Self-assembled molecular cages

Photochemical Reaction with Self-Assembled Molecular Cages... 

M. Yoshizawa, S. Miyagi, M. Kawano, K. Ishiguro, M. Fujita, Alkane oxidation via photochemical excitation of a self-assembled molecular cage, J. Am. Chem. Soc., 2004, 126, 9172. 

Recently, it has been found that the outcome of some cycloadditions can be altered remarkably when performed inside the cavity of cyclodextrins (288), self-assembled molecular capsules (289), or coordination cages (290). This fact intrigued us greatly and stimulated our interest in the Diels-Alder reactivity of the calixarene-like [M2(L19)(L )]+ complexes bearing unsaturated carboxylate coligands L (215). 

Figure 1.11 Fujita s self-assembled coordination cage, which is prepared by simple mixing of an exo-tridentate organic ligand and end-capped Pd (I I) ion in a 4 6 ratio. Cache optimized structure of the ternary complex anthracene-maleimide metallocage. Molecular structure ofthesyn-isomerofthe 1,4-Diels-Alder adduct.

Yoshizawa, M. and Fujita, M. (2005) Self-assembled coordination cage as a molecular fiask. Pure Appl. Chem., 77 (7), 1107-1112. 

Keywords Self-assembly, Molecular recognition. Nanotechnology, Cage, Bowl, Tube, Capsule,... 

Heinz, T. Rudkevich, D.M. Rebek, J., Jr. Molecular recognition within a self-assembled cylindrical host. Angew. Chem., Int. Ed. 1999. 38 (8), 1136-1139. Yoshizawa, M. Kusukawa, T. Fujita, M. Yamaguchi. K. Ship-ill-a-bottle synthesis of otherwise labile cyclic trimers of siloxanes in a self-assembled coordination cage. J. Am. Chem. Soc. 2000. 122 (26), 6311-6312. 

Adamantane can be used to construct peptidic scaffolding and synthesis of artificial proteins. It has been introduced into different types of synthetic peptidic macrocycles, which are useful tools in peptide chemistry and stereochemistry studies and have many other applications as well. Introduction of amino acid-functionalized adamantane to the DNA nanostmctures might lead to construction of DNA-adamantane-amino acid nanostmctures with desirable stiffness and integrity. Diamondoids can be employed to constmct molecular rods, cages, and containers and also for utilization in different methods of self-assembly. In fact, through the development of self-assembly approaches and utilization of diamondoids in these processes, it would be possible to design and constmct novel nanostmctures for effective and specific carriers for each dmg. 

Construction of discrete and well-defined molecular architectures using organic ligands and metal ions through the self-assembly route has received much attention. A dinuclear Pd11 cage,636 includes a hexafluorophosphate ion inside the cavity. Self-assembly of a novel macrotricyclic cage... 

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