The dimeric hand-shake motif in complexes and metallo-supramolecular assemblies of cyclotriveratrylene-based ligands

Article abstract of DOI:10.1002/chem.200801264

A series of clathrate and metal complexes with cyclotriveratrylene-like molecular host ligands show a similar dimeric homomeric inclusion motif in which a ligand arm of one host is the intra-cavity guest of another and vice versa. This hand-shake motif is found in the trinuclear transition metal complex [Cu₃Cl₆(1)]·CH₃CN·1. 5H₂O in which 1 is tris(4-[2,2′,6′,2″-terpyridyl]- benzyl)cyclotriguaiacylene; in the self-included M₄L₄ tetrahedral metallosupramolecular assembly [Ag₄(2)₄] ·(BF₄)₄ in which 2 is tris-(2-quinolylmethyl) cyclotriguaiacylene; in the ID coordination chains [Ag(4)]·ReO ₄ ·CH₃CN and [Ag(5)]·SbF₆· 3 DMF·H₂O in which 4 is tris(1H-imidazol-1-yl)- cyclotriguaiacylene and 5 is tris{4-(2-pyridyl)benzyl}cyclotriguaiacylene ; and in the acetone clathrate of tris{4-(2-pyridyl)benzyl-amino)cyclotriguaiacylene. Clathrates of ligands 2 and 5 do not show the same dimeric motif, although 2 has an extended homomeric inclusion motif that gives a hexagonal network.

Full text of DOI:10.1002/chem.200801264

DOI: 10.1002/chem.200801264
The Dimeric “Hand-Shake” Motif in Complexes and Metallo–
Supramolecular Assemblies of Cyclotriveratrylene-Based Ligands
Christopher Carruthers,[a] Tanya K. Ronson,[a] Christopher J. Sumby,[a, b]
Aleema Westcott,[a] Lindsay P. Harding,[c] Timothy J. Prior,[d, e] Pierre Rizkallah,[d] and
Michaele J. Hardie*[a]
Abstract: A series of clathrate and
metal complexes with cyclotriveratry-
lene-like molecular host ligands show a
similar dimeric homomeric inclusion
motif in which a ligand arm of one host
is the intra-cavity guest of another and
vice versa. This “hand-shake” motif is
found in the trinuclear transition metal
complex [Cu3Cl6(1)]·CH3CN·1.5H2O in
which 1 is tris(4-[2,2’,6’,2’’-terpyridyl]-
benzyl)cyclotriguaiacylene; in the self-
included M4L4 tetrahedral metallo-
supramolecular assembly [Ag4(2)4]
·CH3CN and [Ag(5)]·SbF6·3DMF·H2O
in which 4 is tris(1H-imidazol-1-yl)-
ACHTUNGTRENNcUNG yclotriguaiacylene and 5 is tris{4-(2-
pyridyl)benzyl}cyclotriguaiacylene; and
in the acetone clathrate of tris{4-(2-pyr-
idyl)benzyl-amino}cyclotriguaiacylene.
Clathrates of ligands 2 and 5 do not
show the same dimeric motif, although
2 has an extended homomeric inclusion
motif that gives a hexagonal network.
·
A
N
Keywords: coordination chains
·
cyclotriveratrylene host–guest
·
chemistry · supramolecular chemis-
try · tetrahedral assembly
Introduction
binding[3] and organometallic cryptophanes,[4] organo-gels,[5]
anion sensing,[6] fullerene separations[7] and in metallo-
supramolecular assemblies.[8–12] Like all molecular hosts,
CTV contains an intrinsic molecular cavity that can bind
other molecular species to form host–guest complexes. In
general, clathrate complexes of CTV with small organic
guests form homomeric mis-aligned stacking motifs[13] and
the intra-cavity complexation of a small organic guest mole-
cule is somewhat rarer.[14] Both CTV and its chiral analogue
cyclotriguaiacylene (CTG) can be converted into extended-
arm host molecules through functionalisation at the upper
rim. In their simple crystalline clathrate complexes these
also tend to form homomeric inclusion associations, includ-
ing four reported examples of a dimeric clasping or “hand-
shake” motif in which an arm of one molecule extends into
the molecular cavity of the other and vice versa, as shown
diagrammatically in Scheme 1.[9,15,16] The same dimeric motif
has also been reported for calix[4]- and calix[5]arenes.[17] Di-
merisation usually occurs around a centre of inversion to
give dimers in the case of the chiral CTG analogues. A simi-
lar homomeric inclusion motif which extends to a 1D chain
has also been reported for CTV analogues[9,18] and p-tert-
butyl-calix[5]arene.[19] Other homomeric inclusion motifs in-
volving molecular hosts include self-inclusion, in which the
guest fragment is covalently attached to the host frag-
Cyclotriveratrylene (CTV) is a molecular host with a rela-
tively rigid shallow bowl-shaped cavity.[1] Recent interest in
CTV chemistry includes applications in liquid crystals,[2] gas-
[a] C. Carruthers, Dr. T. K. Ronson, Dr. C. J. Sumby, Dr. A. Westcott,
Dr. M. J. Hardie
School of Chemistry
University of Leeds
Woodhouse Lane, Leeds, LS2 9JT (UK)
Fax : (+44)113-343-6565
E-mail: m.j.hardie@leeds.ac.uk
[b] Dr. C. J. Sumby
Present address: School of Chemistry and Physics
The University of Adelaide
North Terrace, Adelaide, SA 5005 (Australia)
[c] Dr. L. P. Harding
Department of Chemical and Biological Sciences
University of Huddersfield
Huddersfield, HD1 3DH (UK)
[d] Dr. T. J. Prior, Dr. P. Rizkallah
STFC Daresbury Laboratory
Daresbury, Warrington, WA4 4AD (UK).
[e] Dr. T. J. Prior
Present address: Department of Chemistry
University of Hull
Kingston upon Hull, HU6 7RX (UK)
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FULL PAPER
lene 5 required the use of more forcing conditions with reac-
tion in dry dimethylformamide (DMF) with NaH as base,
Scheme 2.
Tris{4-(2-pyridyl)benzyl-amino}cyclotriguaiacy-
lene 6 was synthesised in two steps from the hydrochloride
salt of the precursor 3,8,13-triamino-2,7,12-trimethoxy-10,15-
dihydro-5H-tribenzoACTHNUTRGNEUNG
[a,d,g]cyclononene (aCTG),[24] with ini-
tial formation of the imine through reaction with 4-(2-pyri-
dyl)benzaldehyde followed by reduction with sodium boro-
hydride, Scheme 3.
Scheme 1. Cartoon showing a “hand-shake” dimer formed between two
generic CTG-derived molecular hosts.
