Copper(I)-templated synthesis of [2]catenates bearing pendant porphyrins

Article abstract of DOI:10.1039/a708756j

The copper(I)-templated synthesis of the first [2]catenate incorporating electron-donor and -acceptor porphyrins linked mechanically, though not covalently, has been achieved, along with that of related model compounds incorporating only electron donating zinc(II) porphyrins. The preparations were approached by first constructing macrocycles incorporating 2,9-diphenyl-1,10-phenanthroline residues and pendant porphyrins. An unusual aggregation of one of these macrocycles, incorporating a gold(III) porphyrin, has been observed and appears to be driven by π-π stacking interactions, but proves to be no impediment to the preparation of the catenates. The gross conformation of the catenates in solution seems to be approximately that of the envisaged design where the porphyrins are directed to opposite sides and laterally away from the heart of the catenate, since no inter-porphyrin interactions could be detected by NMR or UV-visible spectroscopy. The removal of the templating copper(I) ion from the catenates is inhibited by the presence of appended zinc(II) porphyrins, while the free catenands may be obtained when the zinc(II) ion is absent.

Full text of DOI:10.1039/a708756j

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Copper(I)-templated synthesis of [2]catenates bearing pendant
porphyrins
David B. Amabilino*,¤ and Jean-Pierre Sauvage*
L aboratoire de Chimie Organo-Minerale (CNRS URA 422), Institut L e Bel, Universite L ouis
Pasteur, 4, rue Blaise Pascal, 67070 Strasbourg, France
The copper(I)-templated synthesis of the Ðrst [2]catenate incorporating electron-donor and -acceptor porphyrins
linked mechanically, though not covalently, has been achieved, along with that of related model compounds
incorporating only electron donating zinc(II) porphyrins. The preparations were approached by Ðrst
constructing macrocycles incorporating 2,9-diphenyl-1,10-phenanthroline residues and pendant porphyrins. An
unusual aggregation of one of these macrocycles, incorporating a gold(III) porphyrin, has been observed and
appears to be driven by pÈp stacking interactions, but proves to be no impediment to the preparation of the
catenates. The gross conformation of the catenates in solution seems to be approximately that of the envisaged
design where the porphyrins are directed to opposite sides and laterally away from the heart of the catenate,
since no inter-porphyrin interactions could be detected by NMR or UV-visible spectroscopy. The removal of the
templating copper(I) ion from the catenates is inhibited by the presence of appended zinc(II) porphyrins, while
the free catenands may be obtained when the zinc(II) ion is absent.
Synthese de [2]catenates porteurs de porphyrines par e†et template de cuivre(I). La synthese par e†et de matrice,
induit par le cuivre(I), du premier [2]catenate incorporant une porphyrine donneur dÏelectron et une porphyrine
accepteur, a ete realisee. Les deux porphyrines sont reliees par un lien mecanique, non covalent. La strategie de
synthese implique, dans un premier temps, la preparation de macrocycles contenant des residus de type 2,9-
diphenyl-1,10-phenanthroline et des porphyrines pendantes. Un processus inhabituel dÏagregation de lÏun des
macrocycles, comportant une porphyrine dÏor(III), a ete observe. Ce phenomene, vraisemblablement favorise par
des interactions dÏempilement pÈp, nÏinhibe pas la preparation des catenates. En solution, la conformation des
catenates semble grossierement correspondre au schema propose, dans lequel les deux porphyrines sont situees
de part et dÏautre du coeur du catenate et dirigees dans des directions opposees. Cette geometrie est en accord
avec les etudes de RMN et de spectroscopie UV-visible, qui ne montrent aucune interaction entre les noyaux
porphyriniques. La decomplexation de lÏion assembleur cuivre(I) nÏa pas pu etre realisee, probablement du fait
que des porphyrines de zinc(II) jouant le role dÏinhibiteur de demetallation. Par contre, lorsque les porphyrines
ne contiennent pas de zinc, le catenand libre peut etre obtenu.
The synthesis and study of synthetic molecules capable of
exhibiting long-range electron transfer is a topical and impor-
tant pursuit.1 The reasons for the interest in such molecules
are twofold: (i) to mimic the primary electron-transfer step at
the heart of the Photosynthetic Reaction Centre2 as well as in
other biological systems,3 in order to aid understanding of
these natural phenomena; (ii) to create molecules exhibiting
new photophysical and photochemical properties.
twined ligands bound to a transition metal ion, which should
be readily and controllably exchangeable for another ion,
thereby modulating its electronic properties. The donor D and
acceptor A chromophores should therefore exhibit a rate of
The synthetic molecules whose photophysical properties
have been studied mainly involve connection of the donor and
acceptor moieties by covalent bonds,4 while alternative
approaches have tackled the problem using non-covalent con-
nections, in the form of hydrogen bonds5 or metal ion com-
plexation.6 In all of these approaches the medium between
donor and acceptor chromophores is invariably modulated by
changing the connectivity of the covalent bonds within the
components, generally requiring repeated synthesis. To avoid
this drawback, a single molecule incorporating donor and
acceptor chromophores separated by a medium whose elec-
tronic properties could be altered by reversible and simple
coordination chemistry is an appealing prospect. The
[2]catenate7 depicted schematically in Fig. 1 may meet these
requirements. The heart of this catenane contains two inter-
Fig. 1 Cartoon representations of
a [2]rotaxane incorporating
donor D and acceptor A chromophores spaced by a bridge B com-
prising a metal complex including a threaded macrocycle (upper), and
the design (lower) of the [2]catenate that is the subject of this work,
¤ New address: Institut de Ciencia de Materials de Barcelona,
Consejo Superior de Investigaciones Cient•Ðcas (CSIC), Campus Uni-
versitari, 08193-Bellaterra, Spain.
comprising two interlocked macrocycles, one bearing
chromophore and the other an acceptor chromophore
a
donor
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395

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electron transfer dependent on the bridge B. The chromo-
phores, for which we have selected porphyrins, are pendant
groups, in an e†ort to exert control over the interporphyrin
distance depending on the geometry of B. The design in Fig. 1
is thus quite unique,8 although many interlocked molecules
incorporating porphyrins have been reported,9 including
rotaxanes with donor and acceptor chromophores in the same
dumbbell-shaped component10 whose properties can be
modulated by varying the metal ion11 (Fig. 1), and a
[2]catenate with identical porphyrins in each ring.12
The chemical realisation of the cartoon system in Fig. 1 is
based on established copper(I) ion-templated [2]catenates13È
incorporating diphenyl-1,10-phenanthroline residuesÈand the
appendage of zinc(II) (D) and gold(III) (A) porphyrins, which
are of proven utility in the study of electron-transfer pheno-
mena.10 The component rings of the series of [2]catenates are
composed of 31 members, as close as possible to that of the
well-documented prototypical [2]catenate comprised of two
30-membered rings.14 Polyethylene spacers between the phe-
nanthroline chelate and the porphyrin a†ord moderate rigid-
ity without inferring conjugation. The porphyrins are of the
tetraaryl variety, substituted at the 3 and 5 positions of one
aryl ring to form the macrocycle, so that the porphyrin is
appended away from the core of the catenate while avoiding
the presence of atropoisomers.
Results and Discussion
Synthesis of precursors and model compounds
The synthetic route chosen for the preparation of the macro-
cycles and catenates reported here was to introduce the
porphyrin moieties in the Ðnal macrocyclisation steps, since
they are the most expensive and potentially chemically sensi-
tive group. This approach, unlike the more usual syntheses of
this family of catenates,13 required the preparation of the new
extended 2,9-bis(4-phenoxy)-1,10-phenanthrolines 2È4, whose
synthesis is depicted in Scheme 1. The diol 2 was a†orded in
86% yield by reaction of 2,9-bis(4-hydroxyphenyl)-1,10-phe-
nanthroline (1)14 with 2-(2-chloroethoxy)ethanol in the pres-
ence of base in DMF. Conversion of this diol into the
ditosylate 3 was achieved using standard conditions for
tosylation15 in 67% yield, and treatment of the ditosylate with
NaI in acetone gave 4 almost quantitatively.
The macrocycle 6, required for the synthesis of a model
[2]catenate bearing a porphyrin (vide infra), was prepared by
the reaction of the ditosylate 5 (prepared in two steps from
methyl 3,5-dihydroxybenzoate) with 1 in the presence of
Cs CO (Scheme 2).16 The Ðnal macrocyclisation a†orded the
Scheme 1
uents of 8 were removed (Scheme 3) by using BBr under stan-
dard conditions18 to a†ord the dihydroxy derivative 9 in 93%
2
3
3
desired 6 in 36% yield. The chromatographic separation also
yielded 2% of the poorly soluble dimeric macrocycle 7 with 62
ring members and two phenanthroline residues.
yield.
In the catenations (vide infra) it is desirable to ““protectÏÏ the
free base porphyrins because of the possibility of forming
copper(II) porphyrins during the templated reaction. There-
fore, the simple tetraaryl porphyrin 9 was reacted with zinc(II)
acetate to a†ord almost quantitatively the desired zinc(II)
porphyrin 10. Conversely, attempted metallation of 9 with
gold(III) was unsuccessful; the major products resulted from
decomposition of the porphyrin prior to entry of the metal
Synthesis and properties of porphyrin components
The tetraaryl porphyrin 8, in which three of the aryl groups
bear tert-butyl groups at positions 3 and 5 while the other has
methoxy moieties at the same positions, was prepared in 8.9%
yield by reaction (Scheme 3) of four equivalents of pyrrole
with three of 3,5-di-tert-butylbenzaldehyde17 and one of 3,5-
dimethoxybenzaldehyde in propionic acid. The two corre-
ion. On the other hand, treatment of 8 with KAuCl in acetic
4
acid in the presence of NaOAc19 a†orded the corresponding
sponding isomeric A B porphyrins (bearing two aryl groups
gold(III) porphyrin 11 in 80% yield, the remainder of the
product corresponding to the starting porphyrin.
2 2
with tert-butyl groups at positions 3 and 5 and two with
methoxy moieties at the same positions) were also isolated
The macrocycle 12 bearing a pendant free base porphyrin
was prepared by the reaction of the diphenoxy porphyrin 9
with the extended phenanthroline ditosylate 3 in the presence
of Cs CO in DMF with an optimised yield of 47%.20 This
from the chromatographic separation of the desired A B
3
porphyrin in yields of approximately 1% for each. The iden-
tity of these compounds, which have virtually identical UV-
visible spectra, was conÐrmed by 1H NMR and mass
spectrometry. The two methyl groups in the methoxy substit-
2
3
free base porphyrin was converted almost quantitatively (as in
the preparation of 10) into the corresponding zinc(II) porphy-
396
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Scheme 3
tion (Fig. 2). The observation that the hydrogen atoms in the
aromatic phenanthroline and porphyrin ring systems become
increasingly shielded as the temperature of solutions of 14 is
lowered and the concentration is raised indicates aggregation
of the molecule. The proximity of the aromatic systems was
conÐrmed by a ROESY NMR experiment, in which signiÐ-
cant nOes were observed (amongst others) between the reso-
nances arising from the phenanthroline H , H
and H
5, 6
4, 7 3, 8
hydrogen atoms and those for the hydrogen atoms attached
to the phenyl rings adjacent to the porphyrin. From these
data it seems clear that the aggregation is driven by pÈp inter-
actions involving the gold(III) porphyrin and the phenanthrol-
ine moiety; to our knowledge this is the Ðrst observation of
noncovalent interactions between these groups.21
Scheme 2
rin 13, and into the gold(III) porphyrin 14 in an optimised
yield of 91%, by treatment with KAuCl in acetic acid in the
4
presence of NaOAc, followed by a work-up to a†ord the
product as its hexaÑuorophosphate salt (Scheme 4).
