Communications
DOI: 10.1002/anie.200703789
Cage Compounds
Rational Design of a Double-Walled Tetrahedron Containing Two
Different C3-Symmetric Ligands**
Iris M. Oppel (nØe Müller)* and Kirsten Föcker
The rapidly growing field of supramolecular coordination
chemistry can be divided into two classes. Polymers are
already well-known because of their possible applications as
new materials, heterogeneous catalysts, and ion exchangers.[1]
The rational design of the second class, discrete cage
molecules, can be carried out using the molecular library
method,[2] in which the stoichiometry and symmetry elements
of the product are predetermined by the molecular starting
fragments, as illustrated by tetrahedral cages. In the oldest
and most common system [M4L6], the metal centers form the
corners, which are linked by doubly bridging ligands along the
edges.[3] Building blocks that cover the faces of the cage have
been reported far less often and result in the formation of
[M4L4] or [M6L4] systems.[4,5] Nearly all examples for the last
case can be seen as truncated tetrahedra or adamantanoid
cages with wide openings at their corners, allowing guest-
exchange reactions.[5]
formed in high purity and yield. This design principle can be
used for the construction of even more complex coordination
compounds with additional ligands, such as octahedral or
trigonal-bipyramidal cages.[7,8] However, we are just starting
to understand the reactions that take place when the ligands
and metal centers do not match exactly, and a prediction of
the products is not usually possible. Herein, we report the
rational design of the first double-walled tetrahedron con-
taining a ligand–metal pair that is not perfectly matched.
Coordination cages with tetrahedral shapes have been
prepared using tris(2-hydroxybenzylidene)triaminoguanidi-
nium [H6L1]+ and tris(5-bromo-2-hydroxybenzylidene)tri-
aminoguanidinium [H6L2]+, in which the triangular faces are
linked by (CdO)2 four-membered rings (O stands for a
phenolate oxygen atom), resulting in [{(CdCl)3L1}4]8À and
[{(CdCl)3L2}4]8À, respectively.[6] The formation of a compara-
ble discrete single-walled tetrahedron containing Zn2+ was
impossible owing to the much smaller size of the Zn2+ ion
compared to the Cd2+ ion (Zn2+: 0.74 , Cd2+: 0.97 [9]).
Because of this size difference, the faces would come in closer
contact in a Zn2+ compound, which is sterically unfavorable.
On the other hand, it has been demonstrated that [H6L1]+
and [H6L2]+ are able to bind the smaller Zn2+ ions, resulting in
cationic, neutral, or anionic coordination compounds with
one or two ligands, for example [{Zn(NH3)(H2O)}3L1]+,[10]
We are interested in C3-symmetric ligands such as [H6L1]+,
[H6L2]+, and [H6L3], which cover the faces of a cage nearly
completely. We were able to construct tetrahedral coordina-
tion cages,[6] for which an exact match of the ligands to the
steric requirements of the metal centers was shown to be
essential. The supramolecular reaction then leads to products
[Zn{Zn2(H2O)3(NH3)L2}2],
and
[{{Zn(NH3)}3L2}2{m-
(OH)}3]À.[11] In these structures, the metal ions are not located
at ideal positions within the plane of the ligand but are up to
0.87(1) above or below this plane. Especially the last,
dimeric compound (Figure 1) suggested that it might be
possible to obtain a novel tetrahedral cage containing
Zn2+ ions instead of Cd2+. With the Zn2+ centers twisted out
of the ligand plane, it should be possible to link these ions
through the phenolate oxygen atoms to form a double-walled
tetrahedron. Moreover, the overall charge would be reduced
from 8À to 4À, as each building block carries only one
negative charge. This charge reduction should have an
additional stabilizing effect. However, the reaction of
[H6L2]Cl with even a large excess of ZnCl2 leads only to the
formation of the known dimeric compound.
[*] Dr. I. M. Oppel (nØe Müller), K. Föcker
Lehrstuhl für Analytische Chemie
NC 4/27
This result is likely due to a missing stabilization at the
corners, which can be changed by the introduction of addi-
tional side chains on the aromatic ring. As depicted in
Figure 1, the proton bound to C(4) in each dimer is in close
contact with the Br atom at C(5) in the neighboring ligand. If
this proton at C(4) is exchanged for a stabilizing group (e.g. a
methoxy group), the corner of the cage should be closed more
Ruhr-Universität Bochum
44780 Bochum (Germany)
Fax: (+49)234-321-4420
E-mail: iris.oppel@rub.de
[**] We gratefully acknowledge financial support from BayerMaterial-
Science and a doctoral fellowship from the FCI (grant 176291).
À
tightly and stabilized by weak O CH3···Br interactions.
Comparable stabilizing effects have been described.[12]
Supporting information for this article is available on the WWW
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ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2008, 47, 402 –405