A [2]-catenane whose rings incorporate two differently metallated porphyrins

Article abstract of DOI:10.1039/b100275a

A [2]-catenane made with Zn(II) and Au(III) porphyrin-incorporating marcrocycles has been synthesized using the transition metal templated technique, starting from either preformed Au or Zn porphyrin-containing macrocycles. The highest yield (11.5%) was o

Full text of DOI:10.1039/b100275a

View Article Online / Journal Homepage / Table of Contents for this issue
A [2]-catenane whose rings incorporate two di†erently metallated
porphyrins¤
Myriam Linke, Norifumi Fujita, Jean-Claude Chambron,*
Valerie Heitz and Jean-Pierre Sauvage*
L aboratoire de Chimie Organo-Minerale, UMR 7513 du CNRS, Universite L ouis Pasteur,
Institut L e Bel, 4, rue Blaise Pascal, 67000 Strasbourg, France
Received (in Strasbourg, France) 4th January 2001, Accepted 21st March 2001
First published as an Advance Article on the web 21st May 2001
A [2]-catenane made with Zn(II) and Au(III) porphyrin-incorporating marcrocycles has been synthesized using the
transition metal templated technique, starting from either preformed Au or Zn porphyrin-containing macrocycles.
The highest yield (11.5%) was obtained in the latter case. Removal of the copper(I) template metal a†orded the free
[2]-catenane, whose 1H-NMR properties di†er dramatically from those of the parent Cu(I) complex, suggesting a
changeover in the molecular structure upon demetallation.
Molecular systems capable of showing intramolecular photo-
induced electron transfer between donor and acceptor com-
ponents have been the subject of intense interest since the
early eighties.1 One of our approaches to this topic has been
the use of Zn(II) porphyrin donors in the excited state and
Au(III) porphyrin acceptors in the ground state2 in com-
bination with the so-called mechanical bond found in
catenanes and rotaxanes. Only relatively few porphyrin-
containing catenanes3 and rotaxanes4 have been described in
the literature. As shown schematically in Fig. 1, the com-
pounds synthesized in our laboratory are either [2]-
rotaxanes5 made with a Au(III) porphyrin-containing macro-
cycle threaded onto a Zn(II) porphyrin-stoppered dumbbell
[Fig. 1(a) and (b)] or a [2]-catenane,6 made from macrocycles
with pendent Zn and Au porphyrins [Fig. 1(c)].
The target Cu(I)-complexed [2]-catenate [Cu1](PF ) con-
6 2
tains two di†erent macrocycles. Therefore, two routes can be
envisaged for its construction by the transition metal templat-
ed strategy;7 these are shown in Fig. 3. Both involve the prep-
aration of an intermediate precatenate species (C) or (F), in
which either a Zn or Au porphyrin-containing macrocycle (A)
or (E) is threaded onto chelate (B), as a result of copper(I)
coordination. Formation of the second, interlocking macro-
cycle is achieved in the next step, by reaction of the preca-
A natural extension of this work was the preparation of the
analogous Cu(I)-complexed [2]-catenate with macrocycles
incorporating the Zn and Au porphyrins [Fig. 1(d)]. Here, we
describe the di†erent routes used for the preparation of the
[2]-catenate [Cu1](PF ) (Fig. 2) and its demetallation to the
6 2
[2]-catenane species.
Fig. 1 Schematic representation of metal-complexed [2]-rotaxanes
(a, b) and [2]-catenanes (c, d). The thick lines represent chelating frag-
ments, the black disk is a metal cation, the open diamonds are Zn(II)
porphyrins, and the hatched diamonds are Au(III) porphyrins.
¤ Electronic supplementary information (ESI) available: 1H-NMR
spectra (1D, 2D ROESY and COSY) of [Cu1](PF ) and [1]PF . See
6 2
6
http:CCwww.rsc.orgCsuppdataCnjCb1Cb100275aC
Fig. 2 Chemical structure of [Cu1](PF ) .
6 2
790
New J. Chem., 2001, 25, 790È796
DOI: 10.1039/b100275a
This journal is ( The Royal Society of Chemistry and the Centre National de la Recherche ScientiÐque 2001

View Article Online
phenanthroline 25c and 4 in DMF at 55 ¡C in the presence of
Cs CO , and was obtained in 28% yield after chromatog-
2
3
raphy. Reaction of 7 with Zn(OAc) É 2H O in reÑuxing
2
2
CHCl /CH OH a†orded the zinc porphyrin-containing
3
3
macrocycle 8 in 85% yield. Alternatively, this compound
could be prepared directly from phenanthroline 2 and Zn
porphyrin 5 under conditions similar to those described for 7,
and was obtained in 13% yield after chromatography.
The three steps of the most efficient route leading to the
Cu(I) complexed [2]-catenate [Cu1](PF ) are shown in Fig.
