The use of just two types of building blocks, linear and angular, in conjunction with symmetry
considerations allows the rational design of a wide range of metallocyclic polygons and polyhedra
via the coordination motif.1-3 We have used this approach to self-assemble a variety of 2D
supramolecular polygons such as triangles, rectangles, squares, hexagons, etc. as well as a number
of 3D supramolecular polyhedra: truncated tetrahedra, triginal prisms, cubooctahedra4 and
dodecahedra.5 An example of the methodology is illustrated in Figure 1. More recently we have
functionalized these rigid supramolecular scaffolds with different electroactive, host-guest, dendritic
(Figure 2), and hydrophobic/hydrophilic moieties and have investigated the properties of these
multifunctionalized supramolecular species. Additionally, we have begun to explore the selfassembly
of 2D polygons and 3D polyhedra on a variety of surfaces with the aim of developing
their potential to be used in device settings. These novel, supramolecular ensembles are
characterized by physical and spectral means. The design strategy, formation, characterization and
potential uses of these novel metallocyclic assemblies will be discussed, along with our recent
results in crystal engineering.
1. High Symmetry Coordination Cages via Self-Assembly, S.R. Seidel, P.J. Stang, Acc. Chem.
Res., 2002, 35, 972-983.
2. Self-Assembly of Discrete Cyclic Nanostructures Mediated by Transition Metals, S. Leininger,
B. Olenyuk, P. J. Stang, Chem. Rev., 2000, 100, 853-908 .
3. Self-Assembly, Symmetry and Molecular Architecture: Coordination as the Motif in the Rational
Design of Supramolecular Metallocyclic Polygons and Polyhedra, P. J. Stang, B. Olenyuk, Acc.
Chem. Res., 1997, 20, 502-518.
4. Self-Assembly of Nanoscale Cuboctahedra by Coordination Chemistry, B. Olenyuk, J. A.
Whiteford, A. Fechtenkötter, P. J. Stang, Nature, 1999, 398, 796-799.
5. Self-Assembly of Nanoscopic Dodecahedra from 50 Predesigned Components, B. Olenyuk, M.
D. Levin, J. A. Whiteford, J. E. Shield, P. J. Stang, J. Am. Chem. Soc., 1999, 121, 10434-10435