Discrete metal complexes and related ligand clathrates: Re-
action of CuCl2 with the terpyridyl-derived ligand 1 in aceto-
nitrile under solvothermal conditions results in the isolation
of green crystals of complex [Cu3Cl6(1)]·CH3CN·1.5H2O 7.
The crystals were extremely small and their structure was
determined using synchrotron radiation. [Cu3Cl6(1)] is a dis-
crete trinuclear complex with CuII centres bound at each ter-
pyridyl arm of the ligand. The asymmetric unit of the crystal
structure comprises one complete trinuclear complex along
with solvent acetonitrile and water positions. All three CuII
coordination spheres are similar, each with a distorted
square pyramidal geometry from a chelating terpyridyl
group and terminal ClÀ ligands in the apical and one basal
site (Figure 1). In the case of Cu3, the basal Cl is approxi-
mately coplanar with the 3N-plane of the terpyridyl group,
ment,[20] and head-to-tail inclusion motifs leading to poly-
meric assemblies.[21,22]
Our major interest in CTV chemistry is in exploiting the
pyramidal shape of CTG extended-arm hosts as ligands for
discrete metallo-supramolecular prisms and/or coordination
polymers with transition metals. Following on from Shinkaiꢁs
earlier report of [M3L2] capsules involving CTV-type li-
gands,[8] we have reported a [Ag2L2]2+ capsule,[9] a [M3L2]2
[2]catenane,[11] a [Ag4L4]4+ star-burst tetrahedron[9,10] and a
[Pd6L8]12+ stella octangula,[12] along with 1D, 2D and 3D co-
ordination polymers.[9,23] We report herein a series of metal
complexes with CTG-based ligands that exhibit the dimeric
“hand-shake” motif. These in-
clude a discrete trinuclear com-
plex which is dimeric in nature
in both solid and solution
states; an unusual M4L4 metal-
lo-supramolecular assembly in
which the hand-shake interac-
tion results in a tightly packed
assembly with no significant in-
ternal space; and 1D coordina-
tion polymers.
Results and Discussion
Ligand synthesis: The synthesis
of tris(4-[2,2’,6’,2’’-terpyridyl]-
benzyl)cyclotriguaiacylene
1
has been previously reported.[15]
Tris-(2-quinolylmethyl)cyclotri-
guaiacylene 2 and tris-(4-quino-
lylmethyl)cyclotriguaiacylene 3
were synthesised by reaction of
cyclotriguaiacylene (CTG) with
the appropriate chloromethyl-
quinoline hydrochloride in the
presence
of
base
and
[18]crown-6 in acetonitrile at
reflux, Scheme 2. The synthesis
of tris(1H-imidazol-1-yl)cyclo-
triguaiacylene 4 and tris{4-(2-
pyridyl)benzyl}cyclotriguaiacy-
Scheme 2. Ligand 1 (box) and synthesis of ligands 2–5.
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M. J. Hardie et al.
NiII, CuII, PtII or PdII.[26,27] There
are only two crystal structures
of prior examples of simple tri-
nuclear
coordination
com-
plexes,[26] and in both cases the
extended metalled arms of the
complexes point outwards from
the CTG-bowl in a symmetric
or near symmetric fashion. This
is not the case in complex 7 in
which the asymmetric confor-
Scheme 3. Synthesis of ligand 6.
mation produces an extended
host with a C-shaped cavity or
cleft in the solid state. This conformation allows the trinu-
clear [Cu3Cl6(1)] complexes to form dimers with the “hand-
shake” motif. The benzyl-terpyridyl-CuCl2 arm of Cu3 of
one complex within the dimer occupies the molecular cavity
of the other and vice versa, giving a racemic dimer
(Figure 2). There are no p–p stacking interactions between
the two complexes within a dimer. In the extended structure
columns of dimers form along the crystallographic c-axis
through extensive p–p stacking interactions. These interac-
tions occur between the benzyl-terpyridyl-CuCl2 arms of
Cu1 and Cu2 at aryl ring centroid separations ranging from
Figure 1. Trinuclear [Cu3Cl6(1)] species from the crystal structure of
[Cu3Cl6(1)]·CH3CN·1.5H2O. Intramolecular p–p stacking interaction is
À
shown as dashed line. Selected bond lengths [ꢂ] and angles [8]: Cu1 N1
À
À
À
À
2.062(8), Cu1 N2 1.955(7), Cu1 N3 2.049(8), Cu1 Cl1 2.250(2); Cu1
À
À
À
Cl2 2.434(3), Cu2 N4 2.039(9), Cu2 N5 1.942(7), Cu2 N6 2.052(9),
À
À
À
À
Cu2 Cl3 2.254(3), Cu2 Cl4 2.415(9), Cu3 N7 2.075(10), Cu3 N8
À
À
À
1.922(10), Cu3 N9 2.077(9), Cu3 Cl5 2.206(4), Cu3 Cl6 2.647(4); N2-
Cu1-Cl1 154.9(2), N1-Cu1-Cl1 99.5(2), N3-Cu1-Cl1 98.7(2), N2-Cu1-Cl2
99.3(2), N3-Cu1-Cl2 96.7(2), N1-Cu1-Cl2 93.3(2), Cl1-Cu1-Cl2
105.80(10), N5-Cu2-Cl3 153.3(2), N4-Cu2-Cl3 98.4(2), N6-Cu2-Cl3
98.8(3), N5-Cu2-Cl4 99.6(2), N4-Cu2-Cl4 96.9(3), N6-Cu2-Cl4 92.4(3),
Cl3-Cu2-Cl4 107.07(12), N8-Cu3-Cl5 172.2(3), N7-Cu3-Cl5 100.3(4), N9-
Cu3-Cl5 99.0(3), N8-Cu3-Cl6 85.7(3), N7-Cu3-Cl6 89.9(3), N9-Cu3-Cl6
99.2(2), Cl5-Cu3-Cl6 102.15(16).
whereas for Cu1 and Cu2 it is below the 3N-plane. The ori-
entation of the benzyl-terpyridyl-CuCl2 arms is quite distinct
for each group. In one case it is approximately coplanar
with its associated guaicol group, another is twisted around
À
its CH2 Cphenyl bond putting the benzyl-terpyridyl fragment
approximately perpendicular to the guaicol. For the third
À
group (of Cu3), rotation has occurred around the O CH2
bond, which folds the benzyl-terpyridyl-CuCl2 fragment in-
wards such that it forms an intramolecular face-to-face p–p
stacking interaction with the benzyl-terpyridyl-CuCl2 frag-
ment of Cu2 at an aryl ring centroid separation of 3.54 ꢂ
(Figure 1). The orientation of the Cu3 coordination sphere
is inverted with respect to the other two, and this unusual
orientation of one of the extended arms forces one of the
neighbouring methoxy groups of the ligand to be bent about
608 away from the adjoining aromatic ring.