The nOe data for the aggregates of 14 allow for the pres-
ence of two conformations for the macrocycle: (i) stacking of
the molecules in a head-to-tail fashion such that the aggregate
is comprised entirely of intermolecular interactions or (ii)
folding of the molecules as a result of an intramolecular stack-
ing of the phenanthroline and porphyrin moieties (Fig. 3), fol-
lowed by stacking in this conformation. The concentration
dependence of the chemical shift of the resonance arising from
The macrocycles 12 and 13 had spectroscopic character-
istics corresponding to the sum of their phenanthroline-
containing macrocycle and porphyrin component parts. The
UV-visible spectrum of the gold(III) porphyrin 14 at room
temperature in CH Cl also corresponds to that of a molecule
2
2
with noninteracting phenanthroline and gold(III) porphyrin
moieties. However, the 1H NMR spectrum of 14 in CD Cl is
2
2
very di†erent from that of the components and the other
porphyrin-bearing macrocycles. The di†erences are even more
pronounced when the 1H NMR spectrum of 14 is recorded in
CD CN (Fig. 2, the abbreviations H and H refer to the
the H
hydrogen atoms of the phenanthroline moiety indi-
5, 6
cates that even at very low concentration this signal is at very
high Ðeld compared with its more usual position (5.8 vs.
approx. 7.7 ppm), and therefore in a folded conformation, con-
sistant with the latter type of aggregate. This form of aggre-
gation proves to be no barrier to the generation of the
extremely stable threaded complexes of 14 with copper(I) and
phenanthroline-containing strings,7d and to catenate forma-
tion.
3
o
m
hydrogen atoms attached to the ortho and meta positions,
respectively, of the phenyl ring attached to the phenanthroline
ring system, whose hydrogen atoms are numbered H , H
3, 8
4, 7
and H , respectively). In particular, the resonances arising
5, 6
from the H
and H
hydrogen atoms appear at extremely
5, 6
4, 7
high Ðeld, while those arising from the hydrogen atoms
attached to the pyrrolic rings of the porphyrin are at high Ðeld
relative to those of the gold(III) porphyrin 11 in the same
solvent. The 1H resonances from 14 in CD CN are strongly
dependent on both temperature (all resonances are shifted to
Synthesis and properties of porphyrin-bearing [2]catenates
The synthesis of the [2]catenate 18 (Scheme 5), incorporating
two 31-membered rings that both have an appended tetraaryl
zinc(II) porphyrin, was approached by two routes.14 In the
3
high Ðeld as the temperature is lowered) as well as concentra-
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Scheme 4
Fig. 2 The 1H NMR spectrum of the macrocycle bearing a gold(III)
porphyrin 14 : PF in CD CN at room temperature and at concentra-
Fig. 3 A probable conformation for the macrocycle 14 : PF in
6
dilute CD CN, which results in the formation of aggregates at higher
6
3
3
tions of (a) 28 (b) 5.8 and (c) 0.74 mM
concentrations
398
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Scheme 5
Ðrst, the ditosylate 3 was treated with half an equivalent of
copper(I) ions to generate the intertwined red complex 15 as
its hexaÑuorophosphate salt. This complex was reacted
(Scheme 5) at 60 ¡C with the diphenolic zinc(II) porphyrin 10
in the presence of Cs CO and KI, which was added to
exchange with the tosylate leaving group. The [2]catenate 18
was isolated in 14% yield, rather low compared with that
expected for this kind of reaction,14 partially owing to diffi-
culties in separation.22
The approach involving the more stable copper(I) complex
17 was employed (Scheme 5) by forming the copper(I) complex
16 of the macrocycle 13, followed by threading the reactive
diiodide thread 4 and reaction at 50 ¡C with the diphenolic
porphyrin 10. This method a†orded the [2]catenate 18 as its
hexaÑurophosphate salt in 33% yield. Under similar condi-
tions, this compares with 45% for the original [2]catenate14
and 31% for a related catenate prepared by Momenteau and
coworkers,12 which incorporated zinc(II) porphyrins within
the component macrocycles. As in that case, the zinc(II) ions
could be removed from the two porphyrins, in this instance by
treatment with triÑuoroacetic acid, to a†ord the bis-free-base
porphyrin catenate 19.
Both 18 and 19 have 1H NMR spectra (Fig. 4) in which the
chemical shifts of the resonances resulting from the porphyrin
moieties are similar to those arising from the simple porphy-
rins 9 and 10, respectively. The resonances corresponding to
the hydrogen atoms attached to the phenyl phenanthroline
systems entwined around the templating metal ion are also in
similar positions to those for related copper(I) catenates.14 The
UV-visible spectrum has absorption bands characteristic of
the separated porphyrins. Therefore, the gross conformation
of the molecule approximates that required for the design pre-
sented in Fig. 1, in which the porphyrin moieties are linearly
disposed.
2
3
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As a model reaction for the preparation of the donor-
acceptor catenate depicted schematically in Fig. 1, the mixed
[2]catenate 20 was prepared (Scheme 6) using the two-step
method from the ester-functionalised macrocycle
6 and
forming the other component macrocycle 13. The desired
catenate 20 was isolated as its hexaÑuorophosphate salt after
column chromatography in a yield of 27%. In addition, the
component porphyrin-bearing macrocycle 13 was isolated in
10% yield, as well as the [2]catenate 18 bearing two zinc(II)
porphyrins in 16% yield. The total yield of catenated products
was therefore 43%.
Fig. 4 The partial 1H NMR spectrum of the [2]catenate 18 : PF in
It is clear that the formation of the symmetric catenate 18
during the reaction to prepare the dissymmetric 20 is a result
of ““scramblingÏÏ of the intermediate complexes as a conse-
quence of the decomposition of the initial precatenate under
the basic reaction conditions (Scheme 7). Thus, macrocycle 13
is formed in its ““freeÏÏ state and subsequently forms the
entwined complex 17 with 4 and a copper(I) ion. From a syn-
thetic point of view, the ratio of dissymmetric : symmetric
catenate generated in this case (2 : 1) is a drawback, which
brings into question the future utility of the Williamson ether
synthesis for the construction of this type of catenate.23
The main object of this work was to create the [2]catenate
schematised in Fig. 1, bearing donor and acceptor porphyrins.
The chemical realisation of this aim, the catenate 22 com-
prised of macrocyclic components, one bearing a gold(III)
porphyrin and the other a zinc(II) porphyrin, was achieved
using the synthesis depicted in Scheme 8. The precatenate 21
incorporating the macrocycle bearing a gold(III) porphyrin
was Ðrst generated quantitatively by formation of the
copper(I) complex of 14 and subsequent threading of 4. This
6
CD Cl
2
2
complex was then reacted with the diphenolic porphyrin 10 in
the presence of cesium carbonate to a†ord the desired
[2]catenate in 16% yield in the form of its bishexaÑuorop-
hosphate salt after counter-ion exchange and column chroma-
tography. In addition, the component macrocycles and the
bis-zinc(II) porphyrin catenate 18 were isolated. As in the pre-
vious catenation, these are formed as a result of decomposi-
tion and ““scramblingÏÏ of the initial precatenate 21.
The donorÈacceptor catenate 22 has a fast atom bombard-
ment mass spectrum with peaks corresponding to ions in
which one and two hexaÑuorophosphate counter ions are lost
from the molecule, as well as to ions of the copper complexes
of the component macrocycles as a result of fragmentation of
the molecule in the spectrometer. In contrast, the electrospray
mass spectrum (Fig. 5) shows a single group of peaks centered
at 1649 mass units, assignable to the doubly charged ion of 22
Scheme 6
400
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Scheme 7
after loss of its hexaÑuorophosphate counter ions. The 1H
436 nm. The corresponding absorption bands of the purple
MeCN solution of the bis-zinc(II) porphyrin 18 are located at
597, 557 and 425 nm, respectively, and have di†erent relative
intensities to those of the species formed with KCN. An elec-
trospray mass spectrum of the green reaction mixture for the
attempted demetalation of 22 shows signals of a complex of
the catenate with KCN, as well as for the potassium catenate.
However, work-up of these reaction mixtures only a†orded
the starting copper(I) catenates.
NMR spectrum of the compound in CD Cl shows the reso-
2
2
nances expected for the interlocked phenyl phenanthroline
units and those for noninteracting zinc(II) and gold(III) porphy-
rins. The UV-visible spectrum of the [2]catenate in CH Cl
2
2
exhibits absorptions in the visible region equivalent to the
sum of those for the component gold(III) and zinc(II) porphy-
rins and the copper(I) chelate complex.
In contrast, treatment of the bis-free-base porphyrin cate-
nate 19 with KCN (Scheme 9) resulted in a red organic solu-
tion that a†orded the desired [2]catenand 23 almost
quantitatively. The electrospray mass spectrum of this com-
pound gave peaks corresponding to doubly protonated
doubly charged and triply protonated triply charged species at
1488 and 992 mass units, respectively. The 1H NMR spectrum
has resonances arising from the phenanthroline residue at par-
ticularly high Ðeld compared with their more usual values in
catenands. In addition, the signal arising from the NH
protons at [ 3.18 ppm is at slightly higher Ðeld than the cor-
responding resonance in the catenate 19, probably reÑecting
Removal of the templating copper(I) ion from [2]catenates
Removal of the templating metal ion from the catenates syn-
thesised in this study is an attractive prospect, since it would
allow tuning of the distance and nature of the space between
the porphyrins. The templating copper(I) ion is routinely
removed from nonfunctionalised [2]catenates of this family by
treatment with KCN.24 All attempts to remove the template
from either 18 or 22 were unsuccessful. When either was
treated with KCN, intensely coloured green solutions formed
with UV-visible absorptions, in the case of 18, at 618, 576 and
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Scheme 8
the proximity of the porphyrin to other aromatic residues, and
therefore a change in the relative arrangement of the two rings
upon removal of the templating metal ion.