6 2
5.7 Mixing of equimolar solutions of [Cu(CH CN) ]PF in
3
4
6
acetonitrile and Zn porphyrin-containing macrocycle 8 in
dichloromethane, followed by addition of phenanthroline
derivative 2 in dichloromethane a†orded in quantitative yield
precatenate [Cu(2,8)]PF . Subsequently, this complex was
combined with a stoichiometric amount of gold(III) 5,10-di(p-
6
hydroxyphenyl)-15,20-di(3,5-di-tert-butylphenyl)porphyrinate
[6]PF in DMF. The resulting solution was heated to 60 ¡C
6
and treated portionwise with a suspension of Cs Co in
2
3
DMF. This procedure allows the relative instability of the
Fig. 3 Two strategies for the transition metal-templated synthesis of
a [2]-catenane made with Zn and Au porphyrin-incorporating inter-
locked macrocycles. Symbols are as in Fig. 1. The black disk symbol-
ises copper(I). See text for details.
present precatenate in basic media to be overcome.8 Under
these conditions, Cu(I) complexed [2]-catenate [Cu1](PF )
6 2
was isolated in 11.5% yield after chromatography. The alter-
native route, which involves Au porphyrin-containing macro-
tenate with the appropriate porphyrin, (D) in the case of (C),
(G) in the case of (F), to produce the desired Cu(I)-complexed
[2]-catenate (H). Finally, removal of the metal template
a†ords the free catenane species (I).
cycle [9]PF and Zn porphyrin 5 as reactants a†orded the
6
same copper catenate in 5% yield. Demetallation leading to
the free [2]-catenane species [1]PF , was carried out by treat-
6
ing the Cu(I) complex with 100 mol% KCN in a ternary
The precursors of the target Cu(I) complexed [2]-catenate
mixture of CHCl / CH CN/H O at 40 ¡C.7 [2]-Catenane
3
3
2
[Cu1](PF ) are shown in Fig. 4. 5,10-Di(p-hydroxyphenyl)-
[1]PF was obtained in 83% yield after chromatography (Fig.
6 2
6
15,20-di(3,5-di-tert-butylphenyl)porphyrin
4
was obtained
6).
quantitatively by reaction of 5,10-di(p-anisyl)-15,20-di(3,5-di-
tert-butylphenyl)porphyrin 35c with BBr in CH Cl at
The target compounds [1]PF and its Cu(I) complex were
6
characterized by FAB-MS and 1H-NMR spectroscopy. The
3
2 2
[78 ¡C, and its zinc complex 5 was obtained in 79% yield
FAB mass spectra in the positive mode show the molecular
peak corresponding to singly charged species resulting from
by treatment of
4 with Zn(OAc) É 2H O in reÑuxing
2
2
CHCl /CH OH. Free base-incorporating macrocycle 7 was
the loss of one PF ~ anion, at m/z 3041.0 for the Cu(I) [2]-
3
3
6
prepared by combining 2,9-bis[p-(2-iodoethoxy)phenyl]-1,10-
catenate, and 2832.2 for the free [2]-catenane. Peaks corre-
Fig. 4 Precursors to [2]-catenate [Cu1](PF ) . (i) BBr , CH Cl , [78 ¡C, 100%; (ii) Zn(OAc) É 2H O, CHCl /CH OH, reÑux, 79%; (iii) same
6 2
3
2
2
2
2
3
3
as (ii), 85%.
New J. Chem., 2001, 25, 790È796
791

View Article Online
Fig. 5 Two-step preparation of Cu(I)-complexed [2]-catenate [Cu1](PF ) .
6 2
sponding to the Au porphyrin-containing macrocycle 9` and
the protonated Zn porphyrin-containing macrocycle 8 are
observed at m/z 1481.6 and 1349.5, respectively.
and [1]PF [Fig. 7(b)]. Labelling of the protons is indicated
6
in Fig. 6. The di†erent signals were assigned using 2D ROESY
experiments. To distinguish between protons belonging to the
interlocked Zn and Au porphyrin-containing macrocycles, it
was assumed, as observed previously, that the b-pyrrolic
Fig. 7 shows a comparison of the room temperature
1H-NMR spectra (low Ðeld region) of [Cu1](PF ) [Fig. 7(a)]
6 2
792
New J. Chem., 2001, 25, 790È796

View Article Online
Fig. 6 Demetallation of [2]-catenate [Cu1](PF ) to [2]-catenane [1]PF . Double bonds omitted for clarity. Double-headed arrows show
6 2
6
selected ROESY correlations.
protons of the latter resonate at lower Ðeld than the
former.2b,9 This is in agreement with the strong withdrawing
e†ect of gold(III). Typical of the mutual “Ðt inÏ of the 2,9-
diphenyl-1,10-phenanthroline chelates in the Cu(I) complexed
[2]-catenate, are the upÐeld-shifted (6.4 ppm) signals of the
meta protons (m and m@) belonging to the phenyl substituents,
as compared to the other aromatic protons.10 With the excep-
tion of the pyrrolic protons, which are the most sensitive to
the nature of the porphyrinic metal, analogous protons of
both macrocycles have similar chemical shifts. The spectrum
macrocycle are shifted upÐeld to a much greater extent than
the corresponding protons [3È8] of the Au porphyrin-
containing macrocycle. This is true, in particular, for the pairs
4@,7@ and 5@,6@, which undergo shifts of [0.82 and [0.66 ppm
respectively.