A handful of discrete coordination and organometallic
complexes of CTV- or aCTG-based ligands have been previ-
ously reported,[25–27] including trinuclear complexes with AgI,
Figure 2. Two views of the homomeric hand-shake dimer of complex
[Cu3Cl6(1)] from the crystal structure of [Cu3Cl6(1)]·CH3CN·1.5H2O.
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Metallo-Supramolecular Assemblies
FULL PAPER
3.58 to 3.82 ꢂ. Similar solid-state self-complementary dimer-
isation of coordination complexes with molecular clefts have
been reported by Steel and co-workers,[28] and Bosnich and
co-workers.[29] Both examples are dinuclear with the com-
plexes adopting
a C-shaped conformation, and, like
[Cu3Cl6(1)], the latter example also involves terpyridyl coor-
dinating groups.
Electrospray mass spectrometry (ES-MS) studies indicate
that the trinuclear [Cu3Cl6(1)] complex exists in solution,
and that dimerisation of the complexes occurs in solution as
well as in the solid state. An overlapping 1+/2+ peak at
m/z:1739.16 corresponds to a single trinuclear complex
[Cu3Cl5(1)]+ and the dimeric species {[Cu6Cl10(1)2]}2+ (calcd
1739.89); there is a further peak corresponding to the single
complex [Cu3Cl4(1)]2+ at m/z:852.11 (calcd 853.56). Within
the mass spectrometer, the [Cu3Cl6(1)] complexes fragment
through the loss of a single benzyl-terpyridyl-CuCl2 arm.
Remarkably, this does not lead to the dissociation of the
dimer and peaks occur for the loss of one arm from one
complex of the dimer and for the loss of two arms from the
dimer; namely at m/z:1512.16 corresponding to
[Cu5Cl8(1)(1ÀC22H16N3)]2+ (calcd 1512.08) and an overlap-
ping signal at m/z:1283.18 for [Cu4Cl6(1ÀC22H16N3)2]2+ and
the single complex [Cu2Cl3(1ÀC22H16N3)]2+ (calcd 1283.71).
From inspection of Figure 2b of the crystal structure, it is
evident that the hand-shake dimer could lose a single
benzyl-terpyridyl-CuCl2 arm, or indeed one such arm from
each complex, and still retain its integrity as a dimer. Nota-
bly, the analogous dimers of Steel[28] and Bosnich[29] are both
shown to dissociate in solution.
Scheme 4. Schematic diagram of the “star-burst” [Ag4L4]4+ tetrahedral
metallo-supramolecular assembly.
10.1 ꢂ for structures of the star-burst [Ag4L4]4+ assem-
bly.[9,10] Whereas in the star-burst tetrahedron the Ag centres
form the corners of tetrahedron and each ligand forms a
face of the tetrahedron coordinating to three AgI centres,
for complex 8 each ligand only coordinates to two AgI cen-
tres with only two of the three quinoline arms coordinating.
Furthermore, for the star-burst assembly, the basal (CH2)3
plane of the ligand is coplanar with the Ag3 face of the tet-
rahedron; here the ligand is twisted away from alignment
with the tetrahedronꢁs face. This twisting occurs to accom-
modate the coordination geometry of the ligand and the di-
meric homomeric motif formed by the ligands. The dimeric
motif involves a quinoline arm of one ligand acting as the
intracavity guest for the other ligand and vice versa, Fig-
ure 3a. The guest quinoline arm is not positioned directly
over the centre of the host ligandꢁs cavity, but rather posi-
tioned to one side where it forms a p–p stacking interaction
with one of the host ligandꢁs quinoline arms at an aryl cent-
roid separation of 3.49 ꢂ. The two ligands involved in this
“hand-shake” motif are both of the same enantiomer and
are not linked together through metal coordination. The for-
mation of a chiral hand-shake is quite unusual, with all
other examples involving a racemic pair of ligands. There
are two such hand-shake ligand pairs in the [Ag4(2)4]4+ as-
sembly, and the ligands in the second pair are of the oppo-
site enantiomer. The two sets of ligand pairs are linked to-
gether by coordinating to the AgI centres, to give the
[Ag4(2)4]4+ assembly (Figure 3b). The non-coordinating
quinoline group of each ligand forms p–p stacking interac-
tions with one of the coordinating quinolines of another
ligand (aryl centroid separation 3.490 ꢂ) and its C6 aryl ring
is positioned above a AgI centre, effectively blocking the
metal centre from any further coordination interactions. The
closest Ag···C separation to this quinoline is 3.48 ꢂ, which is
too long to indicate the presence of an organometallic inter-
action.
A tetrahedral metallo-supramolecular assembly is afford-
ed by reaction of tris-(2-quinolylmethyl)cyclotriguaiacylene
2 with AgBF4 in CF3CH2OH. Complex [Ag4(2)4]·
ACHTUGNRTNE(NUNG BF4)4 8 is
isolated as small single crystals. The single crystal X-ray
structure of [Ag4(2)4]·ACHTNUTRGNE(NUG BF4)4 reveals that the complex is a
discrete [Ag4L4]4+ tetrahedral metallo-supramolecular as-
sembly, but one that is structurally quite distinct from the
previously reported “star-burst” [Ag4L4]4+ assembly (L=
tris(4-pyridylmethylamino)cyclotriguaiacylene).[9,10]
The
structure of [Ag4(2)4]4+ is complicated and easiest to under-
stand by comparison with the simpler star-burst assembly,
which is shown diagrammatically in Scheme 4. The star-
burst assembly is an M4L4 tetrahedron with metal centres at
the corners of the tetrahedron and ligands (L) taking up the
facial positions. There have only been a relatively small
number of tetrahedral M4L4 assemblies reported with tripo-
dal ligands (L).[9,10,30–32]
The asymmetric unit of [Ag4(2)4]·ACTHNUGTRNEG(UN BF4)4 consists of one
À
ligand, one AgI centre and one BF4 counter-anion. The
ligand is asymmetric with all three quinoline arms having
different orientations. The AgI centres have linear geometry
À
À
À
with Ag N distances 2.205(10) and 2.169(10) ꢂ and N Ag
N angle 176.0(4)8. In complex 8 the four crystallographically
equivalent AgI centres of the [Ag4(2)4]4+ assembly are ar-
ranged in a distorted tetrahedron with respect to one anoth-
er at Ag···Ag separations 9.31 and 10.34 ꢂ (Figure 3). This
compares with shorter typical Ag···Ag separations of ꢀ8.7–
There is no significant internal space within the
[Ag4(2)4]4+ assembly. In contrast, most other examples of
M4L4 assemblies, including, the “star-burst” tetrahedron, do
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M. J. Hardie et al.
