Adv Polym Sci (2013) 261: 229–248
DOI: 10.1007/12_2013_244
© Springer-Verlag Berlin Heidelberg 2013
Published online: 6 November 2013
Coordination-Driven Supramolecular
Macromolecules via the Directional Bonding
Approach
Timothy R. Cook and Peter J. Stang
Abstract Coordination-driven self-assembly is a process that generates supramolecular architectures from molecular precursors by exploiting the favorable
properties of metal–ligand bonding. The discrete supramolecular coordination
complexes (SCCs) thus obtained have enjoyed multiple decades of development,
focused initially on the design and reactivity of rigid building blocks with specific
directionalities and angularities, thereby populating a molecular library of complementary donor and acceptor subunits. More recently, efforts have broadened to
encompass pre- and post-self-assembly modifications, which have lead to new
routes for obtaining functionalized metallacages and metallacycles, multicomponent assemblies incorporating multiple types of ligands in a single scaffold, and
supramolecular transformations that quantitatively alter the structure of a given
SCC, furnishing an entirely new architecture.
Keywords Coordination-driven self-assembly Á Directional bonding Á Metallacage Á
Metallacycle Á Supramolecular coordination complex
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
2 Molecular Squares: Establishing a Molecular Library . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
3 Triangles, Hexagons, and Other 2D Metallacycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
4 Supramolecular Polyhedra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4.1 Platonic and Archimedean Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4.2 Prismatic Metallacages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . 238
T.R. Cook (*) and P.J. Stang
Department of Chemistry, University of Utah, Salt Lake City, UT, USA
e-mail: timcook@chem.utah.edu
DOI: 10.1007/12_2013_244
© Springer-Verlag Berlin Heidelberg 2013
Published online: 6 November 2013
Coordination-Driven Supramolecular
Macromolecules via the Directional Bonding
Approach
Timothy R. Cook and Peter J. Stang
Abstract Coordination-driven self-assembly is a process that generates supramolecular architectures from molecular precursors by exploiting the favorable
properties of metal–ligand bonding. The discrete supramolecular coordination
complexes (SCCs) thus obtained have enjoyed multiple decades of development,
focused initially on the design and reactivity of rigid building blocks with specific
directionalities and angularities, thereby populating a molecular library of complementary donor and acceptor subunits. More recently, efforts have broadened to
encompass pre- and post-self-assembly modifications, which have lead to new
routes for obtaining functionalized metallacages and metallacycles, multicomponent assemblies incorporating multiple types of ligands in a single scaffold, and
supramolecular transformations that quantitatively alter the structure of a given
SCC, furnishing an entirely new architecture.
Keywords Coordination-driven self-assembly Á Directional bonding Á Metallacage Á
Metallacycle Á Supramolecular coordination complex
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
2 Molecular Squares: Establishing a Molecular Library . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
3 Triangles, Hexagons, and Other 2D Metallacycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
4 Supramolecular Polyhedra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4.1 Platonic and Archimedean Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4.2 Prismatic Metallacages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . 238
T.R. Cook (*) and P.J. Stang
Department of Chemistry, University of Utah, Salt Lake City, UT, USA
e-mail: timcook@chem.utah.edu