2D ROESY maps of catenate [Cu1](PF ) indicate dipolar
6 2
couplings between protons py of the Au porphyrin-
1
containing macrocycle and protons 5@,6@ of the Zn porphyrin-
containing macrocycle. The same is true for protons py@ and
1
5,6. These observations are in agreement with the structure
of the free [2]-catenane [1]PF is dramatically di†erent from
depicted in Fig. 6. These correlations disappear in the case of
6
that of its parent Cu(I) complex. The signals of the pyrrolic
catenane [1]PF , which shows only very weak cross peaks
6
protons move upÐeld, and the signals of protons o and o@, and
m and m@ of the phenyl substituents belonging to the phenan-
throline nuclei move downÐeld by 0.8 ppm. This latter shift is
typically observed when passing from metallocatenates to free
catenanes, and indicates that the phenyl substituent of a given
phenanthroline chelate is no longer in the shielding Ðeld of the
other phenanthroline upon removal of the metal template.11
In addition to the above noted changes, the signals of the phe-
nanthroline protons [3@È8@] of the Zn porphyrin-containing
between protons of one macrocycle and protons of the other
macrocycle, e.g., py@ (py ) and m (m@), mA (mÓ), or a (a@). VT
1
1
1H-NMR spectra at temperatures down to [95 ¡C performed
on the free catenane [1]PF show only increasing broadening
of the peaks, indicating that the molecule exists in many
6
exchanging conformations.
The study of photoinduced electron transfer between the Zn
porphyrin component in the excited state and the Au porphy-
rin component in the ground state by fast laser Ñash photo-
New J. Chem., 2001, 25, 790È796
793

View Article Online
Zinc(II)5,10-di(p-hydroxyphenyl)-15,20-di(3,5-di-tert-butyl-
phenyl)porphyrinate 5. A solution of 4 (0.174 g, 0.2 mmol) and
Zn(OAc) É 2H O (0.045 g, 0.2 mmol) in CHCl /CH OH 2 : 1
2
2
3
3
(145 mL) was reÑuxed for 1 h. After evaporation of the sol-
vents, the residue was dissolved in CH Cl , washed twice with
2
2
water and the solution evaporated to dryness. PuriÐcation by
chromatography (alumina, hexane/CH Cl 50 : 50) a†orded 5
2
2
(0.147 g, 79% yield) as a purple solid. 1H-NMR (200 MHz,
CDCl ): d 9.01 (s, 2H, H
or H ), 8.99 (AB, 4H, H
and
3
py{1
py{4
py{2
H
), 8.98 (s, 2H, H
or H ), 8.09 (d, 4H, 3J \ 8.5 Hz,
py{3
py{4
py{1
H ), 8.09 (d, 4H, 4J \ 1.8 Hz, H ), 7.80 (t, 2H, 4J \ 1.8 Hz,
o`
op{
H
), 7.19 (d, 4H, 3J \ 8.5 Hz, H ), 5.14 (br s, 2H, OH@), 1.53
pp{
m`
(s, 36H, CH@ ). UV-visible (j /nm): 423, 551, 592. Anal. Calc.
3
max
for C
H
N O É H O: C, 75.65; H, 6.56; N, 5.88%. Found:
60 60
4
2
2
C, 75.88; H, 6.39; N, 5.84%.
Macrocycle 7. A solution of 2 (0.850 g, 1.26 mmol) and 4
(1 g, 1.15 mmol) in DMF (50 mL) was added dropwise to a
stirred suspension of Cs CO (1.87 g, 5.75 mmol) in DMF
2
3
(750 mL) at 55 ¡C, over 24 h. After further stirring for 16 h at
55 ¡C, the solvent was evaporated under reduced pressure. The
residue was partitioned between CH Cl and H O. The
2
2
2
organic layer was washed three times with H O, separated
2
Fig. 7 1H-NMR spectra (500 MHz, CD Cl ) of (a) [Cu1](PF ) and
and evaporated to dryness. The crude product was puriÐed by
repeated chromatography (silica gel, hexane/CH Cl 50 : 50,
then alumina, hexane/CH Cl 80 : 20), a†ording macrocycle 7
2
2
6 2
(b) [1]PF . Atom numbering as shown in Fig. 6.
