Coordination-driven self-assembly

A self-assembled coordination cage and micelles were found to accelerate Diels-Alder reactions in an aqueous media. The catalysis of Diels-Alder reactions via noncovalent binding by synthetic, protein, and nucleic acid hosts has been surveyed and compared to explore the origin of the noncovalent catalysis. These catalysts consist of binding cavities that form complexes containing both the diene with the dienophile and the reaction occurring in the cavity. The binding requires no formation of covalent bonds and is driven principally by the hydrophobic (or solvophobic) effect. ... 

Figure 86 The coordination-driven carborane-containing self-assembled polymers,...

This chapter gives a short history of coordination-driven self-assembly, with a special attention to organometallic metalla-cycles, especially those composed of half-sandwich complexes. These metalla-assemblies have been used as sensors, as anticancer agents, as well as drug carriers. 

Northrop BH, Zheng Y-R, Chi K-W, Stang PJ (2009) Self-organization in coordination-driven self-assembly. Acc Chem Res 42 1554—1563... 

A large and diverse number of transition-metal coordination numbers and geometries can be used in the construction of coordination-driven assemblies, giving access to different topologies rather difficult to obtain with the classical synthetic methods. The synthetic process is under thermodynamic control when relatively labile metal centers are used (true supramolecular self-assembly), while it is under kinetic control with inert metals (unless high temperatures are used). 

The metal-mediated synthetic approach has recently provided many examples of large discrete assemblies of porphyrins [39-41] and of solid-state arrays as well [39-48]. For the purpose of metal-driven synthesis, porphyrins and metal centers are to be considered essentially as rigid modules. Thus, in principle, the final shape, dimension, and topology of the self-assembled architecture will be defined by the number and relative geometries of the coordination sites on the building blocks. Within this framework, meso-pyridylporphyrins (PyPs, Fig. 1) are largely exploited as they can provide... 

Kryschenko. Y.K. Seidel. R.S. Arif. A.M. Stang. P.J. Coordination-driven self-assembly of predesigned supra-molecular triangles. J. Am. Chem. Soc. 2003. 125 (17), 5193-5198. 

The self-assembling process involves noncovalent or weak interactions (van der Waals, electrostatic, and hydrophobic interactions, hydrogen and coordination bonds, and r-7T stacking). This process corresponds to a variation of reversed pore structures. Most ordered mesoporous materials are derived from the thermodynamically stable and ordered a regates spontaneously driven by the noncovalent interactions between molecules. These aggregates come from the cationic, anionic and nonionic surfactants, neutral amines, block copolymers, or their mixtures (Figure 13.1). They are disordered on the atomic or... 

Coordination-driven self-assembly of arene—ruthenium compounds 13EJI5222. 

Bimetallic platinum complexes are known as unique building blocks and are widely utilized in the coordination-driven self-assembly of functionalized supramolecular metallacycles. A detailed photophysical study of some bimetallic platinum compounds (see formula below) has been carried out, evidencing the role of H bonding with the solvent. 

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