Figure 3. Views of the [Ag4(2)4]4+ assembly: a) and b) are from the crystal structure of complex 8, with each ligand shown in a different colour scheme,
in which a) shows the [Ag4(2)4]4+ cage (left) and an exploded view (right) highlighting the two pairs of hand-shake ligand dimers; and b) gives a space-
filling view of the [Ag4(2)4]4+ assembly. c) Is a ball-and-stick stereo-view of the [Ag4(2)4]4+ assembly.
possess sufficient space to act as supramolecular
hosts.[9,10,30,32] A further exception to this is a series of com-
plexes reported by Raymond and co-workers,[32] which fea-
ture small internal cavities owing to the relatively small size
of the tripodal ligands used. In most cases however, cationic
or anionic guests are encapsulated inside the tetrahedral as-
semblies,[30] and exchange of cationic guests has been report-
ed.[31]
value of 1965.50 corresponding to a dimeric [Ag2(2)2]ACHTUNGTRENNUNG
(BF4)+
species (calcd 1966.44).
The crystal structure of a clathrate complex of ligand 2,
obtained by its recrystallisation from 2,2,2-trifluroethanol,
also displays a homomeric inclusion motif, but one that is
quite distinct from the dimeric hand-shake motif. The asym-
metric unit of the structure of complex 2·H2O·4CF3CH2OH
9 is shown in Figure 4a. The ligand within complex 9 has
non-crystallographic C3 symmetry with all three quinoline
arms emanating directly outwards from the CTG frame-
work. Each quinoline forms hydrogen bonding interactions
with water or 2,2,2-trifluoroethanol at N···O separations
ranging from 2.77 to 2.78 ꢂ, Figure 4a. Each ligand acts as a
host for three other crystallographically equivalent ligands,
with a single quinoline arm of each of the “guest” ligands di-
rected into the molecular cavity (Figure 4b). Two of the
three guest quinoline arms show p–p stacking interactions
at an aryl ring centroid separation of 3.65 ꢂ. The orientation
of the “guest” ligand 2 molecules is inverted with respect to
that of the host ligand, hence these homomeric associations
generate a 2D network of ligands. Each ligand also forms
face-to-face p–p stacking interactions to three other ligands
through its exo surface, at aryl centroid separations ranging
from 3.49 to 3.97 ꢂ. The extensive p–p stacking and host-
guest interactions create an overall 3D extended network of
ligands with large channels running along the c axis. The
channels contain solvent water and CF3CH2OH molecules
(Figure 5).
In the crystal lattice of 8 the [Ag4(2)4]4+ assemblies do
not approach each other closely and each [Ag4(2)4]4+ assem-
À
bly is surrounded by six BF4 anions in a distorted hexa-
ACHTUNGTRENNUNGgonal pattern. The crystalline material is likely to be highly
solvated, but the quality of the X-ray data obtained does
not allow for this to be elucidated. The solvent-accessible
void within the crystal lattice is calculated to be approxi-
mately 25% of the unit cell volume.[33]
On titrating AgBF4 into a solution of ligand 2 in
1
CF3CD2OD at room temperature the H NMR signal of the
ligand broadens considerably, indicating the formation of a
solution phase species that is undergoing fast exchange on
the NMR timescale. The spectrum begins to sharpen at
lower temperatures, but, unfortunately, has not sufficiently
sharpened at the freezing limit of the solvent to allow for
identification of any solution species. There is no significant
change to the room temperature 1H NMR signal of the
ligand when AgBF4 is added in the coordinating solvent
CD3CN. It is also notable that 1:1 mixtures of AgBF4 and 2
in 2,2,2-trifluoroethanol sometimes results in the formation
of a gel, and that crystals were isolated after using an excess
of metal salt. ES-MS studies do not give any evidence of the
[Ag4(2)4]4+ tetrahedron, with the highest observed m/z
The previously reported isomer of ligand 2, tris-(8-quino-
lylmethyl)cyclotriguaiacylene, forms an acetonitrile clathrate
complex that displays the dimeric hand-shake motif.[15]
A
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Metallo-Supramolecular Assemblies
FULL PAPER
linear chain of ligands is formed through host-guest associa-
tions (Figure 6). Only one of the three quinoline arms is in-
volved in this interaction. The linear chain motif found here
Figure 6. Section of the crystal packing diagram of complex 3·CH3CN 10
showing the formation of a head-to-tail inclusion chain.
is more akin to linear head-to-tail associations of functional-
ised calixarenes[21] than other reported 1D inclusion chains
of CTG-derivatives. Examples of the latter usually involve a
mis-aligned self-stacking giving a zig-zag rather than a linear
chain.[18] There are face-to-face p–p stacking interactions be-
tween quinoline groups of different inclusion chains of com-
plex 10 at a ring centroid separation of 3.89 ꢂ, as well as be-
tween quinoline and core benzene groups at a ring centroid
separation of 3.81 ꢂ.
Figure 4. Crystal structure of 2·H2O·4 CF3CH2OH 9. a) The asymmetric
unit with hydrogen bonds indicated as dashed lines; b) An illustration of
the three homomeric associations of the ligand with the “host” ligand
shown in lighter shading.
Polymeric metal complexes and related ligand clathrates:
Complexes [Ag(4)]·ReO4·CH3CN 11, and [Ag(5)]·SbF6
·3DMF·H2O 12 were isolated from reaction of their respec-
tive ligands with AgI salts. Both complexes show topologi-
cally identical coordination chains that incorporate dimeric
homomeric inclusion motifs. The crystal structures of both
complexes are of low symmetry with a metal cation, anion,
complete ligand and solvent positions comprising the asym-
metric units. In both cases, the orientation of the ligand
side-arms is asymmetric. One of the pyridyl groups and
most of the solvent DMF molecules of [Ag(5)]·SbF6
·3DMF·H2O were modelled as disordered.
The AgI cation of [Ag(4)]·ReO4·CH3CN has a T-shaped
geometry, being coordinated by imidazole groups from three
different, though crystallographically equivalent, ligands.