6
2
2
lysis techniques should allow more insight into the
conformational properties of the [2]-catenane, as shown
recently for a related [2]-rotaxane.5c
2
2
(0.412 g, 28% yield) as a purple solid. 1H-NMR (200 MHz,
CDCl ): d 9.02 (d, 2H, 3J \ 5.1 Hz, H ), 8.92 (d, 2H,
3
py{2
3J \ 5.1 Hz, H ), 8.91 (s, 2H, H ), 8.91 (s, 2H, H ), 8.45
py{3
(d, 4H, 3J \ 8.9 Hz, H ), 8.27 (d, 2H, 3J \ 8.6 Hz, H ), 8.19
o` 4{7{
(d, 4H, 3J \ 8.6 Hz, H ), 8.10 (d, 4H, 4J \ 2 Hz, H ), 8.09 (d,
o{ op{
2H, 3J \ 8.4 Hz, H ), 7.81 (t, 2H, 4J \ 2 Hz, H ), 7.74 (s,
3{8{ pp{
2H, H ), 7.44 (d, 4H, 3J \ 8.6 Hz, H ), 7.26 (d, 4H, 3J \ 8.9
5{6{ m{
Hz, H ), 4.86 (t, 4H, 3J \ 3.9 Hz, H ), 4.53 (t, 4H, 3J \ 4.7
m` b{
Hz, H ), 1.50 (s, 36H, CH@ ), [2.68 (br s, 2H, NH@). FAB-MS:
a{
m/z 1287.7 (M ] H`).
py{4
py{1
Experimental
General
1H-NMR spectra were obtained on either Bruker AC200 (200
MHz), AC300 (300 MHz), Avance 400 (400 MHz), or ARX500
(500 MHz) spectrometers. Chemical shifts in ppm are refer-
enced downÐeld from tetramethylsilane. Labels of the protons
of the [2]-catenane and some of its precursors are provided in
Fig. 6. Mass spectral data were obtained on a ZAB-HF (FAB)
spectrometer. UV-visible absorption spectra were recorded
with a Kontron-Uvikon 860 spectrophotometer. Elemental
analyses were performed by the Service de Caracterisation of
the Institut Charles Sadron (Strasbourg).
3
Macrocycle 8. Method A. A solution of macrocycle 7 (0.375
g, 0.29 mmol) and Zn(OAc) É 2H O (0.064 g, 0.29 mmol) in
CHCl /CH OH 2 : 1 (220 mL) was reÑuxed for 1 h. After
evaporation of the solvents, the residue was dissolved in
CH Cl , washed twice with water, and the organic layer
evaporated to dryness. PuriÐcation by column chromatog-
raphy (alumina, hexane/CH Cl 40 : 60) a†orded macrocycle
2
2
3
3
2
2
All reactions were performed under an atmosphere of
argon, using standard Schlenk techniques. CH Cl was dis-
2
2
2
2
8 (0.330 g, 85% yield) as a purple solid. 1H-NMR (300 MHz,
tilled from P O and DMF (analytical grade) was Ðltered
2
5
CDCl ): d 9.126 (d, 2H, 3J \ 4.61 Hz, H ), 9.039 (s, 2H,
through a pad of alumina prior to use. 2,9-Bis[p-(2-iodo-
ethoxy)phenyl]-1,10-phenanthroline 2,5c 5,10-di(p-anisyl)-15,
20-di(3,5-di-tert-butylphenyl)porphyrin 3,5c gold(III) 5,10-di(p-
hydroxyphenyl)-15,20-di(3,5-di-tert-butylphenyl)porphyrinate
[6]PF ,5c macrocycle [9]PF ,5c and [Cu(CH CN) ] PF ,12
3
py{2
H
), 9.038 (d, 2H, 3J \ 5.02 Hz, H ), 9.029 (s, 2H, H ),
py{4
py{3
py{1
8.445 (d, 4H, 3J \ 8.83 Hz, H ), 8.257 (d, 2H, 3J \ 8.43 Hz,
o`
H
), 8.194 (d, 4H, 3J \ 8.63 Hz, H ), 8.122 (d, 4H, 4J \ 1.81
4{7{
o{
Hz, H ), 8.082 (d, 2H, 3J \ 8.43 Hz, H ), 7.812 (t, 2H,
op{
3{8{
6
6
3
4
6
4J \ 1.81 Hz, H ), 7.724 (s, 2H, H ), 7.426 (d, 4H,
pp{ 5{6{
3J \ 8.63 Hz, H ), 7.254 (d, 4H, 3J \ 9.64 Hz, H ), 4.854 (t,
were prepared according to literature procedures.
m{
m`
Syntheses
4H, 3J \ 4.01 Hz, H ), 4.520 (t, 4H, 3J \ 4.21 Hz, H ), 1.548
b{
a{
(s, 36H, CH@ ). FAB-MS: m/z 1350.6 (M ] H`).
5,10-Di(p-hydroxyphenyl)-15,20-di(3,5-di-tert-butylphenyl)-
3
Method B. A solution of 2 (1.17 g, 1.74 mmol) and 5 (1.625
g, 1.74 mmol) in DMF (76 mL) was added dropwise to a
vigorously stirred suspension of Cs CO (5.67 g, 17.4 mmol)
porphyrin 4. A solution of 3 (1.03 g, 1.13 mmol) in dry CH Cl
2
2
(170 mL) was added dropwise to a solution of BBr (17 mL of
3
a 1 M solution in CH Cl , 17 mmol) in CH Cl (110 mL) at
2
3
2
2
2
2
in DMF (1.135 L) at 60 ¡C over 9 h. After further stirring for 2
days at 60 ¡C, the solvent was evaporated under reduced pres-
sure. The residue was partitioned between CH Cl and H O.