The difficulty associated with the removal of the templating
copper(I) ion from the catenates 18 and 22 seems to be associ-
ated with the presence of the zinc(II) ion within the porphyrin,
since formation of the free [2]catenand is possible when this
ion is absent. This result could be associated with the ability
of zinc(II) porphyrins to accept axial ligands.25 Cyanide ions
acting in this way may a†ect the removal of the copper(I) ion
from the centre of the catenates or accelerate the re-entry of
the metal ion in this chemically and topologically24,26
complex system.
Conclusions
The Ðrst catenate incorporating electron-donor and -acceptor
porphyrins linked mechanically, though not covalently, has
been achieved, along with related model compounds incorpor-
ating only electron-donating zinc(II) porphyrins. These latter
molecules are important model systems for understanding the
photophysical properties of the interlocked compounds, which
will be related in upcoming work.27 The overall conformation
of the catenates in solution seems to be approximately that of
the design illustrated in Fig. 1, since no intraporphyrin inter-
actions could be detected by NMR or UV-visible spectros-
copy. The removal of the templating copper(I) ion from the
catenates is extremely inhibited by the presence of appended
zinc(II) porphyrins, while the free catenands may be obtained
when the zinc(II) ion is absent. During this work, an unusual
aggregation of one of the components, a macrocycle incorpor-
ating a gold(III) porphyrin, has been documented. The use of
these and related components for incorporation into other
interlocked compounds, and the study of their photophysical
properties, is currently underway.
Fig. 5 Part of the electrospray mass spectrum of the [2]catenate
22 : 2PF , showing the peak resulting from the [M [ 2PF ]2` ion
6
6
402
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Scheme 9
a degassed and vigourously stirred suspension of freshly
ground K CO (10.4 g, 75.2 mmol) in DMF (250 mL) under
Experimental
General
2
3
an atmosphere of Ar. The temperature of the mixture was
raised to 60 ¡C, and after 30 min 2-(2-chloroethoxy)ethanol
(7.66 g, 61.5 mmol) was added by syringe. The temperature of
the mixture was raised to 100 ¡C and these conditions were
maintained for 20 h. The reaction mixture was Ðltered at the
pump while still warm, and the residual solid was washed with
DMF (100 mL) and EtOAc (100 mL). The mixture of organic
solvents was removed in vacuo to leave a yellow oily residue,
which was partitioned between CH Cl (100 mL) and H O
The following chemicals were obtained commercially and used
without further puriÐcation: 2-(2-chloroethoxy)ethanol
(Aldrich), 3,5-dimethoxybenzaldehyde (98%, Lancaster), pro-
pionic acid (99%, Acros), 4-toluenesulfonyl chloride (Fluka).
Immediately prior to use, commercial pyrrole (Acros) was
passed through an alumina column in the dark and was col-
lected under argon. Cu(MeCN) PF ,28 3,5-di-tert-butyl-
benzaldehyde17 and 2,9-bis(4-hydroxyphenyl)-1,10-phenan-
throline (1)14,15 were prepared according to literature pro-
cedures. NMR spectra were recorded using Bruker WP200SY
4
6
2
2
2
(100 mL). The solid that formed was Ðltered under gravity and
then dissolved in acetone (50 mL). The acetone-soluble
material (1.80 g) was found to be the desired product in pure
form. The CH Cl solution was stripped of solvent, and the
or AM400 spectrometers. In the 1H NMR assignment (d), H
o
and H refer to the hydrogen atoms attached to the ortho and
m
2
2
residue was subjected to column chromatography (SiO ,
meta positions, respectively, of the phenyl ring attached to the
2
CHCl ÈEtOAcÈMeOH, gradient from 20 : 1 : 0 to 20 : 2 : 0.5),
3
phenanthroline ring system, whose hydrogen atoms are num-
leading to a total of 3.56 g (86%) of pure 2,9-bis(4-M2-[2-
bered H , H
and H , respectively, and Ar is used as an
3, 8
4, 7
5, 6
hydroxyethoxy(ethoxy)]Nphenyl)-1,10-phenanthroline.
abbreviation for aromatic ring. Mass spectra were recorded in
the positive-ion mode of operation with ZAB-HF (FAB) and
VG BIOQ triple quadrupole (ES) spectrometers. Melting
points were measured using a Buchi SMP20 apparatus and
are uncorrected.
White solid (mp 124È126 ¡C). 1H NMR (CDCl , 200.13
3
MHz) 3.50È3.65 (m, 8H), 3.95 (t, 4H), 4.28 (t, 4H), 7.14 (d,
J \ 8.9 Hz, 4H, H ), 7.75 (s, 2H, H ), 8.09 (d, J \ 8.5 Hz,
m
5, 6
2H, H ), 8.27 (d, J \ 8.5 Hz, 2H, H ), 8.44 (d, J \ 8.9 Hz,
3, 8
4, 7
4H, H ). 13C NMR (CDCl , 50.32 MHz) 61.9, 67.6, 69.8, 72.7
(all CH O), 114.9 (CH ), 119.4 125.7, 127.6, 129.1 (CH ), 133.1,
136.9, 156.3, 160.0. Anal. Calcd for C
5.97; N, 5.18%. Found: C, 71.02; H, 6.18; N, 5.22%.
o
3
Preparations
2
m
o
N O : C, 71.10; H,
2,9-Bis(4-{2-[2-hydroxyethoxy(ethoxy)]}phenyl)-1,10-phen-
anthroline (2). The diphenol 2,9-bis(4-hydroxyphenyl)-1,10-
phenanthroline (1) (2.80 g, 7.68 mmol) was added as a solid to
H
32 32
2 6
FAB-MS: m/z found 541.1 ([M ] H]`) calcd, 541.2.
New J. Chem., 1998, Pages 395È409
403

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2,9-Bis(4-{2-[2-(4-toluenesulfonyl)ethoxy(ethoxy) ]}phenyl)-
1,10-phenanthroline (3). The diol 2 (815 mg, 1.50 mmol) was
dissolved in dry CH Cl (150 mL) under a silica gel guard.
Methyl-3,5-{2- [2-(4-toluenesulfonyl)ethoxy(ethoxy)]}-ben-
zoate (5). Methyl 3,5-dihydroxybenzoate (6.00 g, 35.7 mmol)
was added as a solid to a degassed and vigourously stirred
suspension of freshly ground K CO (31.1 g, 225 mmol)
2
2
The solution was cooled to 0 ¡C in an ice/salt mixture, then
2
3
Et N (1.0 mL) and 4-dimethylaminopyridine (5 mg) were
in DMF (250 mL) at 40 ¡C under an atmosphere of Ar. The
temperature of the mixture was raised to 60 ¡C and was
maintained at this temperature for 30 min, after which 2-(2-
chloroethoxy)ethanol (17.81, 143 mmol) was added by syringe.
The temperature of the mixture was raised to 110 ¡C and these
conditions were maintained for 6 h. The reaction mixture was
Ðltered at the pump while still warm, and the residual solid
was washed with DMF (100 mL) and EtOAc (100 mL). The
mixture of organic solvents was removed in vacuo to leave a
yellow oily residue, which was subjected to column chroma-
tography (SiO , CH Cl Èethyl acetate, 1 : 1). Methyl 3,5-M2-
3
added. The subsequent addition of 4-toluenesulfonyl chloride
(680 mg, 3.57 mmol) was made portionwise over a period of
15 min. The solution was then allowed to stir at 0 ¡C for 3 h,
and after warming to room temperature was stirred for a
further 12 h. TLC indicated that the reaction had not pro-
ceeded to completion, so the reaction mixture was cooled to
0 ¡C, and an additional portion of 4-toluenesulfonyl chloride
(350 mg, 1.83 mmol) was added. After stirring for 2 h at 0 ¡C
and 6 h at room temperature, the reaction mixture was
poured onto a mixture of ice (75 g) and HCl (10% aq). The
organic layer was separated, and the acid layer was washed
2
2 2
[2-hydroxyethoxy(ethoxy)]Nbenzoate was isolated as an oil
with CHCl (100 mL). The organic layers were combined,
(3.69 g, 30%). 1H NMR (CDCl , 200.13 MHz) 3.08 (bs, 2H,
OH), 3.54È3.60 (m, 4H, CH O), 3.63È3.69 (m, 4H, CH O),
3.73È3.79 (m, 4H, CH O), 3.81 (s, 3H, OCH ), 4.02È4.09 (m,
4H, CH O), 6.64 (t, J \ 2.3 Hz, 1H), 7.13 (d, J \ 2.3 Hz, 2H).
Without further puriÐcation, this product (2.60 g, 7.55
3
3
washed with H O (150 mL), and dried (MgSO ). After Ðl-
2
4
2
2
tration, the solvent was removed in vacuo. The resulting oily
2
3
residue was subjected to column chromatography (SiO ,
2
CHCl ) a†ording two products.
2
3
The desired ditosylate (858 mg, 67%) was obtained as an oil
mmol) was dissolved in dry CH Cl (100 mL) and cooled in
2
2
that solidiÐed upon standing. 1H NMR (CDCl , 200.13 MHz)
an ice/salt mixture under a CaCl guard tube. Following addi-
3
2
2.38 (s, 6H), 3.75È3.87 (m, 8H), 4.11È4.25 (m, 8H), 7.08 (d,
tion of dry Et N (4 mL), 4-toluenesulfonyl chloride (3.60 g,
18.9 mmol) was added portionwise over a period of 15 min;
3
J \ 8.7 Hz, 4H, H ), 7.30 (d, J \ 8.3 Hz, 4H, H ), 7.73 (s, 2H,
m
Ts
H
H
), 7.81 (d, J \ 8.3 Hz, 4H, H ), 8.07 (d, J \ 8.5 Hz, 2H,
the mixture was then stirred under the same conditions for 4 h,
after which it was allowed to warm slowly to ambient tem-
perature and then stirred for 1 day. The reaction mixture was
poured onto a mixture of ice (75 g) and HCl (10% aq, 300
mL). After addition of further CH Cl (100 mL) and thawing,
5, 6
3, 8
Ts
), 8.25 (d, J \ 8.5 Hz, 2H, H ), 8.43 (d, J \ 8.7 Hz, 4H,
4, 7
H ). 13C NMR (CDCl , 50.32 MHz) 21.7 (CH ), 67.5, 69.0,
o
3
3
69.3, 69.9 (all CH O), 114.9 (CH ), 119.4, 125.7, 127.6, 128.0,
2
m
129.1, 129.9, 132.5, 133.1, 136.9, 144.9, 146.0, 156.3, 160.1.
2
2
FAB-MS: m/z found 849.1 ([M ] H]`), calcd for
the organic layer was separated and washed with H O (100
2
mL), and then dried (MgSO ). After Ðltration, the solvent was
4
C
H
N O S , 849.3.
46 44
2
10 2
The corresponding monotosylate (273 mg, 26%) was a
removed in vacuo and the resulting oily residue was subjected
yellow oil. 1H NMR (CDCl , 200.13 MHz) 2.17 (t, J \ 6 Hz,
to column chromatography (SiO , 20 : 1 CH Cl ÈEtOAc)
3
2
2 2
1H, OH), 2.40 (s, 6H), 3.68È3.88 (m, 8H), 3.94 (t, J \ 5 Hz,
giving 3.30 g (67%) of the desired ditosylate 5.