Each ligand bridges between three crystallographically
equivalent AgI centres to create a polymeric complex (Fig-
ure 7a). The polymer is a snaking 1D chain with ladder-like
topology, with both the ligand and metal acting as a 3-con-
necting centre. The [Ag(5)]+ chain within the complex
[Ag(5)]·SbF6·3DMF·H2O is topologically identical to that of
the [Ag(4)]+ chain, although the geometry around the AgI
centre is quite different. Here, the AgI has a distorted geom-
etry closer to trigonal than T-shaped, with coordination by
three pyridyl groups of different ligands and one bond
length much longer than the others, Figure 7b. The [Ag(5)]+
1D coordination chain is considerably straighter than that
seen for [Ag(4)]+ (Figure 7).
Figure 5. Extended packing diagram for complex 9 viewed down the c
axis with solvent molecules excluded.
new isomer of 2, ligand tris-(4-quinolylmethyl)cyclotriguaia-
cylene 3, also forms an acetonitrile clathrate as complex
3·CH3CN 10, but one in which the crystal structure shows a
different type of association between the ligands. Ligand 3
in complex 10 has C1 symmetry and one upper rim methyl
group is significantly rotated away with a CO···O angle of
898 between the methoxy group and O-methylquinoline. A
For both [Ag(4)]+ and [Ag(5)]+ the orientation of the
molecular cavities of the ligands alternates along the chain
and each ligand is involved in one pairwise host–guest inter-
Chem. Eur. J. 2008, 14, 10286 – 10296
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www.chemeurj.org
10291

M. J. Hardie et al.
the a axis and form face-to-face p–p stacking interactions
between chains in the bc plane at an aryl centroid distance
À
3.80 ꢂ. The channels contain well-ordered ReO4 anions
À
and solvent acetonitrile (Figure 8). Each ReO4 anion forms
a weak interaction to the exposed face of a AgI cation at
À
Re O···Ag separation 2.91 ꢂ.
Figure 8. Packing diagram for the crystal structure of complex 9 shown
slightly displaced from the a axis.
Figure 7. Coordination chains with homomeric pair-wise inclusion motifs
between the ligands. Each ligand within a pair is shown with different
shading. a) [Ag(4)]+
chain from the crystal structure of
A simple clathrate complex of ligand 4 has yet to be iso-
[Ag(4)]·ReO4·CH3CN 11; b) From the crystal structure of
[Ag(5)]·SbF6·3DMF·H2O 12: AgI coordination sphere and pyridyl disor-
der (top) and [Ag(5)]+ chain (bottom, with only one disorder fragment
shown for clarity). Selected bond lengths [ꢂ] and angles [8]: complex 11:
lated, however
a
clathrate of ligand 5, complex
5·DMF·0.25CH3OH, 13, can be isolated by recrystallisation
of the ligand from a methanol-DMF mixture. The asymmet-
ric unit of the crystal structure of 13 is shown in Figure 9,
Ag1 N2 2.607(4); Ag1 N4 2.140(3), Ag1 N6 2.133(3); N2-Ag1-N4i
86.24(13), N2-Ag1-N6ii 98.91(13), N4i-Ag1-N6ii 171.25(14); complex 12:
Ag1-N1 2.229(6), Ag1-N2iii 2.246(6), Ag1-N3iv 2.505(7), N1-Ag1-N2iii
150.6(2), N1-Ag1-N3iv 113.3(2), N2iii-Ag1-N2iv 95.9(3). Symmetry opera-
tions: i: 2ÀX, 2ÀY, 1ÀZ; ii: X, 1+Y, Z; iii: 1ÀX; ÀY; ÀZ; iv: 1+X, Y,
1+Z.
i
ii
À
À
À
action across an inversion centre with one other ligand. This
takes the form of the familiar hand-shake motif. In [Ag(4)]+
the guest imidazole group is oriented such that it forms a
À
Figure 9. Asymmetric unit of the crystal structure of 5·DMF·0.25CH3OH
13 illustrating the intra-cavity DMF guest complexation, and disorder of
the pyridyl groups. Hydrogen atoms are excluded from ligand 5 for
single C H···p edge-to-face interaction with
a guaicol
À
moiety of the host fragment (C H···ring centroid distance
2.46 ꢂ at 153.68 at H, C···ring centroid separation 3.34 ꢂ).
In [Ag(5)]+ face-to-face p–p stacking interactions occur be-
tween the guaicol host and pyridyl guest fragments at a ring
centroid separation of 3.56 ꢂ, and between the linking
benzyl groups at 3.97 ꢂ between the aryl ring centres. This
chain topology along with the same inclusion motif has been
observed once before within a coordination chain involving
a CTG-related ligand, in the chain structure of [Ag-
AHCTUNGTRENNcGUN larity.
and comprises a complete molecule of each of the compo-
nents. The orientation of each (2-pyridyl)benzyl side-arm
within ligand 5 are all distinct and two pyridyl groups show
disorder. The DMF is the intra-cavity guest for the host
ligand thus excluding the possibility of forming dimeric
hand-shake inclusion motifs between the ligands. As expect-
ed, a hydrophobic methyl group of the guest DMF is orient-
ed into the hydrophobic cavity of the ligand. Examples of
intra-cavity guest complexation with CTV or simple extend-
ed-arm CTV complexes are relatively limited. There are no
face-to-face p-stacking interactions within the extended lat-
tice of 13.
ACHTUNGTRENNUNG
(H2O)L]+ in which L=tris(3-pyridylmethyl-amino)cyclotri-
guaiacylene.[9] In that case the AgI had tetrahedral geometry
with a terminal aquo ligand and bridging L ligands.
The snaking, zig-zagging shape of the [Ag(4)]+ chain
within [Ag(4)]·ReO4·CH3CN leads to an interesting packing
motif whereby channels are formed along the crystallo-
graphic a-axis. The chains stack in an aligned fashion along
10292
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ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 10286 – 10296

Metallo-Supramolecular Assemblies
FULL PAPER
Although ligand 5 does not show the hand-shake motif in
a simple clathrate complex, the closely related ligand 6—
with an amine link to the (2-pyridyl)benzyl group in place
of the ether link of 5—does form a clathrate complex with
the dimeric hand-shake motif. The acetone clathrate of
complished by appending more hydrophilic metal binding
arms to the CTV to minimize inclusion by a second host
cavity.
ligand 6, complex 6·2 COACHTNUGTRNEGNU(CH3)2, 14, has the given composi-
Experimental Section
tion as the asymmetric unit. All three (2-pyridyl)benzyl
arms show a different orientation, and a racemic dimer is
formed across an inversion centre whereby a (2-pyridyl)ben-
zyl arm of one ligand is oriented into the molecular cavity
of the other and vice versa (Figure 10). Acetone guest mole-
cules occupy clefts within the dimer. Reaction of ligand 6
with a variety of metal salts did not lead to the isolation of
any metal complexes, and the reaction mixture discoloured
indicating decomposition of the ligand.