[78 ¡C. After 2.5 h stirring at [78 ¡C and 1 h at room tem-
perature, the red solution was cooled to 0 ¡C, quenched with
water (20 mL) and neutralized with aqueous Na CO . The
2
2
2
2
3
The organic layer was washed three times with water and
evaporated to dryness. The remaining solid was triturated
with toluene and Ðltered on a millipore Ðlter. Dissolution of
the cake in CH Cl a†orded almost pure macrocycle 8, that
was further puriÐed by chromatography (silicagel, 1%
CH OH in CH Cl ). Yield: 0.310 g (13%).
organic layer was washed three times with water and evapo-
rated to dryness to leave porphyrin 4 in pure form (0.995 g,
quantitative). 1H-NMR (200 MHz, CDCl ): d 8.89 (s, 2H,
3
H
or H ), 8.87 (s, 2H, H
or H ), 8.87 (br s, 4H, H
2
2
py{1
py{4
py{4
py{1
py{2
and H ), 8.09 (d, 4H, 3J \ 8.4 Hz, H ), 8.07 (d, 4H, 4J \ 1.7
py{3
o`
Hz, H ), 7.79 (t, 2H, 4J \ 1.8 Hz, H ), 7.20 (d, 4H, 3J \ 8.4
3
2 2
op{ pp{
Hz, H ), 5.13 (br s, 2H, OH@), 1.52 (s, 36H, CH@ ), [2.73 (br s,
Precatenate [Cu(2,8)]PF . A solution of [Cu(CH CN) ]-
6
m`
3
3 4
PF (27.1 mg, 0.0727 mmol) in CH CN (6 mL) was transferred
2H, NH@). UV-visible (j /nm): 421, 518, 554, 594, 649. Anal.
max
6
3
Calc. for C
C, 82.27; H, 7.18; N, 6.30%
H
N O : C, 82.72; H, 7.17; N, 6.43%. Found:
via cannula to a solution of macrocycle 8 (99.1 mg, 0.0733
mmol) in CH Cl (34 mL). After 40 min stirring, a solution of
60 62
4 2
2
2
794
New J. Chem., 2001, 25, 790È796

View Article Online
2 (49.3 mg, 0.0733 mmol) in CH Cl (17 mL) was added via
(t, 4H, 3J \ 4.08 Hz, H ), 1.566 (s, 36H, CH or CH@ ), 1.555
2
2
a{
3
3
cannula to the reaction mixture. After stirring for 5 h, the sol-
(s, 36H, CH@ or CH ). FAB-MS: m/z 3041.02 [M [ PF ~]`,
3
3
6
vents were removed in vacuo, leaving a quantitative amount of
calc. 3042.1 (10%); 2896.07 [M [ 2PF ~ ] e~]`, calc.
6
pure precatenate [Cu(2,8)]PF as a red solid. 1H-NMR (300
2897.17 (33%); 1545.5 [9` ] Cu` ] e~]`, calc. 1546.1 (13%);
6
MHz, CD Cl ): d 9.14 (d, 2H, 3J \ 4.6 Hz, H ), 9.06 (d, 2H,
1481.6 [9]`, calc. 1482.6 (63%); 1448.6 [M [ 2PF ~]2`/2,
2
2
py{2
6
3J \ 4.4 Hz, H ), 9.03 (s, 2H, H ), 8.94 (s, 2H, H ), 8.52
calc. 1448.6 (61%); 1413.5 [8 ] Cu`]`, calcd. 1414.6 (23%);
py{3
py{4
py{1
(d, 2H, 3J \ 8.2 Hz, H ), 8.45 (d, 2H, 3J \ 8.2 Hz, H
),
1349.5 [8 ] H`]`, calc. 1351.0 (8%).
4, 7
4{,7{
8.28 (d, 4H, 3J \ 8.2 Hz, H ), 8.12 (d, 4H, 4J \ 1.8 Hz, H ),
Method B. A solution of porphyrin 5 (95 mg, 0.102 mmol)
o`
op{
8.05 (s, 2H, H
5{,6{
7.89 (d, 2H, 3J \ 8.4 Hz, H
3{,8{
), 7.91 (d, 2H, 3J \ 8.4 Hz, H
or H
),
and precatenate [Cu(2,9)](PF ) (0.261 g, 0.104 mmol) in
3,8
3{,8{
6 2
or H ), 7.86 (t, 2H, H ), 7.81
DMF (20 mL) was added dropwise to a stirred suspension of
3,8
pp{
(s, 2H, H ), 7.49 (d, 4H, 3J \ 8.6 Hz, H ), 7.44 (d, 4H,
5,6 m`
3J \ 8.8 Hz, H or H ), 7.43 (d, 4H, 3J \ 8.8 Hz, H or H ),
o{ o{
6.30 (d, 4H, 3J \ 8.4 Hz, H ), 6.11 (d, 4H, 3J \ 8.6 Hz, H ),
m{
4.77 (br t, 4H, H ), 4.14 (br t, 4H, H ), 3.89 (t, 4H, 3J \ 6.3
Cs CO (0.170 g, 0.52 mmol) in DMF (80 mL) at 50 ¡C at a
2
3
rate of one drop every 30 s. After stirring for 16 h at 50 ¡C, the
solvent was evaporated under reduced pressure, and the
residue partitioned between CH Cl and H O. The organic
o
o
m
b{
a{
2
2
2
Hz, H ), 3.33 (t, 4H, 3J \ 6.2 Hz, H ), 1.55 (s, 36H, CH@ ).