2H), 4.13È4.31 (m, 6H), 7.09 (d, J \ 8.7 Hz, 2H, H ), 7.13 (d,
Clear oil, which solidiÐed upon standing. 1H NMR
m
J \ 8.7 Hz, 2H, H ), 7.31 (d, J \ 8.3 Hz, 2H, H ), 7.75 (s, 2H,
(CDCl , 200.13 MHz) 2.34 (s, 6H, CH ), 3.65È3.76 (m, 8H,
m@
Ts
3
3
H
H
), 7.82 (d, J \ 8.3 Hz, 2H, H ), 8.08 (d, J \ 8.5 Hz, 2H,
CH O), 3.84 (s, 3H, OCH ), 4.00 (t, J \ 5.0 Hz, 4H, CH O),
5, 6
3, 8
Ts
4, 7
2
3
2
), 8.27 (d, J \ 8.5 Hz, 2H, H ), 8.43 (d, J \ 8.7 Hz, 4H,
4.14 (t, J \ 5.0 Hz, 4H, CH O), 6.59 (t, J \ 2.3 Hz, 1H), 7.11
2
H ). 13C NMR (CDCl , 50.32 MHz) 21.6 (CH ), 61.8, 67.5,
(d, J \ 2.3 Hz, 2H), 7.25 (d, J \ 8.2 Hz, 4H), 7.72 (d, J \ 8.2
o
3
3
69.0, 69.4, 69.7, 69.9, 72.7 (all CH O), 114.9 (CH ), 119.4,
Hz, 4H). FAB-MS: m/z found 652.1 ([M]`), calcd for
2
m
125.7, 127.6, 128.0, 129.1, 129.9, 132.4, 133.0, 136.9, 144.9,
C H O S , 652.1.
30 36 12 2
145.9, 156.2, 160.0. FAB-MS: m/z found 695.1 ([M ] H]`),
calcd for C
H
N O S, 695.2.
39 38
2 8
Macrocycle 6. To a vigourously stirred degassed suspension
of Cs CO (3.80 g, 11.6 mmol) in DMF (150 mL) at 50 ¡C was
2
3
added a DMF (50 mL) solution of 5 (880 mg, 1.34 mmol) and
1 (490 mg, 1.34 mmol) over a period of 1 h under argon. The
temperature of the reaction mixture was then raised to 100 ¡C
and these conditions were maintained for 1 day. The warm
suspension was Ðltered and the solid residue was washed with
DMF (100 mL), then the combined solutions were stripped of
solvent in vacuo. The white solid residue was subjected to
column chromatography (SiO , 20 : 1 CH Cl ÈEtOAc), which
2,9 -Bis(4 -{2 -[2 - iodoethoxy(ethoxy)]}phenyl)-1,10-phenan -
throline (4). The ditosylate 3 (552 mg, 0.65 mmol) was dis-
solved in acetone (40 mL) and NaI (230 mg, 1.5 mmol) was
added as a solid. The resulting mixture was heated at reÑux
with stirring under a silica gel guard tube for 2 h, when a
second portion of solid NaI (420 mg, 2.8 mmol) was added to
the turbid mixture. After a further 4 h at reÑux, the solvent
was evaporated in vacuo, and the residue was partitioned
between CH Cl (50 mL) and H O (50 mL). The separated
2
2 2
a†orded two main products in pure form.
The functionalised macrocycle 6 (320 mg, 36%). White
2
2
2
organic layer was washed once more with H O (50 mL) and
solid. 1H NMR (CDCl , 200.13 MHz) 3.83 (s, 3H, OMe),
2
3
was then dried (MgSO ), Ðltered, and stripped of solvent. The
3.90È4.00 (m, 8H, CH O), 4.21 (t, J \ 5.0 Hz, 4H), 4.34 (t,
4
2
diiodide was puriÐed by column chromatography (SiO ,
J \ 5.0 Hz, 4H), 6.85 (t, J \ 2.3 Hz, 1H, H of Ar bearing 2
2
CHCl ), which gave the product (474 mg, 97%).
3
2
OÏs), 7.16 (d, J \ 8.8 Hz, 4H, H ), 7.23 (d, J \ 2.3 Hz, 2H,
m
Yellow oil, which solidiÐed upon standing. 1H NMR
H
of Ar bearing 2 OÏs), 7.31 (s, 2H, H ), 8.06 (d, J \ 8.5
4, 6
5, 6
4, 7
(CDCl , 200.13 MHz) 3.32 (t, J \ 7.0 Hz, 4H, CH I), 3.88 (t,
Hz, 2H, H ), 8.24 (d, J \ 8.5 H, 2H, H ), 8.42 (d, J \ 8.8
3
2
3, 8
J \ 7.0 Hz, 4H, CH CH I), 3.94 (t, J \ 4.9 Hz, 4H, CH O),
Hz, 4H, H ). 13C NMR (CDCl , 50.32 MHz) 52.2 (OMe), 67.8,
2
2
2
o
3
4.27 (t, J \ 4.9 Hz, 4H, CH O), 7.14 (d, J \ 8.9 Hz, 4H, H ),
67.8, 67.0, 69.6 (all CH O), 107.8 (C
of Ar bearing 2 OÏs),
2
m
2
4, 6
7.75 (s, 2H, H ), 8.09 (d, J \ 8.5 Hz, 2H, H ), 8.27 (d,
5, 6 3, 8
J \ 8.5 Hz, 2H, H ), 8.44 (d, J \ 8.9 Hz, 4H, H ). 13C NMR
4, 7
(CDCl , 50.32 MHz) 3.7 (CH I), 68.1, 69.7, 72.5 (all CH O),
108.0 (C of Ar bearing 2 OÏs), 115.5 (CH ), 119.2, 125.6, 127.5,
129.1 (CH ), 132.1, 132.7, 136.7, 146.1, 156.3, 159.9, 160.6, 168.8
(CxO). ES-MS: m/z found 673.1 ([M ] H]`), calcd for
2
m
o
o
3
2
2
115.3 (CH ), 119.7, 126.1, 128.1, 129.3 (CH ), 132.8, 137.2,
C
H
N O , 673.2.
m
o
40 37
2
8
146.5, 156.3, 160.5. FAB-MS: m/z found 760.8 ([M ] H]`),
The dimeric macrocycle 7 (21 mg, 2.3%). White solid. 1H
NMR (CDCl , 200.13 MHz) 3.88 (s, 6H, OMe), 3.90È3.99 (m,
calcd for C
H
N O I , 761.0.
32 30
2
4 2
3
404
New J. Chem., 1998, Pages 395È409

View Article Online
16H, CH O), 4.15È4.27 (m, 16H, CH O), 6.75 (t, J \ 2.3 Hz,
cooled to 0 ¡C, and, after stirring exposed to air for 10 min.
2
2
2H, H of Ar bearing 2 OÏs), 7.10 (d, J \ 8.9 Hz, 8H, H ), 7.23
H O (10 mL) was added dropwise to it, not allowing the tem-
2
m
2
(d, J \ 2.3 Hz, 4H, H
of Ar bearing 2 OÏs), 7.73 (s, 4H,
perature of the mixture to rise above 5 ¡C. The two-phase
4, 6
H
H
), 8.06 (d, J \ 8.5 Hz, 4H, H ), 8.24 (d, J \ 8.5 Hz, 4H,
mixture was further diluted with CH Cl (50 mL) and H O
5, 6
4, 7
3, 8
2
2
2
), 8.41 (d, J \ 8.9 Hz, 8H, H ). ES-MS: m/z found 1408.6
(50 mL), then Et N (5 mL) was added, causing the green
o
3
([M ] Cu]`),29 1345.4 ([M ] H]`), calcd for C
H
N O
,
organic phase to turn red. The separated organic layer was
80 73
4
16
1345.5.
extracted once again with a mixture of H O (50 mL) and
2
Et N (5 mL), then it was separated, dried over Na SO and
3
2
4
5, 10, 15 - Tris[3, 5 -di(tert - butyl)phenyl]-20 -(3,5-dimethoxy -
phenyl)porphyrin (8). Pyrrole (4.7 mL, 67.8 mmol), 3,5-di-tert-
butylbenzaldehyde (11.00 g, 50.4 mmol) and 3,5-dimethoxy-
benzaldehyde (2.90 g, 17.5 mmol) were added to propionic
acid (1 L), and the resulting solution was heated at reÑux in
air in the dark for 3 h. After cooling, the propionic acid was
evaporated from the reaction mixture in vacuo. The black
residue was partitioned between CH Cl (400 mL) and
Ðltered. The solvent was removed thoroughly in vacuo, then
the purple residue was subjected to column chromatography
(SiO , CH Cl ) to give the desired diphenolic porphyrin (607
2
2 2
mg, 93%).
Deep purple solid (mp [ 300 ¡C). 1H NMR (CDCl , 200.13
3
MHz) [2.66 (bs, 2H, NH), 1.52È1.59 (m, 54H, ButCH ), 5.05
3
(bs, 2H, OH), 6.71 (t, J \ 2.2 Hz, 1H, H of Ar bearing 2
4
OHÏs), 7.27 (d, J \ 2.2 Hz, 2H, H
of Ar bearing 2 OHÏs),
2
2
2, 6
NaHCO (5% aq, 400 mL). After two further extractions
7.77È7.82 (m, 3H, H of Ar bearing 2 ButÏs), 8.06È8.11 (m, 6H,
3
4
with NaHCO (5% aq, 400 mL), the organic layer was
dried (Na SO ), Ðltered, and applied to SiO for column
chromatography. Preliminary chromatography (SiO ,
hexaneÈtoluene, gradient elution from 5 : 1 to 2 : 1) separated
H
of Ar bearing 2 ButÏs), 8.87È8.92 (m, 6H, pyrollic CHÏs),
3
4
2, 6
8.94 (d, J \ 4.7 Hz, 2H, pyrollic CHÏs). 13C NMR (CDCl ,
2
2
3
50.32 MHz) 31.9 (CH ), 35.2 [C(CH ) ], 102.1, 115.3, 118.7,
2
3
3 3
121.1, 121.6, 121.8, 129.8, 130.0, 131.2, 131.5 (v br), 141.3,
the symmetrical tetrakis-3,5-di-tert-butylphenyl porphyrin30
(0.91 g, 5.6%) from the later-running porphyrins. This latter
mixture was subjected to further chromatographies on
144.5, 147.2 (v br), 148.9, 154.7. UV/VIS (CH Cl ) k/nm (e/mol
L~1 cm~1) 283 (15 060), 302 (15 360), 421 (540 000), 517
(19 120), 553 (9280), 592 (5590), 647 (4880). FAB-MS: m/z
2
2
alumina (hexaneÈtoluene, 5 : 1) and then SiO (hexaneÈ
found 983.3 ([M ] H]`), calcd for C
H
N O , 983.6.
