Metal-templated synthesis of rigid and conformationally restricted cyclic bisporphyrins: specific retention times on a cyanopropyl-modified silica gel column

A series of rigid and conformationally restricted cyclic bis(zinc porphyrin)s connected via 2,2′-bipyridine and phthalamide, isophthalamide, or terephthalamide moieties were prepared by metal-templated synthesis. The yields were significantly improved when compared with those obtained under metal-free conditions. In particular, phthalamide and terephthalamide derivatives were obtained only by metal-templated synthesis. Structural analyses and dynamics of the exchange between the conformers in each cyclic porphyrin were examined by NMR spectroscopy. Although the distances between the two zinc porphyrins were extended in the order of phthalamide, isophthalamide, and terephthalamide derivatives, the order of the specific retention of the cyclic porphyrins on cyanopropyl-modified silica gel (CN-MS) chromatography columns varied. Thus, this order was reversed in the isophthalamide and terephthalamide derivatives. Based on the rigid structure of the terephthalamide derivative, the origin of the specific retention on the CN-MS chromatography column was attributed to both the distance and rigidity of the cyclic porphyrins. Both the distance and rigidity are important for strong retentions on a cyanopropyl-modified silica gel column.