layer was washed three times with water, stirred with a 6.5%
a
b
3
aqueous solution of KPF and evaporated to dryness. The
6
crude product was puriÐed by repeated column chromatog-
Precatenate [Cu(2,9)](PF ) .
A
solution of [Cu-
raphy (alumina, hexane/CH Cl 20 : 80) to a†ord [2]-catenate
6 2
2 2
(CH CN) ]PF (38 mg, 0.103 mmol) in CH CN (5 mL) was
[Cu1](PF ) in 5% yield (14 mg) as a red solid.
3
4
6
3
6 2
transferred via cannula to a solution of macrocycle [9]PF
6
(170 mg, 0.104 mmol) in CH Cl (10 mL). After 20 min stir-
ring, a solution of 2 (70 mg, 0.104 mmol) in CH Cl (6 mL)
2
2
[2]-Catenane [1]PF . A mixture of catenate [Cu1](PF )
2
2
6
6 2
was added via cannula to the reaction mixture. After stirring
for 2 h, the solvents were removed in vacuo. The residue was
dissolved in CH Cl and stirred overnight with a 5% aqueous
(15.62 g, 4.904 lmol) and KCN (31.2 mg, 0.4791 mmol) in a
ternary mixture of CH CN/CHCl /H O 5.5 : 1.5 : 1.5 (8.5 mL)
3
3
2
was heated at 40 ¡C for 50 min. The reaction mixture was
diluted with CH Cl , the organic layer washed twice with
2
2
solution of KPF . The organic layer was separated, washed
6
2
2
with water, and evaporated to leave pure precatenate
water, and evaporated to dryness. The residue was dissolved
in CH Cl (10 mL) and stirred for 8 h with a 5% solution of
KPF in water (10 mL). The product [1]PF was puriÐed by
column chromatography on alumina (CH Cl as eluent) and
[Cu(2,9)](PF ) as
a red solid (0.261 g, quantitative).
6 2
2
2
1H-NMR (400 MHz, CH Cl ): d 9.55 (d, 2H, 3J \ 5.2 Hz,
2
2
6
6
H
), 9.41 (d, 2H, 3J \ 5.2 Hz, H ), 9.38 (s, 2H, H ), 9.26
py2 py3 py4
(s, 2H, H ), 8.52 (d, 4H, 3J \ 8.4 Hz, H and H ), 8.33 (d,
py1 4,7 4{,7{
4H, 3J \ 8.6 Hz, H ), 8.12 (d, 4H, 4J \ 1.8 Hz, H ), 8.05 (s,
2
2
isolated in 83% yield (12.08 mg). 1H-NMR (500 MHz,
CD Cl ): d 9.329 (d, 2H, 3J \ 5.08 Hz, H ), 9.280 (s, 2H,
o_
op
2
2
py2
2H, H ), 8.00 (t, 2H, 4J \ 1.8 Hz, H ), 7.88 (d, 2H, 3J \ 8.4
H
), 9.209 (d, 2H, 3J \ 5.24 Hz, H ), 9.034 (d, 2H,
5,6
pp
py4
py3
Hz, H
), 7.89 (d, 2H, 3J \ 8.4 Hz, H ), 7.76 (s, 2H, H
),
3J \ 4.63 Hz, H ), 8.942 (s, 2H, H ), 8.929 (d, 2H,
3{,8{
3,8
5{,6{
py{2
py{3
py{4
7.66 (d, 4H, 3J \ 8.9 Hz, H ), 7.46 (d, 4H, 3J \ 8.6 Hz, H ),
3J \ 4.62 Hz, H ), 8.882 (s, 2H, H ), 8.686 (s, 2H, H ),
m_
o
o{
py1
py{1
7.40 (d, 4H, 3J \ 8.6 Hz, H ), 6.33 (d, 4H, 3J \ 8.9 Hz, H ),
8.304 (d, 4H, 3J \ 8.79 Hz, H ), 8.188 (d, 4H, 3J \ 8.63 Hz,
m
b
o
6.12 (d, 4H, 3J \ 8.6 Hz, H ), 4.82 (t, 4H, 3J \ 3.8 Hz, H ),
m{
4.20 (t, 4H, 3J \ 4.3 Hz, H ), 3.90 (t, 4H, 3J \ 6.39 Hz, H ),
a{
H ), 8.169 (d, 4H, 3J \ 8.78 Hz, H ), 8.128 (d, 4H, 3J \ 8.63
o_
o{
Hz, H ), 8.075 (d, 4H, 3J \ 8.48 Hz, H ), 8.027 (d, 4H,
a
4,7
4J \ 1.69 Hz, H ), 8.010 (d, 4H, 4J \ 1.70 Hz, H ), 7.966 (t,
op{ op
o`
3.32 (t, 4H, 3J \ 5.9 Hz, H ), 1.54 (s, 36H, CH@ ).