2
toluene, 3 : 1), which yielded the desired pure A B dimethoxy
3
68 78
4
2
porphyrin 5,10,15-tris[3,5-di(tert-butyl)phenyl]-20-(3,5-dimeth-
oxyphenyl)porphyrin (1.52 g, 8.9%).
5, 10, 15 - Tris[3,5-di(tert - butyl)phenyl]-20 -(3, 5 - dihydroxy -
phenyl)zinc(II) porphyrin (10). A solution of Zn(OAc) Æ 2H O
(143 mg, 0.65 mmol) in MeOH (5 mL) was added dropwise
over a period of 15 min to a stirred and reÑuxing CH Cl (20
2
2
Deep purple solid (mp [ 300 ¡C). 1H NMR (CDCl , 200.13
3
MHz) [2.70 (s, 2H, NH), 1.54 [s, 54H, C(CH ) ], 3.96 (s, 6H,
3 3
2
2
OCH ), 6.89 (t, J \ 2.3 Hz, 1H, H of Ar bearing 2 OÏs), 7.43
mL) solution of the diphenolic porphyrin 9 (188 mg, 0.19
mmol), all under an atmosphere of Ar in the dark. After the
addition was complete, the solution was maintained under
these conditions for a further 3 h, after which all solvents were
removed in vacuo. The residue was partitioned between
CH Cl (50 mL) and NaHCO (aq, 5%, 50 mL) and the
3
2
(d, J \ 2.3 Hz, 2H, H
of Ar bearing 2 OÏs), 7.78È7.82 (m,
4, 6
3H), 8.05È8.11 (m, 6H), 8.85È8.91 (m, 6H), 8.95 (d, J \ 4.8 Hz,
2H). 13C NMR (CDCl , 50.32 MHz) 31.8 (CH ), 35.1
[C(CH ) ], 55.7 (OCH ), 100.2, 113.8, 118.7, 121.0, 121.4,
3
3
3 3
3
121.5, 129.7, 129.9, 131.4 (v br), 141.3, 144.6, 147.3 (v br), 148.8,
2
2
3
149.1, 158.9. UV-vis (CH Cl ) k/nm (e/mol L~1 cm~1) 283
organic layer was washed with NaHCO (aq, 5%, 50 mL) and
2
2
3
(15 030), 302 (15 340), 421 (540 000), 517 (19 100), 553 (9260),
then H O (50 mL), dried (Na SO ), Ðltered and stripped of
2
2
4
592 (5580), 647 (4870). FAB-MS: m/z found 1011.5
solvent. The resulting solid residue was subjected to column
chromatography (SiO , CH Cl ) to a†ord the pure zinc
([M ] H]`), calcd for C
H
N O , 1011.6.
70 82
4
2
2
2 2
In addition, the A B porphyrin 5,15-bis[3,5-di(tert-butyl)
2 2
porphyrin 10 (194 mg, 97%).
phenyl]-10,20-bis(3,5-dimethoxyphenyl)porphyrin was isolated
Purple solid (mp [ 300 ¡C). 1H NMR (CDCl , 200.13
3
(166 mg, 1.1%) as a purple solid (mp [ 300 ¡C). 1H NMR
MHz) 1.53È1.55 (m, 54H, ButCH ), 5.16 (bs, 2H, OH), 6.64 (t,
3
(CDCl , 200.13 MHz) [ 2.75 (s, 2H, NH), 1.54 [s, 36H,
J \ 2.2 Hz, 1H, H of Ar bearing OHÏs), 7.25 (d, J \ 2.2 Hz,
3
4
C(CH ) ], 3.97 (s, 12H, OCH ), 6.89 (t, J \ 2.3 Hz, 2H, H of
2H, H
of Ar bearing OHÏs), 7.78È7.84 (m, 3H, H of Ar
3 3
3
2
2, 6
4
Ar bearing 2 OÏs), 7.43 (d, J \ 2.3 Hz, 4H, H
of Ar bearing
bearing ButÏs), 8.09È8.13 (m, 6H, H
of Ar bearing ButÏs),
4, 6
2, 6
2 OÏs), 7.80 (t, J \ 1.8 Hz, 2H), 8.09 (d, J \ 1.8 Hz, 4H), 8.88
(d, J \ 4.8 Hz, 4H), 8.94 (d, J \ 4.8 Hz, 4H). UV-vis (CH Cl )
8.99 (d, J \ 4.7 Hz, 2H, pyrollic CHÏs), 9.03 (s, 4H, pyrollic
CHÏs), 9.05 (d, J \ 4.7 Hz, 2H, pyrollic CHÏs). 13C NMR
(CDCl , 50.32 MHz) 31.8 (CH ), 35.1 (C(CH ) ), 102.2, 115.3,
2
2
k/nm (e/mol L~1 cm~1) 283 (15 080), 302 (15 460), 421
(530 000), 517 (19 160), 553 (9360), 592 (5580), 647 (4880).
FAB-MS: m/z found 959.4 ([M ] H]`), calcd for
3
3
3 3
119.1, 120.6, 122.5, 122.9, 129.7, 129.8, 131.6, 132.2, 132.3,
141.9, 148.6, 149.7, 150.4, 150.5, 154.7. UV/VIS (CH Cl ) k/nm
(e/mol L~1 cm~1) 424 (400 000), 551 (20 700), 592 (5800).
FAB-MS: m/z found 1046.4 ([M]`), calcd for
2
2
C
H
N O , 959.5.
64 70
4 4
Also, the A B porphyrin 5,10-bis[3,5-di(tert-butyl)phenyl]-
2 2
15,20-bis(3,5-dimethoxyphenyl)porphyrin was isolated (199
C
H
N O Zn, 1046.4.
68 76
4 2
mg, 1.3%) as a purple solid (mp [ 300 ¡C). 1H NMR (CDCl ,
3
200.13 MHz) [2.73 (s, 2H, NH), 1.54 [s, 36H, C(CH ) ], 3.97
3 3
5, 10, 15 -Tris[3, 5-di(tert-butyl)phenyl]-20- (3, 5 -dimethoxy -
(s, 12H, OCH ), 6.91 (t, J \ 2.3 Hz, 2H, H of Ar bearing 2
phenyl)porphyrinatoaurate hexaÑuorophosphate (11). The
3
2
OÏs), 7.43 (d, J \ 2.3 Hz, 4H, H
of Ar bearing 2 OÏs), 7.81 (t,
dimethoxy porphyrin 8 (20 mg, 0.02 mmol), KAuCl (15 mg,
4, 6
4
J \ 1.8 Hz, 2H), 8.09 (d, J \ 1.8 Hz, 4H), 8.88È9.00 (m, 8H).
FAB-MS: m/z found 959.4 ([M ] H]`), calcd for
0.04 mmol) and NaOAc (11 mg, 0.13 mmol) were combined as
solids in a small pear-shaped Ñask. Immediately after the addi-
C
H
N O , 959.5.
tion of CH COOH (2.5 mL), the suspension was Ñushed with
64 70
4
4
3
argon and the vessel was Ðtted with a condenser. The appar-
5,10,15-Tris[3,5-di(tert-butyl)phenyl] -20-(3,5-dihydroxy-
atus was plunged into an oil bath, which had been preheated
to 160 ¡C, and the mixture was then reÑuxed under argon with
vigourous stirring for 2 h. After cooling slightly, the solvent
was removed in vacuo and the residue was partitioned
between CH Cl (30 mL) and NaHCO (aq, 5%, 20 mL). The
phenyl)porphyrin (9). The dimethoxy porphyrin 8 (668 mg,
0.66 mmol) in dry CH Cl (50 mL) was added dropwise over
2
2
30 min to a stirred CH Cl solution of BBr (1 M, 3.0 mL) at
2
2
3
[78 ¡C under an atmosphere of argon. The resulting deep
green solution was maintained under the same conditions for
3 h and then allowed to warm slowly to room temperature,
after which it was stirred for 20 h. The mixture was then
2
2
3
separated organic layer was washed again with NaHCO (aq,
3
5%, 20 mL) and was then stirred for 16 h with KPF (aq,
6
saturated, 5 mL). The organic layer was separated, washed
New J. Chem., 1998, Pages 395È409
405

View Article Online
with H O (30 mL), dried (Na SO ), Ðltered and stripped of
Purple solid (mp [ 300 ¡C). 1H NMR (CDCl , 200.13
2
2
4
3
solvent. The resulting solid residue was subjected to column
chromatography (SiO ) using CH Cl as eluent to elute the
MHz) 1.54 (s, 54H, CH ), 3.99 (bt, J \ 5.1 Hz, 8H, CH O),
3
2
4.34 (bt, J \ 5.1 Hz, 4H, CH O), 4.42 (t, J \ 5.1 Hz, 4H,
2
2
2
2
starting free base porphyrin (3.0 mg, 15% was recovered) and
CH O), 7.11 (t, J \ 2.3 Hz, 1H, H of Ar bearing OÏs), 7.26 (d,
2
2
then 1% MeOH in CH Cl to elute 11 as its hexa-
J \ 8.8 Hz, 4H, H ), 7.47 (d, J \ 2.3 Hz, 2H, H
of Ar
2
2
m
4, 6
2
Ñuorophosphate salt (21.4 mg, 80%).