Cyclotriguaiacylene,[34] tris(4-[2,2’,6’,2’’-terpyridyl]benzyl)cyclotriguaiacy-
lene,[15]
3,8,13-triamino-2,7,12-trimethoxy-10,15-dihydro-5H-tribenzo-
AHCTUNGTRENNUNG
[a,d,g]cyclononene hydrochloride (aCTG.3HCl),[24] 1-chloromethylimida-
zole hydrochloride,[35] and 4-bromomethyl-2-phenylpyridine[36] were syn-
thesised by literature methods.
Synthesis
Tris-(2-quinolylmethyl)cyclotriguaiacylene
2:
Cyclotriguaiacylene
(216 mg, 0.52 mmol), potassium carbonate (777 mg, 5.6 mmol) and
[18]crown-6 (62 mg, 0.25 mmol) were stirred together at reflux in acetoni-
trile (40 mL) under nitrogen for 30 minutes. 2-(Chloromethyl)quinoline
monohydrochloride (389 mg, 1.8 mmol) was then added and the mixture
heated at reflux under nitrogen for 24 h. After this time another 3 equiv-
alents of the quinoline salt was added and heating at reflux was contin-
ued until NMR monitoring indicated that the reaction was complete (a
further 48 h). Water (50 mL) was then added, precipitating the product,
which was collected, washed with methanol (20 mL) then diethyl ether
(10 mL) and dried under vacuum to give 2 (280 mg, 64%), as a white
solid. m.p. 110–1148C; 1H NMR (300 MHz, CDCl3) d=3.27 (s, 9H; O-
CH3), 3.35 (d, J=13.8 Hz, 3H; CH2), 4.60 (d, J=13.8 Hz, 3H; CH2), 5.41
(s, 6H; CH2-O), 6.47 (s, 3H; Ar CH), 6.78 (s, 3H; Ar CH), 7.55 (t, J=
7 Hz, 3H; quin.H9) 7.6 (d, J=8 Hz, 3H; quin.H3), 7.75 (t, , J=7 Hz 3H;
quin.H8), 7.83 (d, J=8 Hz, 3H; quin.H10), 8.06 (d, J=8.5 Hz, 3H;
quin.H4), 8.13 ppm (d, J=8.5 Hz, 3H; quin.H7); 13C NMR (75 MHz,
CDCl3) d=36.5, 55.6, 72.4, 113.3, 115.0, 118.9, 126.5, 127.7, 127.9, 128.8,
129.8, 131.5, 132.5, 137.1, 146.6, 147.6, 148.0, 158.7 ppm; ES-MS: m/z:
Figure 10. View from the crystal structure of 6·2 COACHTNUGTRNEG(UN CH3)2 14 showing
+
832.3353 [M+H+] C54H46N3O6 requires 832.9597; elemental analysis
the formation of a “hand-shake” dimer and position of one acetone
guest. The two symmetry related ligands have different shading. Only the
major disorder positions are shown and hydrogen atoms have been ex-
cluded from 6 for clarity.
calcd (%) for C54H45N3O6·5H2O: C 70.3, H 6.0, N 4.6; found C 70.4, H
5.7, N 4.3.
Tris-(4-quinolylmethyl)cyclotriguaiacylene 3: A similar procedure to the
synthesis of 2 was employed using 4-(chloromethyl)quinoline monohy-
drochloride (300 mg, 1.4 mmol). NMR monitoring indicated that the re-
action required 72 h of heating at reflux after the second addition of
quinoline salt. Compound 3 was isolated as a white solid (251 mg, 62%).
m.p. 136–1408C; 1H NMR (300 MHz, CDCl3) d=3.43 (d, J=13.8 Hz,
3H; CH2), 3.55 (s, 9H; O-CH3) 4.68 (d, J=13.8 Hz, 3H; CH2), 5.58 (dd,
4JHH =26.9 Hz, 2JHH =14.3 Hz, 6H; CH2O), 6.58 (s, 3H; Ar CH), 6.81 (s,
3H; Ar CH), 7.54 (d, J=4.3 Hz, 3H; quin.H3) 7.59 (t, J=7.5 Hz, 3H;
quin.H9), 7.76 (t, J=7.3 Hz, 3H; quin.H8), 7.96 (d, J=8.3 Hz, 3H;
quin.H10), 8.18 (d, J=8.3 Hz, 3H; quin.H7), 8.89 ppm (d, J=4.4 Hz, 3H;
quin.H2); 13C NMR (75 MHz, CDCl3) d=36.8, 56.4, 69.2, 114.1, 117.3,
119.4, 123.1, 126.0, 127.3, 129.8, 130.8, 132.1, 133.9, 142.9, 147.0, 149.5,
Conclusion
The dimeric association of two molecular hosts had been
previously observed for a small number of cycotriveratry-
lene-based and calixarene molecular hosts. This inclusion
motif has been shown to also be exhibited by different types
of metal complexes of CTV-type ligands, including a discrete
trinuclear complex, metallo-supramolecular tetrahedron and
1D coordination polymers. The interaction is sufficiently
robust that it can be observed by mass spectrometry even
with fragmentation of the coordination complex. The two
pairs of metal connected hand-shake dimers of [Ag4(2)4]4+
lead to a very unusual self-included tetrahedral prism with
no significant internal space. These results indicate that in
future studies of discrete and polymeric metallo-supramolec-
ular species featuring CTV-derived host ligands, simultane-
ous prevention of the two common modes of CTV inclusion
will have to be investigated to enable the full realization of
the host cavity for inclusion of other entities. Upper rim
functionalization with large metal coordinating groups, as
described here, generally limits the aligned and misaligned
stacking of the CTV core moieties commonly seen for the
parent molecular hosts CTV and CTC, but engages this
second “hand-shake” motif of inclusion. This could be ac-
+
149.2, 150.9 ppm; ES-MS: m/z: 832.4562 [M+H+] C54H46N3O6 requires
832.9597; elemental analysis calcd (%) for C54H45N3O6.H2O: C 76.3, H
5.6, N 4.9; found C 76.4, H 5.5, N 4.9.
