 1H NMR (300 MHz, CD3CN, 298 K, ppm):
d=8.89 (d, J=4.9 Hz, 4H), 8.79 (d, J=4.9 Hz, 4H), 8.26 (d, J=8.1 Hz,
4H), 8.09 (d, J=1.7 Hz, 4H), 7.90 (t, J=1.7 Hz, 2H), 7.79 (d, J=8.1 Hz,
4H), 7.52 (d, J=8.4 Hz, 4H), 7.11 (d, J=8.4 Hz, 4H), 4.81 (d, J=2.4 Hz,
4H), 4.50 (s, 4H), 4.33 (s, 4H), 2.85 (t, J=2.4 Hz, 2H), 1.53 ppm (s,
36H); HRMS (ESI, m/z): Calcd for C82H84N6O2Zn: 624.2968; found:
8.05 (s, 4H), 8.00–7.00 (m, 104H), 6.90–6.50 (m, 14H), 5.70–5.30 (m,
12H), 4.99 (s, 8H), 4.60–3.50 (m, 56H), 3.00 (s, 12H), 2.16 (s, 12H), 1.51
(s, 36H), 0.95–0.82 (m, 72H), 0.64–0.54 ppm (m, 60H); 13C NMR
(100 MHz, CDCl3, 298 K): d=160.3, 158.6, 154.3, 150.5, 149.7, 148.6,
147.6, 147.5, 145.3, 141.7, 140.4, 139.9, 139.7, 138.5, 138.2, 138.0, 137.3,
136.5, 136.3, 130.9, 129.0, 128.7, 128.6, 128.5, 128.3, 127.9, 127.7, 127.5,
127.3, 127.0, 126.5, 125.1, 124.9, 120.5, 120.3, 114.8, 112.7, 107.5, 102.6,
70.1, 68.0, 55.8, 37.1, 35.0, 31.9, 31.7, 31.5, 29.7, 29.5, 29.4, 29.3, 27.2, 23.9,
22.7, 22.3, 22.2, 14.1, 13.9 ppm; HRMS (ESI, m/z): Calcd for
C372H416N18O22Zn: 2775.5634; found: 2775.5682 [MÀ2PF6]2+
.
624.2981 [MÀ2PF6]2+
Compound B
.
Acknowledgements
This work was supported by the Major State Basic Research Develop-
ment Program from the MOST (No. 2009CB623601) and National Natu-
ral Science Foundation of China.
To a solution of 16 (50 mg, 0.0422 mmol) in a mixture of CHCl3 and
MeOH (10 mL/10 mL) was added Zn(OAc)2·2H2O (19 mg,
AHCTUNGTRENNUNG
0.0844 mmol). The mixture was stirred at room temperature for 3 h and
then washed with aqueous NaHCO3 and water three times. The organic
layer was dried over anhydrous Na2SO4. After removal of the solvents
under reduced pressure, the residue was dissolved in 20 mL of CH2Cl2,
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and then 18 (38 mg, 0.106 mmol) and [CuACTHNURGTNEUNG(MeCN)4]PF6 (2 mg,
0.005 mmol) were added. After the mixture was heated at reflux for 24 h,
aqueous NH4Cl (20 mL) was added. The organic layer was washed with
water and dried over anhydrous Na2SO4, and the solvent was evaporated
under reduced pressure. The red solid was purified by column chroma-
tography over silica gel (CH2Cl2/Et3N=30:1) and then by preparative
GPC (eluent: CHCl3) to afford the diamide, which was dissolved in DMF
(1 mL). Dilute aqueous HCl (50 mL, pH 1) was added. After 5 min,
water was evaporated off. The residue was dissolved in MeOH (10 mL),
and saturated aqueous NH4PF6 (10 mL) was added to provide purple pre-
cipitate immediately. The solid was filtrated and washed with water suffi-
ciently to afford 60 mg (64%) of B. The 13C NMR spectrum was not ob-
tained due to the poor solubility of B in common organic solvents.
1H NMR (300 MHz, CD3CN, 298 K): d=8.91 (d, J=4.2 Hz, 4H), 8.81 (d,
J=4.2 Hz, 4H), 8.28 (d, J=7.5 Hz, 4H), 8.12 (s, 4H), 7.93 (s, 2H), 7.87–
7.81 (m, 6H), 7.54 (d, J=8.4 Hz, 4H), 7.37–7.31 (m, 20H), 7.17 (d, J=
8.4 Hz, 4H), 6.55 (s, 2H), 6.47 (s, 4H), 5.39 (s, 4H), 5.21 (s, 4H), 5.00 (s,
8H), 4.55 (s, 4H), 4.37 (s, 4H), 1.52 ppm (s, 36H); HRMS (ESI, m/z):
Calcd for C124H124N12O6Zn: 970.4524; found: 970.4489 [MÀ2PF6+2H]2+
Compound D
.
To
a
solution of 18 (2.00 g, 5.79 mmol) and dodec-1-yne (1.44 g,
(MeCN)4]PF6 (216 mg,
8.69 mmol) in 50 mL of CH2Cl2 was added [CuACHTUNGTRENNNUG
0.058 mmol). The mixture was heated at reflux for 20 h, and then aque-
ous NH4Cl (50 mL) was added. The organic layer was washed with
NH3·H2O and water and dried over anhydrous Na2SO4. After the solvent
was removed under reduced pressure, the residue was purified by column
chromatography over silica gel (CH2Cl2/EtOAc=4:1) to afford 2.54 g
(86%) of D as a white solid. 1H NMR (300 MHz, CDCl3, 298 K): d=
7.28–7.20 (m, 10H), 7.05 (s, 1H), 6.48 (s, 1H), 6.37 (s, 2H), 5.27 (s, 2H),
4.87 (s, 4H), 2.58 (t, J=7.5 Hz, 2H), 1.57–1.51 (m, 2H), 1.30–1.00 (m,
14H), 0.78 ppm (t, J=6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3, 298 K):
d=160.2, 148.8, 137.1, 136.3, 128.5, 128.0, 127.4, 120.4, 106.9, 101.9, 70.0,
53.8, 31.8, 29.5, 29.4, 29.3, 29.1, 25.6, 22.6, 14.0 ppm; HRMS (ESI, m/z):
Calcd for C33H42N3O2: 512.3271; found: 512.3266 [M+H]+.
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Received: May 19, 2012
Published online: && &&, 0000
Chem. Asian J. 2012, 00, 0 – 0
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
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FULL PAPER
Porphyrins
It’s a ringer: A porphyrin-containing
[3]rotaxane was synthesized that exhib-
ited energy transfer from the wheel to
the porphyrin unit on the axis. Addi-
tionally, the conformation could be
modulated by changing concentration.
This concentration-dependent confor-
mational change is reversible in
Xiao-Ye Wang, Ji-Min Han,
Jian Pei*
&&&& — &&&&
Energy Transfer and Concentration-
Dependent Conformational Modula-
tion: A Porphyrin-Containing
[3]Rotaxane
CH2Cl2 but was inhibited in THF.
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www.chemasianj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!