bearing OÏs), 7.76 (s, 2H, H ), 7.78È7.81 (m, 3H, H of Ar
5, 6
Purple solid (mp [ 300 ¡C). 1H NMR (CD Cl , 200.13
bearing ButÏs), 8.06È8.14 (m, 6H, H
and H
of Ar bearing
2
2
3, 8
4, 7
4, 6
MHz) 1.55 (s, 54H, ButCH ), 3.99 (s, 6H, OMe), 7.02 (t, J \ 2.2
ButÏs), 8.28 (d, J \ 8.4 Hz, 2H, H ), 8.49 (d, J \ 8.8 Hz, 4H,
3
Hz, 1H, H of Ar bearing OMeÏs), 7.40 (d, J \ 2.2 Hz, 2H,
H ), 3.97 (d, J \ 4.7 Hz, 2H, pyrrollic CH), 9.01 (s, 4H, pyrrol-
4
o
H
of Ar bearing OMeÏs), 7.96È8.01 (m, 3H, H of Ar
lic CH), 9.06 (d, J \ 4.7 Hz, 2H, pyrrollic CH); (CD Cl ,
2, 6
4
2 2
bearing ButÏs), 8.08 (d, J \ 1.7 Hz, 6H, H
of Ar bearing
200.13 MHz) 1.51 (s, 36H, CH ), 1.53 (s, 18H, CH ), 3.94È4.02
2, 6
3
3
ButÏs), 9.30È9.39 (m, 6H, pyrrollic CHÏs), 9.45 (d, J \ 5.3 Hz,
2H, pyrrollic CHÏs); (CD CN, 200.13 MHz) 1.53 (s, 54H,
(m, 8H, CH O), 4.30È4.44 (m, 8H, CH O), 7.08 (t, J \ 2.3 Hz,
2
2
1H, H of Ar bearing OÏs), 7.24 (d, J \ 8.8 Hz, 4H, H ), 7.44
3
2
m
of Ar bearing OÏs), 7.79 (s, 2H, H ),
4, 6 5, 6
ButCH ), 3.95 (s, 6H, OMe), 7.03 (t, J \ 2.2 Hz, 1H, H of Ar
(d, J \ 2.3 Hz, 2H, H
3
4
bearing OMeÏs), 7.42 (d, J \ 2.2 Hz, 2H, H
of Ar bearing
7.80È7.85 (m, 3H, H of Ar bearing ButÏs), 8.06È8.14 (m, 6H,
2, 6
2
OMeÏs), 8.00È8.06 (m, 3H, H of Ar bearing ButÏs), 8.12 (d,
H
H
and H
of Ar bearing ButÏs), 8.31 (d, J \ 8.4 Hz, 2H,
4
3, 8
4, 7
4, 6
J \ 1.7 Hz, 6H, H
of Ar bearing ButÏs), 9.27È9.33 (m, 6H,
), 8.46 (d, J \ 8.8 Hz, 4H, H ), 8.95 (d, J \ 4.7 Hz, 2H,
2, 6
o
pyrrolic CHÏs), 9.42 (d, J \ 5.3 Hz, 2H, pyrrollic CHÏs). 13C
pyrrollic CH), 8.99 (s, 4H, pyrrollic CH), 9.05 (d, J \ 4.7 Hz,
2H, pyrrollic CH). 13C NMR (CD Cl , 50.32 MHz) 31.9 (Me),
NMR (CD CN, 50.32 MHz) 31.8 (CH ), 35.5 (C(CH ) ), 56.2
3
3
3 3
2 2
(OCH ), 101.3, 114.3, 123.2, 123.7, 125.4, 129.8, 132.6, 132.8,
132.9, 137.2, 137.6, 137.7, 138.2, 141.2, 150.7, 160.3. UV/VIS
35.4 (CMe ), 68.2, 69.9, 70.3 (all CH O), 102.4, 114.3, 115.9,
3
3
2
119.5, 120.8, 121.5, 122.8, 123.0, 126.0, 127.9, 129.4, 130.1,
132.2, 132.5, 132.6, 133.2, 137.0, 142.3, 145.4, 146.5, 149.2,
150.3, 150.8, 150.9, 156.4, 158.5, 160.5. UV/VIS (CH Cl ) k/nm
(CH Cl ) k/nm (e/mol L~1 cm~1) 303 (14 100), 416 (270 000),
2
2
524 (18 100). FAB-MS: m/z found 1205.5 ([M [ PF ]`), calcd
6
2 2
for C
H
N O Au, 1205.6.
(e/mol L~1 cm~1) 285 (59 000), 424 (280 000), 551 (20 300), 593
70 80
4 2
(5700). FAB-MS: m/z found 1550.7 ([M ] 2H]`), calcd for
Macrocycle bearing a 5,10,15-tris[3,5-di(tert-butyl)phenyl]-
20-(3,5-dioxyphenyl)porphyrin (12). A vigourously stirred sus-
pension of Cs CO (850 mg, 2.61 mmol) in DMF (100 mL)
C
H
N O Zn, 1550.4.
100 104
6 6
Macrocycle bearing a 5,10,15-tris[3,5-di(tert-butyl)phenyl]-
2
3
was degassed with a Ñow of Ar for 15 min and then heated to
100 ¡C. A similarly degassed solution of 9 (428 mg, 0.44 mmol)
and 3 (370 mg, 0.44 mmol) in DMF (100 mL) was added drop-
wise over a period of 2.5 h to the hot suspension under an
atmosphere of Ar. The mixture was then stirred at 100 ¡C for 4
days. The crude mixture was Ðltered at the pump and the
solid was washed with DMF (50 mL). After removal of solvent
in vacuo, the solid residue was washed with water (3 ] 100
mL), Ðltered, dissolved in CH Cl (200 mL), dried over
20-(3,5-dioxyphenyl)porphyrinatoaurate hexaÑuorophosphate
(14). The macrocycle bearing the free base porphyrin (12) (184
mg, 0.123 mmol) was reacted with KAuCl (90 mg, 0.238
4
mmol), and NaOAc (70 mg, 0.853 mmol) in vigourously
reÑuxing CH COOH (3 mL) as described for 11, except that
3
the reaction period was extended to 12 h. After work-up as
described for the gold(III) porphyrin 11 above, the resulting
solid was subjected to column chromatography (SiO ) using
2
0.5% MeOH in CH Cl as eluent. The product was isolated
2
2
Na SO , Ðltered, concentrated and subjected to column chro-
2
2
pure (206 mg, 91%).
Deep red solid (mp [ 300 ¡C). 1H NMR (CD Cl , 200.13
MHz) 1.53 (s, 54H, CH ), 3.95È4.07 (bm, 8H, CH O), 4.34È
2
4
matography (SiO , CH Cl ), which a†orded 305 mg of pure
2
2 2
product (47%).
2
2
Deep purple solid (mp [ 300 ¡C). 1H NMR (CDCl , 200.13
3
2
4.48 (bm, 8H, CH O), 7.14È7.25 (m, 7H, H of Ar bearing OÏs,
3
MHz) [2.74 (bs, 2H, NH), 1.49 (s, 54H, CH ), 3.96 (t, J \ 5.4
3
2
2
H , H ), 7.52 (d, J \ 2.3 Hz, 2H, H
5, 6 4, 6
7.82 (bs, 4H, H , H ), 7.96 (t, J \ 1.7 Hz, 2H, H Ïs of Ar
of Ar bearing OÏs),
Hz, 8H, CH O), 4.31 (bt, J \ 5.4 Hz, 4H, CH O), 4.39 (t,
m
2
2
J \ 5.1 Hz, 4H, CH O), 7.08 (t, J \ 2.3 Hz, 1H, H of Ar
3, 8
4, 7
2
bearing ButÏs), 7.99È8.03 (m, 5H, H and H Ïs of Ar bearing
2
2
bearing OÏs), 7.22 (d, J \ 8.9 Hz, 4H, H ), 7.42 (d, J \ 2.3 Hz,
2
4, 6
4, 6
ButÏs), 8.10 (d, J \ 1.7 Hz, 2H, H
of Ar bearing ButÏs), 8.20
m
2H, H
of Ar bearing OÏs), 7.71 (s, 2H, H ), 7.74È7.78 (m,
(d, J \ 8.8 Hz, 4H, H ), 9.15 (d, J \ 5.2 Hz, 2H, pyrrolics),
4, 6
2
5, 6
3H, H of Ar bearing ButÏs), 8.04 (d, J \ 8.4 Hz, 2H, H ),
o
9.28 (d, J \ 5.2 Hz, 2H, pyrrolics), 9.31 (d, J \ 5.2 Hz, 2H,
3, 8
8.05 (d, J \ 1.8 Hz, 6H, H
of Ar bearing ButÏs), 8.22 (d,
pyrrolics), 9.34 (d, J \ 5.2 Hz, 2H, pyrrolics). Note: The
4, 6
J \ 8.4 Hz, 2H, H ), 8.45 (d, J \ 8.9 Hz, 4H, H ), 8.83 (d,
spectra in CD CN show a very marked concentration and
4, 7
o
J \ 4.8 Hz, 2H, pyrrollic CH), 8.87 (s, 4H, pyrrollic CH), 8.92
3
temperature dependence, see Results and Discussion. 13C
(d, J \ 4.8 Hz, 2H, pyrrollic CH). 13C NMR (CDCl , 50.32
NMR (CD Cl , 50.32 MHz) 31.8 (Me), 35.5 (CMe ), 68.5,
3
MHz) 31.9 (Me), 35.2 (CMe ), 67.8, 69.6, 70.2 (all CH O),
2
2
3
69.0, 70.4 (all CH O), 103.2, 115.8, 116.0, 118.1, 118.9, 123.6,
3
2
102.7, 114.2, 115.6, 119.2, 119.4, 121.1, 121.5, 121.7, 125.6,
127.5, 129.2, 129.8, 129.9, 131.5 (v br), 132.8, 136.7, 141.4,
144.4, 146.1, 147.0 (v br), 148.8, 156.4, 158.2, 160.1. UV/VIS
(CH Cl ) k/nm (e/mol L~1 cm~1) 285 (63 000), 323 (38 000),
2
125.0, 127.0, 129.3, 129.7, 132.7, 136.2, 137.0, 137.4, 138.3,
141.0, 145.2, 150.7, 153.7, 156.0, 159.7, 160.7; (CD CN, 50.32
3
MHz) 32.0 (Me), 36.0 (CMe ), 69.0, 69.5, 70.8, 71.0 (all CH O),
3
2
102.5, 116.3, 122.8, 124.1, 125.0, 129.2, 130.2, 130.6, 131.8,
132.4, 132.9, 133.5, 135.0, 136.9, 137.0, 138.8, 141.0, 151.3,
154.5, 160.6, 161.4. UV/VIS (CH Cl ) k/nm (e/mol L~1 cm~1)
2
2
421 (540 000), 517 (18 330), 553 (9000), 592 (5500), 647 (4830).
FAB-MS: m/z found 1488.8 ([M ] 2H]`), calcd for
C
H
N O , 1486.8.
2
2
285 (61 800), 323 (38 800), 416 (280 200), 525 (18 300).
100 106
6 6
FAB-MS: m/z found 1682.6 ([M [ PF ] H]`), calcd for
Macrocycle bearing a 5,10,15-tris[3,5-di(tert-butyl)phenyl]-
6
C
H
N O Au, 1682.7.
20-(3,5-dioxyphenyl)zinc(II) porphyrin (13). Using a procedure
exactly the same as for the preparation of 10, a solution of the
free base porphyrin appended to a macrocycle (12) (85 mg,
100 105
6 6
Copper(I) [2]catenate, 18, bearing two zinc(II) porphyrins.
Method A. 3 (117 mg, 0.138 mmol) and Cu(MeCN) PF (25.6
0.06 mmol) in CH Cl
(20 mL) was treated with
2
2
4
6
Zn(OAc) Æ 2H O (50 mg, 0.22 mmol) in MeOH (5 mL) under
mg, 0.069 mmol) were combined as solids in a Schlenk Ñask
under an atmosphere of Ar and degassed DMF (50 mL) was
added through a double-ended needle, causing instantaneous
formation of a red complex (15). The resulting solution was
stirred at room temperature for 30 min. Meanwhile, to a
2
2
an inert atmosphere. After work-up as described above, the
solid residue was subjected to column chromatography (SiO ,
2
1% MeOH in CH Cl ), from which the product was isolated
(87 mg, 98%).