b{
3
2H, 4J \ 1.77 Hz, H ), 7.935 (d, 2H, 3J \ 8.33 Hz, H ),
pp
3,8
7.813 (t, 2H, 4J \ 1.77 Hz, H ), 7.686 (d, 4H, 3J \ 8.48 Hz,
pp{
[2]-Catenate [Cu1](PF ) . Method A. To a solution of
H ), 7.661 (br s, 4H, H
and H
), 7.613 (s, 2H, H ),
6 2
m
3{,8{
4{,7{
5,6
precatenate [Cu(2,8)]PF (0.163 g, 0.0733 mmol) and gold
7.409 (d, 4H, 3J \ 8.63 Hz, H ), 7.318 (d, 4H, 3J \ 8.79 Hz,
6
m`
porphyrin [6]PF (97.5 mg, 0.0806 mmol) in DMF (10 mL) at
H ), 7.208 (d, 4H, 3J \ 8.78 Hz, H ), 7.014 (s, 2H, H
),
6
m
m{
5{,6{
60 ¡C under argon, was added portionwise, via cannula, a sus-
4.979 (t, 4H, 3J \ 3.47 Hz, H ), 4.880 (t, 4H, 3J \ 3.00 Hz,
b
pension of Cs CO (78.2 mg, 0.240 mmol) in DMF (12 mL)
H ), 4.728 (t, 4H, 3J \ 3.70 Hz, H ), 4.658 (t, 4H, 3J \ 3.85
2
3
b{
a
over 4.5 h. Heating and stirring were maintained overnight.
The reaction was stopped 20 h after the end of the addition of
Cs CO . The solvent was removed by rotary evaporation.
Hz, H ), 1.522 (s, 36H, CH ), 1.494 (s, 36H, CH@ ). FAB-MS:
a{
3
3
m/z 2832.2 [M [ PF ~]`, calc. 2833.6 (31%); 1481.6 [9]`,
6
calc. 1482.6 (100%); 1350.6 [8 ] H`]`, calc. 1351.0 (18%).
2
3
The residue was taken up in CH Cl (100 mL), washed with
2
2
water, and stirred overnight with a 5% solution of KPF in
6
water (50 mL). The crude material was subjected to repeated
column chromatography on alumina (CH Cl /CH OH
Acknowledgements
2
2
3
We warmly thank Roland Gra†, Jean-Daniel Sauer and
Michelle Martigneaux for the high Ðeld 1H-NMR spectra and
Raymond Hueber for the FAB mass spectra. M. L. thanks the
French Ministry of Education, Research and Technology and
N. F. thanks the Japan Scholarship Foundation for fellow-
ships.
100 : 0.5È1 as eluent), and pure [Cu1](PF ) was isolated in
6 2
11.5% yield (26.8 mg). 1H-NMR (500 MHz, CD Cl ): d 9.548
2
2
(d, 2H, 3J \ 5.08 Hz, H ), 9.420 (d, 2H, 3J \ 5.09 Hz, H ),
py2
9.386 (s, 2H, H ), 9.253 (s, 2H, H ), 9.136 (d, 2H, 3J \ 4.47
py4 py1
py3
Hz, H ), 9.058 (d, 2H, 3J \ 4.47 Hz, H ), 9.031 (s, 2H,
py{2
py{3
H
), 8.920 (s, 2H, H ), 8.480 (d, 2H, 3J \ 8.32 Hz, H
),
py{4
py{1
4{,7{
8.424 (d, 2H, 3J \ 8.17 Hz, H ), 8.330 (d, 4H, 3J \ 8.79 Hz,
4,7
H ), 8.283 (d, 4H, 3J \ 8.63 Hz, H ), 8.124 (d, 4H, 4J \ 1.85
o_
o`
References
Hz, H or H ), 8.122 (d, 4H, 4J \ 1.70 Hz, H or H ),
op
op{
op{
op
8.004 (t, 2H, 4J \ 1.77 Hz, H ), 7.979 (d, 2H, 3J \ 8.32 Hz,
1
For early references, see: (a) T.-F. Ho, A. R. McIntosh and J. R.
Bolton, Nature (L ondon), 1980, 286, 254; (b) M. Migita, T. Okada,
N. Mataga, S. Nishitani, N. Kurata, Y. Sakata and S. Misumi,
Chem. Phys. L ett., 1981, 84, 263; (c) P. Pasman, F. Rob and J. W.
Verhoeven, J. Am. Chem. Soc., 1982, 104, 5127; (d) J. R. Miller, L.
