Cyclic porphyrin oligomers

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... 

Research Objectives of Cyclic Porphyrin Oligomers in the Context... 

Based on the working hypothesis described above, the author focuses on the chemistry of cyclic porphyrin oligomers (CPOs). As described in the next section, porphyrin is a multi-functional compound and the nano-sized closed space created by these molecules should therefore be of interest to chemists. 

Thousands of cyclic-shaped molecules are known. Why then must we focus on the cyclic porphyrin oligomers (CPOs) in the context of dendrimer chemistry Are there any specific properties and functions associated with CPOs ... 

To reveal the light-harvesting process, synthetic studies on cyclic porphyrin oligomers, designed based on the information of the protein structure, are considered. Nature adopted the cyclic alignment of chlorophyll. Is the closed cyclic... 

Sanders and coworkers have since used their cyclic porphyrin oligomers to catalyze acyl-transfer reactions (49) and hetero-Diels-Alder reactions (50). 

Metal coordination also enables organic ligands to be used as templates. Sanders and co-workers have synthesized cyclic porphyrin oligomers using Glaser-Hay coupling [16,40]. This reaction oxidatively combines two terminal acetylenes to give a 1,3-buta-diyne link. The syntheses of cyclic porphyrin dimer 38 and trimer 39 were effectively templated by 4,4 -bipyridine 37 and tripyridyltriazine 22, respectively (Scheme 1-10). 

H. L. Anderson, J. K. M. Sanders, Synthesis of cyclic porphyrin oligomers with amines as templates, Angew. Chem., 1990, 102, 1478-1480 Angew. Chem., Int. Ed. Engl, 1990, 29, 1400-1403. 

The first cyclic porphyrin dimer (cyclophane porphyrin) linked with two ester groups 15 was synthesized as a model of antenna chlorophyll dimer by condensation of a 2,12-dipropionate porphyrin and a 2,12-bis-(3-hydroxypropyl) porphyrin in high dilution in 1977." In order to clarify the mechanism of electron-transfer reactions in biological systems, a variety of porphyrin dimers have been reported as model systems of parts of the photosynthetic apparatus in the last two decades. The first synthesis of cyclic porphyrin oligomers was reported by Hamilton, Lehn and Sessler in 1986. ... 

Sanders and coworkers have developed syntheses of rather rigid cyclic oligoporphyrins (porphyrin-linker), (n = 2 4) by catalytic-coupling reactions of acetylene derivatives with copper salts. In particular, incorporation of metal ions into cyclic porphyrin oligomers provides the multi-interaction sites necessary to tightly bind heterocyclic compounds in the inner cavity (see section IV).Rigidity of host molecules is controlled by the structure of the linkage moieties. 

Figure 18. Geometry regulation of cyclic porphyrin oligomer.

Anderson, H.L. and J.K.M. Sanders (1995). Enzyme mimics based on cyclic porphyrin oligomers—strategy, design and exploratory synthesis. J. Chem. Soc. Perkin Trans. 1 2223-2229. 

Our interest in building enzyme mimics based on porphyrins led us to synthesise cyclic porphyrin oligomers using Glaser coupling.[9] This reaction oxidatively combines two terminal acetylenes to give a butadiyne link ... 

Figure 2. Glaser-Hay coupling of 3 to give cyclic porphyrin oligomers.

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