Tris(1H-imidazol-1-yl)cyclotriguaiacylene 4: NaH (60% dispersion in
mineral oil, 390 mg, 9.75 mmol) was added in small portions to a solution
of CTG (200 mg, 0.490 mmol) in dry DMF (7 mL) and the mixture
stirred for 30 min. Solid 1-chloromethylimidazole hydrochloride (600 mg,
3.92 mmol) was added and the mixture stirred at room temperature for
48 h. Water (100 mL) and CH2Cl2 (100 mL) were added and the aqueous
layer washed with CH2Cl2 (2ꢃ100 mL). The combined organic layers
were washed with water (5ꢃ100 mL), dried (MgSO4) and evaporated in
vacuo. The residue was purified by column chromatography (alumina,
5% MeOH in CH2Cl2) to afford 4 as an off-white powder (232 mg,
73%). m.p. 149–1538C; 1H NMR (500 MHz, CDCl3): d=3.40 (d, J=
13.8 Hz, 3H; CH2) , 3.84 (s, 9H; CH3), 4.59 (d, J=13.8 Hz, 3H; CH2),
5.71 (m, 6H; CH2-O) , 6.68 (s, 3H; aryl CH), 6.63 (s, 3H; aryl CH), 6.98
(s, 3H; imidazole CH), 7.02 (s, 3H; imidazole CH), 7.49 ppm (s, 3H; imi-
dazole CH); 13C NMR (75 MHz, CDCl3): d=36.6, 56.4, 114.3 , 119.6,
123.5, 130.3, 131.9, 136.9, 138.1, 143.6, 150.4 ppm; ES-MS: m/z: 649
Chem. Eur. J. 2008, 14, 10286 – 10296
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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10293

M. J. Hardie et al.
[M+H+]; elemental analysis calcd (%) for C36H36N6O6.H2O: C 64.85, H
5.74, N 12.61; found C 65.20, H 5.65, N 12.65.
18CminÀ1 to 1308C in a 23 mL Parr acid digestion vessel. The solution
was kept at this temperature for 48 H; before cooling at 0.18CminÀ1 to
room temperature to give very small green crystals of 7 (4.2 mg, 41%).
IR (solid state): n˜ =788, 1020, 1085, 1145, 1265, 1403, 1443, 1472, 1512,
1606, 1809, 1930, 2105, 2077, 2929, 3077, 3374, 3567, 3854 cmÀ1; ES-MS:
Tris{4-(2-pyridyl)benzyl}cyclotriguaiacylene 5: A similar procedure to the
synthesis of 4 was employed using CTG (200 mg, 0.5 mmol), NaH (60%
dispersion in mineral oil, 200 mg, 8 mmol) and 4-bromomethyl-2-phenyl-
pyridine (610 mg, 2.45 mmol). The crude product was purified by column
chromatography on silica gel using 0.5% methanol in dichloromethane
as an eluent. The off-white solid obtained was suspended in diethyl ether
to give 5 as an off-white solid (130 mg, 30%). m.p. 173–1768C; 1H NMR
(500 MHz, CDCl3): d=3.48 (d, J=13.5 Hz, 3H; CH2), 3.62 (9H; s,
OMe), 4.67 (d J=13.5 Hz, 3H; CH2), 5.17 (s, 6H; OCH2), 6.64 (s, 3H;
aryl H), 6.82 (s, 3H; aryl H), 7.22 (t, J=4.8 and 5.1 Hz 3H; H5), 7.5 (d,
J=8 Hz, 6H; benzyl H), 7.73 (m, 6H; H3, H4), 7.9 (d, J=8 Hz, 6H;
benzyl H), 8.68 ppm (d, J=4.6 Hz, 3H; H6); 13C NMR (75 MHz, CDCl3):
d=36.9, 56.5, 71.7, 114.1, 116.5, 120.8, 122.6, 127.5, 132.0, 133.0, 137.2,
138.9, 139.3, 147.4, 148.8, 150.1, 157.3 ppm; ES-MS: m/z: 910.4 [M+]; ele-
mental analysis calcd (%) for
m/z:
1739.16
{[Cu3Cl5(1)]+/
G
1512.16
{[Cu5Cl8(1)(1ÀC22H16N3)]2+},
1283.18
{[Cu4Cl6(1ÀC22H16N3)2]2+
/ACHTUNGTRENNUNG[-
Cu2Cl3(1ÀC22H16N3)]2+}, 852.11 {[Cu3Cl4(1)]2+}; elemental analysis calcd
(%) for Cu3C92H72O6N10Cl6·8H2O: C 56.35, H 4.52, N 7.14; found: C
55.9, H 4.05, N 6.35.
ACHUTNGRENUN[G Ag4(2)4]·AHCTUNGTERN(NGUN BF4)4 8: A solution of AgBF4 (5 mg, 25 mmol) in MeCN (few
drops) was added to a solution of 2 (11 mg, 13 mmol) in 2,2,2-trifluroetha-
nol (4 mL). Slow evaporation of the solvent gave crystals of 8 (8 mg,
60%) which, after crystals were selected for X-ray analysis, were filtered
and dried in vacuo. IR (solid state): n˜ =485, 519, 555, 585, 622, 660, 746,
763, 781, 827, 880, 914, 929, 943, 1001, 1085, 1141, 1187, 1213, 1276, 1349,
C60H51O6N3.1.5H2O: C 76.89; H 5.82 N
4.48; found C 76.90, H 5.7, N 4.30.
Table 1. Details of data collections and structure refinements for complexes 7–14.
7
8
9
10
Tris{4-(2-pyridyl)benzyl-amino}cyclo-
triguaiacylene 6: aCTG·3HCl (518 mg,
1.01 mmol), 4-(2-pyridyl)benzaldehyde
(570 mg, 3.11 mmol), triethylamine
(2 mL) and ethanol (50 mL) were
heated at reflux for 3 h. The reaction
mixture was cooled to room tempera-
ture, the solvent removed in vacuo to
give a bright yellow solid. This was
dissolved in a 1:1 mixture of dichloro-
methane and ethanol (40 mL), sodium
borohydride (460 mg, 12.1 mmol) was
added in small portions and the reac-
tion mixture stirred at room tempera-
ture for 72 h. The solvent was removed
in vacuo and the solid taken up in di-
chloromethane (150 mL), the chlori-
nated extract washed with water
(50 mL) and then dried over magnesi-
um sulfate. The solvent was removed
and the resulting oily solid triturated
with ethanol. The resulting pale yellow
solid was collected, washed with etha-
nol, then ether, and dried under
vacuum to give 6 (869 mg: 95%). m.p.
