Nano-sized spaces

Sugiura K (2003) An Adventure in Macromolecular Chemistry Based on the Achievements of Dendrimer Science Molecular Design, Synthesis, and Some Basic Properties of Cyclic Porphyrin Oligomers to Create a Functional Nano-Sized Space. 228 65-85 Sun J-Q, Bartlett RJ (1999) Modern Correlation Theories for Extended, Periodic Systems. 203 121-145... 

Dendrimer chemistry has taught us that these molecules create a nano-sized closed space that, presumably, is the origin of the specific physical properties of this class of materials. As the next stage of dendrimer chemistry, a macromolecule capable of creating such a space inside its molecule is proposed. To create the nano-sized space, porphyrin is considered to be the best candidate for the component molecules, because it has versatile properties associated with its expanded 7i-electron system and the incorporated metal. The resultant multi-detectable properties of porphyrin, that is, a number of its properties are detectable by many physical methods, may reveal the function of the nanometer-sized space. 

Keywords. Nano-sized space. Porphyrin, Cyclic oligomer. Multi-detectable molecule. Inverse-template effect... 

CPOs are best characterized by the following three features 1) axial coordination to the incorporated metals, 2) specific nano-sized space created by rigid porphyrin panels, and 3) specific (photo-induced) redox reactions associated with the porphyrin s rr-electron system. In this chapter, some examples are reviewed based on these properties. 

Fig. 10. Enzymatic regioselective Diels-Alder reaction of 22 and 23. The catalyst with a small nano-sized space selectively produces e/ido-adduct, 24, and the other catalyst with a large space produces exo-adduct 25...

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