2
2
406
New J. Chem., 1998, Pages 395È409

View Article Online
degassed suspension of Cs CO (221 mg, 0.678 mmol) in
CH O), 4.42È4.50 (m, 8H, CH O), 6.18 (d, J \ 8.6 Hz, 8H,
2
3
2
2
DMF (50 mL), 10 (144 mg, 138 mmol) was added and the
resulting mixture was heated to 60 ¡C under Ar, resulting in a
green suspension to which four crystals of KI were added. The
solution of entwined CuI complex was added to the basic sus-
pension over 30 min and the resulting suspension was left
under these conditions for 2 days. The warm reaction mixture
was Ðltered at the pump and the solid residue was washed
with DMF (50 mL). Removal of the solvent a†orded a metal-
lic solid that was partitioned between CH Cl (30 mL) and
H ), 7.23 (t, J \ 2.1 Hz, 2H, H of Ar bearing OÏs), 7.40 (d,
m
2
J \ 8.6 Hz, 8H, H ), 7.57 (d, J \ 2.1 Hz, 4H, H
of Ar
o
4, 6
bearing OÏs), 7.80 (t, J \ 1.7 Hz, 4H, H Ïs of Ar bearing ButÏs),
2
7.84 (t, J \ 1.7 Hz, 2H, H Ïs of Ar bearing ButÏs), 7.93 (d,
2
J \ 8.3 Hz, 4H, H ), 8.05È8.10 (m, 12H, H Ïs of Ar bearing
3, 8
4, 6
ButÏs), 8.27 (s, 4H, H ), 8.77 (d, J \ 8.3 Hz, 4H, H ), 8.86
5, 6
4, 7
(d, J \ 4.8 Hz, 4H, pyrrollic CH), 8.90 (s, 8H, pyrrollic CH),
8.94 (d, J \ 4.8 Hz, 4H, pyrrollic CH). UV/VIS (CH Cl )
2
2
k/nm (e/mol L~1 cm~1) 283 (71 000), 323 (62 800), 421
(1 300 000), 517 (33 400), 553 (18 500), 592 (13 400), 647 (9080).
ES-MS: m/z found 3036.9 [M [ PF ]`, 1518.7 [M [ PF
2
2
KPF (aq satd, 10 mL), and this mixture was stirred for 1 h.
6
DMF (30 mL) and H O (200 mL) were added, causing pre-
cipitation of a purple solid, which was collected by Ðltration
2
6
6
for
] Cu]2`,
1013.1
[M [ PF ] 2H]3`,
calcd
6
under gravity. This solid was dissolved in CH Cl (100 mL),
C
H
N
O
Cu, 3036.8.
2
2
200 212 12 12
dried (Na SO ), Ðltered and concentrated. Repeated column
2
4
chromatography (SiO , CH Cl ) a†orded 15 mg (7%) of the
component macrocycle 13 and the pure [2]catenate (32 mg,
Copper(I) [2]catenate, 20, bearing one zinc(II) porphyrin and
2
2 2
one ester. The macrocycle with the appended ester 6 (64 mg,
96 lmol) was mixed with Cu(MeCN) PF (38 mg, 102 lmol)
14%).
4
6
Deep purple solid (mp [ 300 ¡C). 1H NMR (CD Cl ,
in a Schlenk Ñask under an atmosphere of Ar, and dry
degassed DMF (30 mL) was added. After stirring the resulting
pale red solution for 30 min, 4 (73 mg, 96 lmol) was added as
a solid, and the resulting deep red solution was stirred for 30
min. Meanwhile, 10 (100 mg, 96 lmol) was dissolved in DMF
(30 mL) and the solution was degassed, and then combined
with the solution of the copper(I) complex. This mixture was
added over a period of 4 h to a suspension of Cs CO (98 mg,
2
2
200.13 MHz) 1.46 (s, 108H, CH ), 3.75È3.90 (m, 16H, CH O),
3
2
3.96È4.07 (m, 8H, CH O), 4.38È4.49 (m, 8H, CH O), 6.16 (d,
2
2
J \ 8.7 Hz, 8H, H ), 7.24 (t, J \ 2.3 Hz, 2H, H Ïs of Ar
m
2
bearing OÏs), 7.39 (d, J \ 8.7 Hz, 8H, H ), 7.24 (t, J \ 2.3 Hz,
m
2H, H Ïs of Ar bearing OÏs), 7.39 (d, J \ 8.7 Hz, 8H, H ), 7.24
2
m
(t, J \ 2.3 Hz, 2H, H Ïs of Ar bearing OÏs), 7.39 (d, J \ 8.7 Hz,
2
8H, H ), 7.56 (d, J \ 2.3 Hz, 4H, H Ïs of Ar bearing OÏs),
o
4, 6
2
3
7.79 (t, J \ 1.7 Hz, 4H, H Ïs of Ar bearing ButÏs), 7.79 (t,
300 lmol) in DMF (100 mL) maintained at 40 ¡C under Ar in
the dark. The mixture was maintained under these conditions
for 2 days, and then at 50 ¡C for another day. The Ðltered
reaction mixture was stripped of solvent while still warm,
leaving a metallic solid that was washed with water (2 ] 50
mL) and Ðltered. The solid was taken up in CH Cl (30 mL)
2
J \ 1.7 Hz, 2H, H Ïs of Ar bearing ButÏs, 7.94 (d, J \ 8.3 Hz,
2
4H, H ), 8.01È8.09 (m, 12H, H Ïs of Ar bearing ButÏs), 8.28
3, 8
4, 6
(s, 4H, H ), 8.77 (d, J \ 8.3 Hz, 4H, H ), 8.91 (d, J \ 4.7
5, 6
4, 7
Hz, 4H, pyrrolics), 8.96 (s, 8H, pyrrolics), 9.01 (d, J \ 4.7 Hz,
4H, pyrrolics). UV/VIS (CH Cl ) k/nm (e/mol L~1 cm~1) 423
2
2
2 2
(480 000), 552 (42 000), 594 (12 000). FAB-MS: m/z found
and stirred overnight with KPF (aq, satd., 30 mL). The
6
3165.5 [M [ PF ]`, 1614.3 [component macrocycle ] Cu]`,
organic layer was dried over Na SO , Ðltered and the solu-
6
2
4
calcd. for C
H
N
O
Zn Cu, 3164.6.
tion concentrated. Column chromatography (SiO , CH Cl
200 208 12 12
2
2
2 2
Method B. The macrocycle 13 with the appended zinc(II)
porphyrin (53 mg, 34.2 lmol) in dry degassed CH Cl (30 mL)
was combined with a solution of Cu(MeCN) PF (13.1 mg,
then 0.1% MeOH in CH Cl ) a†orded three main products:
2
2
15 mg (10%) of the component porphyrin-bearing macrocycle
13, 25 mg (16%) of the pure bis-zinc(II) porphyrin [2]catenate
18, and 63 mg (27%) of the desired pure [2]catenate.
Deep purple solid (mp [ 300 ¡C). 1H NMR (CD Cl ,
200.13 MHz) 1.48 [s, 36H, C(CH ) ], 1.53 [s, 18H, C(CH ) ],
3.75È3.88 (m, 16H, CH O), 3.91 (s, 3H, OCH ), 3.98È4.11 (m,
4H, CH O), 4.30È4.38 (m, 8H, CH O), 6.04È6.20 (m, 8H, H
2
2
4
6
35.1 lmol) in degassed MeCN (50 mL) in a Schlenk Ñask
under an atmosphere of Ar to form the intermediate complex
16. After stirring for 30 min, 4 (26.0 mg, 34.2 lmol) in MeCN
(30 mL) was transferred into it under argon using the double-
ended needle technique, and the resulting solution was stirred
for 2 h. Removal of the solvent a†orded the entwined complex
17 (by TLC and 1H NMR), which was subsequently
redissolved in DMF (50 mL) along with 10 (35.8 mg, 34.2
lmol); this solution was added over a period of 2 h to a
degassed suspension of Cs CO (80 mg, 245 lmol) in DMF
(50 mL) maintained at 50 ¡C under Ar in the dark. The
resulting mixture was maintained under the same conditions
for 4 days. Following a work-up procedure identical to that
described in Method A, the catenate was isolated in 33% yield
(37.7 mg), giving analytical data identical to that for the
product of the previous method.
2
2
3 3
3 3
2
3
2
2
m
of both rings), 7.02 (t, J \ 2.3 Hz, 1H, H Ïs of Ar bearing OÏs
2
in ester ring), 7.22 (t, J \ 2.3 Hz, 1H, H Ïs of Ar bearing OÏs in
2
o
porphyrin ring), 7.26È7.38 (m, 10H, H Ïs from both rings and
H
H
H
Ïs of Ar bearing OÏs in ester ring), 7.54 (d, J \ 2.3 Hz, 2H,
Ïs of Ar bearing OÏs in porphyrin ring), 7.72È7.82 (m, 4H,
and H Ïs of Ar bearing ButÏs), 7.83 (t, J \ 1.7 Hz, 1H, H
4, 6
4, 6
3, 8
2
3
2
2
in porphy-
from ester ring and H Ïs of
of Ar bearing ButÏs), 7.88 (d, J \ 8.3 Hz, 2H, H
3, 8
rin ring), 8.04È8.13 (m, 8H, H
5, 6
Ar bearing ButÏs), 8.24 (s, 2H, H
5, 6
4, 6
from porphyrin ring), 8.56
(d, J \ 8.3 Hz, 2H, H
4, 7
from ester ring), 8.73 (d, J \ 8.3 Hz,
2H, H
from porphyrin ring), 8.89 (d, J \ 4.7 Hz, 2H,
4, 7
pyrrolics), 8.93 (s, 4H, pyrrolics), 8.98 (d, J \ 4.7 Hz, 2H,
pyrrolics). UV/VIS (CH Cl ) k/nm (e/mol L~1 cm~1) 285
Copper(I) [2]catenate, 19, bearing two free base porphyrins.
2
2
A solution of triÑuoroacetic acid (0.2 mL) in CH Cl (10 mL)
(112 000), 424 (290 000), 551 (20 200), 593 (5600). ES-MS: m/z
2
2
was added to the catenate 18 with two appended zinc(II)
porphyrins (30 mg, 9 lmol), and the resulting green solution
was stirred at ambient temperature for 30 min. Addition of
H O (40 mL), CH Cl (10 mL) and Et N (2 mL) resulted in a
found 2286.6 [M [ PF ]`, calcd for C
H
N O ZnCu,
6
140 142
8
14
2287.6.
Precatenate 21. A solution of the macrocycle bearing the
appended gold(III) porphyrin 14 (44.8 mg, 0.24.5 lmol) in
MeCN (30 mL) was degassed under Ar, then Cu(MeCN) PF
2
2
2
3
biphasic system in which the organic layer was red. This
organic phase was washed with H OÈEt N (50 : 1, 50 mL),
2
3
4
6
and was stirred overnight with KPF (aq, satd., 10 mL). The
(9.13 mg, 25.0 lmol) was added as a solid. The resulting solu-
tion was stirred for 30 min, after which a solution of 4 (18.6
mg, 24.5 lmol) in MeCN (30 mL) was transferred into it under
argon using the double-ended needle technique. The resulting
solution was stirred for a further 30 min. The solvent was
removed in vacuo at room temperature, leaving the preca-
tenate in pure form (68.5 mg, 100%). It was used in the next
6
organic phase was dried over Na SO , Ðltered and the solu-
tion concentrated. Column chromatography (SiO , CH Cl )
a†orded the pure [2]catenate (24 mg, 83%).