formula
Mr
crystal size [mm]
crystal system
space group
a [ꢂ]
b [ꢂ]
c [ꢂ]
a [8]
b [8]
C92H75Cl6Cu3N10O7.5
1843.94
0.13ꢃ0.03ꢃ0.02
triclinic
C216H180Ag4B4F16N12O24
4106.44
0.07ꢃ0.06ꢃ0.6
tetragonal
C62H59F12N3O11
1250.12
0.30ꢃ0.12ꢃ0.12
monoclinic
C2/c
37.637(4)
21.344(2)
16.9385(16)
90
96.731(1)
90
13513(2)
8
1.229
0.106
3.63–26.0
38186
9338, 0.0657
6124
C56H48N4O6
872.98
0.12ꢃ0.07ꢃ0.06
monoclinic
P21/c
15.1168(8)
15.0928(8)
18.9700(10)
90
96.457(1)
90
4300.6(4)
4
1.348
0.088
1.69–22.53
27759
¯
¯
P1
I4
12.8526(13)
17.5353(17)
21.026(2)
103.490(1)
104.237(1)
92.446(1)
4441.3(8)
2
1.379
0.953
3.69–25.0
2379
11025, 0.056
6806
18.5832(9)
18.5832(9)
32.178(3)
90
90
90
11112.2(14)
2
1.227
0.423
1.27–17.82
9792
3702, 0.0568
3032
258
0.0579
0.1624
1.087
g [8]
V [ꢂ3]
Z
1calcd [gcmÀ3
]
m [cmÀ1
q range [8]
]
data collected
unique data, Rint
obs. data [I>2s(I)]
no. parameters
R1 [obs. data]
wR2 [all data]
GOF
6068, 0.0656
4690
776
0.0460
0.1265
1066
0.0824
0.2860
1.031
860
0.1082
0.3038
1.825
1.027
146–1488C;
1H NMR
(500 MHz,
11
12
13
14
CDCl3) d=3.37 (d, J=13.7 Hz, 3H;
CH2), 3.51 (s, 9H; OCH3), 4.38 (m,
6H; NHCH2py), 4.67 (d, J=13.7 Hz,
3H; CH2), 4.64 (bs, 3H; NH), 6.47 (s,
3H; aryl CH), 6.50 (s, 3H; aryl CH),
7.22 (t, J=5.0 Hz, 3H; H5), 7.46 (d,
J=8.1 Hz, 6H; benzyl H), 7.73 (m,
6H; H3 and H4), 7.95 (d, J=8.2 Hz,
6H; benzyl H), 8.54 ppm (d, J=
4.7 Hz, 3H; H6); 13C NMR (75 MHz,
CDCl3) d=36.5, 48.1, 55.4, 111.2,
111.3, 120.3, 122.0, 127.1, 127.4, 128.0,
132.4, 136.7, 138.2, 141.2, 145.5, 149.7,
formula
Mr
crystal size [mm]
crystal system
space group
a [ꢂ]
b [ꢂ]
c [ꢂ]
a [8]
b [8]
C38H39AgN7O10Re
1047.83
C69H74AgF6N6O10Sb
1490.96
C63.25H59N4O7.25
991.14
0.51ꢃ0.03ꢃ0.03
monoclinic
P2/c
31.8023(17)
9.7186(5)
17.5642(9)
90
92.309(3)
90
C66H66N6O5
1023.25
0.12ꢃ0.08ꢃ0.02
triclinic
0.48ꢃ0.03ꢃ0.03
triclinic
0.32ꢃ0.28ꢃ0.09
triclinic
¯
¯
¯
P1
P1
P1
8.9251(6)
15.0298(9)
15.2006(9)
87.473(4)
76.674(4)
83.130(4)
1969.6(2)
2
1.767
3.634
1.36–27.42
45308
8748, 0.0417
6806
14.2674(11)
15.0917(12)
16.9138(13)
111.868(4)
100.442(4)
90.440(4)
3312.5(4)
2
1.495
0.783
2.03–25.0
49406
11641, 0.0595
7443
11.7202(2)
14.6869(2)
17.4095(3)
77.922(1)
77.243(1)
71.433(1)
2739.20(8)
2
1.241
0.079
3.68–27.51
69799
12515, 0.0707
8820
g [8]
V [ꢂ3]
Z
5424.2(5)
4
1.214
1calcd [gcmÀ3
]
157.2 ppm; ES-MS: m/z: 907.4291
m [cmÀ1
q range [8]
]
0.080
+
[M+H+]
C60H55N6O3
requires
1.28–27.50
102003
12466, 0.0912
5853
758
0.1103
907.4330; elemental analysis calcd (%)
for C60H54N6O3·H2O C 77.88, H 6.11,
N 9.09; found C 77.85, H 5.90, N 9.20.
data collected
unique data, Rint
obs. data [I>2s(I)]
no. parameters
R1 [obs. data]
wR2 [all data]
GOF
ACHTUNGTRENNUNG
518
0.0325
0.0806
1.096
813
0.0692
0.2216
1.013
737
0.0707
0.2263
1.034
1
0.3861
1.222
mmol) and CuCl2 (2.8 mg, 11.6 mmol)
in acetonitrile (5 mL) was heated at
10294
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ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 10286 – 10296

Metallo-Supramolecular Assemblies
FULL PAPER
1378, 1399, 1444, 1465, 1479, 1507, 1571, 1599, 1963, 2866, 2935, 3066,
[3] H. A. Fogarty, P. Berthault, T. Brotin, G. Huber, H. Desvaux, J.-P.
Dutasta, J. Am. Chem. Soc. 2007, 129, 10332–10333.
[4] R. M. Fairchild, K. T. Holman, J. Am. Chem. Soc. 2005, 127, 16364–
16365.
ACTHNUTRGNEUNG
3527 cmÀ1; ES-MS: m/z: 1965.50 {[Ag2(2)2](BF4)+}, 1771.60 {[Ag(2)2]+},
940.25
{[Ag(2)]+;
elemental
analysis
calcd
(%)
for
C54H45N3O6BF4Ag·1.5CF3CH2OH: C 58.28, H 4.24, N 3.57; found C 58.7,
H 4.4, N 3.7.
[5] D. Bardelang, F. Camerel, R. Ziessel, M. Schmutz, M. J. Hannon, J.
Mater. Chem. 2008, 18, 489–494.
[6] S. Zhang, L. Echegoyen, J. Am. Chem. Soc. 2005, 127, 2006–2011;
J. A. Gawenis, K. T. Holman, J. L. Atwood, S. S. Jurisson, Inorg.
Chem. 2002, 41, 6028–6031.
[7] E. Huerta, G. A. Metselaar, A. Fragoso, E. Santos, C. Bo, J. de Men-
doza, Angew. Chem. 2007, 119, 206–209; Angew. Chem. Int. Ed.
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dried in vacuo. IR (solid state): n˜ =3129, 2927, 2847, 1611, 1509, 1464,
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Acknowledgements
The authors would like to acknowledge the EPSRC and University of
Leeds for their financial support of this research. The authors thank
STFC Daresbury laboratory for access to micro-diffraction facilities, and
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Received: June 25, 2008
Published online: October 1, 2008
10296
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Chem. Eur. J. 2008, 14, 10286 – 10296