T. Calcaterra and G. L. Closs, J. Am. Chem. Soc., 1984, 106, 3047;
(e) A. D. Joran, B. A. Leland, G. G. Geller, J. J. HopÐeld and P.
B. Dervan, J. Am. Chem. Soc., 1984, 106, 6090; ( f ) T. A. Moore,
D. Gust, P. Mathis, J.-C. Mialocq, C. Chachaty, R. V. Bensasson,
pp
H
), 7.915 (d, 2H, 3J \ 8.32 Hz, H ), 7.870 (t, 2H,
3{,8{
3,8
4J \ 1.85 Hz, H ), 7.733 (s, 2H, H ), 7.673 (d, 4H, 3J \ 8.79
pp{
5,6
Hz, H ), 7.670 (s, 2H, H
), 7.512 (d, 4H, 3J \ 8.63 Hz,
m_
5{,6{
H
), 7.447 (d, 4H, 3J \ 8.64 Hz, H ), 7.392 (d, 4H, 3J \ 8.64
m`
o{
Hz, H ), 6.386 (d, 4H, 3J \ 8.79 Hz, H ), 6.376 (d, 4H,
o
m
3J \ 8.78 Hz, H ), 4.821 (t, 4H, 3J \ 3.85 Hz, H ), 4.780 (t,
m{
4H, 3J \ 4.33 Hz, H ), 4.233 (t, 4H, 3J \ 4.23 Hz, H ), 4.198
b{
b
a
New J. Chem., 2001, 25, 790È796
795

View Article Online
E. J. Land, D. Doizi, P. A. Liddell, G. A. Nemeth and A. L.
Moore, Nature (L ondon), 1984, 307, 630; (g) M. R. Wasielewski,
M. P. Niemczyk, W. A. Svec and E. B. Pewitt, J. Am. Chem. Soc.,
1985, 107, 5562; (h) H. Heitele and M. E. Michel-Beyerle, J. Am.
Chem. Soc., 1985, 107, 8286.
(a) A. M. Brun, A. Harriman, V. Heitz and J.-P. Sauvage, J. Am.
Chem. Soc., 1991, 113, 8657; (b) A. M. Brun, S. J. Atherton, A.
Harriman, V. Heitz and J.-P. Sauvage, J. Am. Chem. Soc., 1992,
114, 4632.
(a) M. J. Gunther and M. R. Johnston, J. Chem. Soc., Chem.
Commun., 1992, 1163; (b) F. Le Bras, B. Loock and M. Momen-
teau, T etrahedron L ett., 1994, 35, 3289; (c) J.-C. Chambron, V.
Heitz and J.-P. Sauvage, Bull. Soc. Chim. Fr., 1995, 132, 340.
(a) P. R. Ashton, M. R. Johnston, J. F. Stoddart, M. S. Tolley and
J. W. Wheeler, J. Chem. Soc., Chem. Commun., 1992, 1128; (b)
J.-C. Chambron, V. Heitz and J.-P. Sauvage, J. Chem. Soc., Chem.
Commun., 1992, 1131; (c) F. Vogtle, F. Ahuis, S. Baumann and J.
L. Sessler, L iebigs Ann., 1996, 921; (d) A. E. Rowan, P. P. M
Aarbs and K. W. M. Koutstaal, Chem. Commun., 1998, 611; (e) K.
Chichak, M. C. Walsh and N. R. Branda, Chem. Commun., 2000,
847.
5
6
(a) M. Linke, J.-C. Chambron, V. Heitz and J.-P. Sauvage, J. Am.
Chem. Soc., 1997, 119, 11329; (b) M. Linke, J.-C. Chambron, V.
Heitz, J.-P. Sauvage and V. Semetey, Chem. Commun., 1998, 2469;
(c) M. Linke, J.-C. Chambron, V. Heitz, J.-P. Sauvage, S. Encinas,
F. Barigelletti and L. Flamigni, J. Am. Chem. Soc., 2000, 122,
11834.
(a) D. B. Amabilino and J.-P. Sauvage, Chem. Commun., 1996,
2441; (b) D. B. Amabilino and J.-P. Sauvage, New J. Chem., 1998,
22, 395.
C. Dietrich-Buchecker and J.-P. Sauvage, T etrahedron, 1990, 46,
503.
(a) T. JÔrgensen, J. Becher, J.-C. Chambron and J.-P. Sauvage,
T etrahedron L ett., 1994, 35, 4339; (b) L. Raehm, J.-M. Kern and
J.-P. Sauvage, Chem. Eur. J., 1999, 5, 3310.
S. Chardon-Noblat and J.-P. Sauvage, T etrahedron, 1991, 47,
5123.
2
3
4
7
8
9
10 C. O. Dietrich-Buchecker, P. A. Marnot, J.-P. Sauvage, J.-P.
Kintzinger and P. Maltese, New J. Chem., 1984, 8, 573.
11 C. O. Dietrich-Buchecker and J.-P. Sauvage, Chem. Rev., 1987,
87, 795.
12 G. J. Kubas, Inorg. Synth., 1990, 28, 90.
796
New J. Chem., 2001, 25, 790È796