2
4
2
2 2
Deep purple solid (mp [ 300 ¡C). 1H NMR (CD Cl ,
2
2
200.13 MHz) [2.78 (bs, 4H, NH), 1.48 (s, 72H, CH ), 1.52 (s,
3
36H, CH ), 3.79È3.90 (m, 16H, CH O), 4.02È4.07 (m, 8H,
3
2
New J. Chem., 1998, Pages 395È409
407

View Article Online
step without further puriÐcation.
[2]Catenand 23 bearing two free base porphyrins. To a solu-
tion of the free base porphyrin catenate 19 (15.0 mg, 4.7 lmol)
in CH Cl (10 mL) was added an aqueous solution (10 mL) of
Deep purple solid. 1H NMR (CD Cl , 200.13 MHz) 1.37 (s,
2
2
36H, CH ), 1.51 (s, 18H, CH ), 3.13 (t, J \ 6.2 Hz, 4H, CH I),
3
3
2
2 2
3.47È3.54 (m, 12H, CH O), 3.58È3.66 (m, 8H, CH O), 3.94È
KCN (20 mg, 3077 lmol) and the mixture was stirred vigour-
ously for 16 h at room temperature in the dark. Additional
KCN (20 mg, 3077 lmol) was added to the mixture, which
was stirred for a further 2 days. Water (20 mL) and CH Cl
2
2
4.03 (m, 4H), 4.48È4.57 (m, 4H, CH O), 5.97È6.07 (m, 8H, H ),
2
m
7.26 (d, J \ 8.6 Hz, 4H, H ), 7.43 (t, J \ 2.1 Hz, 1H, H of Ar
o
2
bearing OÏs), 7.48 (d, J \ 8.6 Hz, 4H, H ), 7.57 (d, J \ 2.1 Hz,
o
2 2
2H, H Ïs of Ar bearing OÏs), 7.79È7.87 (m, 4H, H
and
(10 mL) were added, the organic layer was separated, dried
over Na SO , Ðltered and the solvent was removed, leaving
4, 6
3, 8
H Ïs of Ar bearing ButÏs), 7.91 (d, J \ 8.4 Hz, 2H, H ), 8.00È
2
3, 8
2
4
8.04 (m, 5H, H Ïs and H Ïs of Ar bearing ButÏs), 8.08È8.15
4, 6
the desired catenand (13.1 mg, 93%).
2
(m, 4H, H Ïs of Ar bearing ButÏs and H ), 8.21 (s, 2H,
Purple solid. 1H NMR (CD Cl , 400 MHz) [ 3.18 (bs, 4H,
4, 6
5, 6
2 2
H
H
), 8.60 (d, J \ 8.4 Hz, 2H, H ), 8.66 (d, J \ 8.4 Hz, 2H,
NH), 1.51 (s, 72H, CH ), 1.56 (s, 36H, CH ), 3.72È3.83 (m, 8H,
5, 6
4, 7
4, 7
3
3
), 9.06 (d, J \ 5.4 Hz, 4H, pyrrollics), 9.21 (d, J \ 5.4 Hz,
CH O), 3.88È3.97 (m, 8H, CH O), 4.20È4.33 (m, 8H, CH O),
2
2
2
4H, pyrrollics), 9.24 (d, J \ 5.3 Hz, 4H, pyrrolics), 9.27 (d,
4.35È4.43 (m, 8H, CH O), 6.01 (s, 4H, H ), 7.11 (d, J \ 8.8
5, 6
2
4, 7
J \ 5.3 Hz, 4H, pyrrollics).
Hz, 4H, H
or H ), 7.16 (d, J \ 6.2 Hz, 8H, H ), 7.24 (t,
3, 8
m
J \ 2.4 Hz, 2H, H of Ar bearing OÏs), 7.52 (d, J \ 8.8 Hz, 4H,
2
H
or H ), 7.56 (d, J \ 2.4 Hz, 4H, H
of Ar bearing
3, 8
4, 7
4, 6
Copper(I) catenate, 22, bearing one zinc(II) porphyrin and
one gold(III) porphyrin. The precatenate 21 prepared in the
previous step (68.5 mg, 24.5 lmol) and 10 (25.7 mg, 24.6 lmol)
were dissolved in degassed DMF and the temperature was
raised to 45 ¡C with stirring under an atmosphere of Ar.
Cs CO (5 mg, 15.3 lmol) was added to the solution as a solid
OÏs), 7.67È7.73 (m, 4H, H Ïs of Ar bearing ButÏs), 7.81È7.84 (m,
2
4H, H Ïs of Ar bearing ButÏs), 7.87 (t, J \ 1.8 Hz, 4H, H of
4, 6
2
Ar bearing ButÏs), 8.07È8.13 (m, 8H, H Ïs of Ar bearing
4, 6
ButÏs), 8.57È8.65 (m, 8H, H ), 8.88È8.97 (m, 16H, pyrrollic CH).
o
UV/VIS (CH Cl ) k/nm (e/mol L~1 cm~1) 284 (216 600), 423
2
2
(1 300 000), 519 (33 600), 554 (19 100), 593 (11 900), 648 (8900).
2
3
and the temperature was raised to 60 ¡C. After 30 min, an
additional identical portion of Cs CO was introduced, and
ES-MS: m/z found 1488.4 [M ] 2H]2`, 992.3 [M ] 3H]3`,
calcd for C
H
N
O
, 1487.8.
2
3
200 214 12 12
this procedure was repeated another 5 times. After 16 h more
Cs CO (10 mg, 30.6 lmol) was added and the reaction was
2
3
Acknowledgements
maintained for 24 h. Following a work-up procedure identical
to that described for the catenate 18 (Method A), column
chromatography (SiO , 1% MeOH in CH Cl ) a†orded four
This work was supported by the CNRS in France. DBA was
funded by The Royal Society (London, UK) and the Commis-
sion of the European Union, who both provided postdoctoral
fellowships. We warmly thank Dr. Christiane O. Dietrich-
Buchecker for her kind support, Mr. Patrice Staub for the
preparation of 3,5-di-tert-butylbenzaldehyde, Dr. Fabrice
Odobel for valuable advice, Drs Emmanuelle Leize and Alain
van Dorsselear for ES-MS measurements, and Jean-Daniel
Sauer and Michelle Martigneaux for recording NMR spectra.
2
2 2
main products. In order of elution from the column these were
the zinc(II) porphyrin macrocycle 13 (6.0 mg, 16%), the start-
ing gold(III) porphyrin macrocycle 14 (13 mg, 29%), the bis-
zinc(II) porphyrin catenate 18 (5.9 mg, 15%), all of which had
analytical data identical to those prepared using direct routes,
and Ðnally, the desired catenate 22 with appended zinc(II) and
gold(III) porphyrins (14 mg, 16%) as its bishexaÑuorophosp-
hate salt.
Purple solid, mp [ 300 ¡C. 1H NMR (CD Cl , 200.13
2
2
MHz) 1.49 (s, 36H, CH ), 1.50 (s, 36H, CH ), 1.52 (s, 18H,
References
3
3
CH ), 1.54 (s, 18H, CH ), 3.77È3.92 (m, 16H, CH O), 3.98È4.08
3
3
2
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(m, 8H, CH O), 4.40È4.50 (m, 8H, CH O), 6.18 (d, J \ 8.6 Hz,
2
2
8H, H Ïs), 7.26 (t, J \ 2.3 Hz, 1H, H of Ar bearing OÏs in ZnII
m
2
porphyrin), 7.32 (t, J \ 2.3 Hz, 1H, H of Ar bearing OÏs in
2
AuIII porphyrin), 7.41 (d, J \ 8.6 Hz, 8H, H Ïs), 7.56 (d, J \ 2.3
o
Hz, 4H, H Ïs of Ar bearing OÏs in both porphyrins), 7.80 (t,
4, 6
J \ 1.7 Hz, 2H, H Ïs of Ar bearing ButÏs in ZnII porphyrin),
2
7.84 (t, J \ 1.7 Hz, 1H, H of Ar bearing ButÏs in ZnII
2
porphyrin), 7.92È8.02 (m, 7H, H
of each macrocycle and
3, 8
H Ïs of Ar bearing ButÏs in AuIII porphyrin), 8.05È8.12 (m,
2
12H, H Ïs of Ar bearing ButÏs in both porphyrins), 8.29 (s,
4, 6
5, 6
2H, H
H
of macrocycle bearing ZnII porphyrin), 8.33 (s, 2H,
of macrocycle bearing AuIII porphyrin), 8.77 (d, J \ 6.8
5, 6
Hz, 2H, H
4, 7
J \ 6.8 Hz, 2H, H
4, 7
of macrocycle bearing ZnII porphyrin), 8.81 (d,
of macrocycle bearing AuIII porphyrin),
8.93 (d, J \ 4.7 Hz, 2H, pyrrolics in ZnII porphyrin), 8.98 (s,
4H, pyrrolics in ZnII porphyrin), 9.03 (d, J \ 4.7 Hz, 2H, pyr-
rolics in ZnII porphyrin), 9.31 (d, J \ 5.3 Hz, 2H, pyrrolics in
AuIII porphyrin), 9.35 (s, 4H, pyrrolics in AuIII porphyrin), 9.43
(d, J \ 5.3 Hz, 2H, pyrrolics in AuIII porphyrin). UV/VIS
(CH Cl ) k/nm (e/mol L~1 cm~1) 423 (460 000), 525 (19 000),
2
2
52 (42 000), 594 (6000). FAB-MS: m/z found 3443.2 [M
[ PF ]`, 3297.4 [M [ 2PF ]`, 1745.9 [AuIII porphyrin
6
6
macrocycle ] Cu]`, 1683.3 [AuIII porphyrin macrocycle
[ PF ]`,
1648.7
[M [ 2PF ]2`,
1614.3
[ZnII
6
6
macrocycle ] Cu]; ES-MS: m/z found 1649.3 [M [ 2PF ]2`;
6
calcd for C
H
N O ZnAuCu, 3295.8.
200 208 12 12
A previous experiment in which the reaction temperature
was 40 ¡C, with otherwise identical conditions, produced the
mixed catenate 22 in only 8% yield.
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408
New J. Chem., 1998, Pages 395È409

View Article Online
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washed thoroughly before this spectrum was run. Before washing,
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30 S. Chardon-Noblat, and J.-P. Sauvage, T etrahedron, 1991, 47,
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Received in Montpellier, France, 11th August 1997;
Paper 7/08756J
New J. Chem., 1998, Pages 395È409
409