Synthesis of New Diaryl-Substituted Triple-Decker and Tetraaryl-substituted Double-Decker Lanthanum(III) Porphyrins and Their Porphyrin Ring Rotational Speed as Compared with that of Double-Decker Cerium(IV) Porphyrins

Tetraaryl-substituted cerium(IV) double-decker porphyrin (2D), tetraaryl-substituted lanthanum(III) double-decker porphyrin (3D), and diaryl-substituted lanthanum(III) triple-decker porphyrins (4T•Me and 4T•MeO) were newly synthesized and their porphyrin ring rotation rates were systematically estimated by means of a VT NMR spectroscopic method. In 2D the coalescence temperature (Tc) for the porphyrin ring rotation was higher than 110 °C, whereas in 3D it appeared at ca. 0 °C. In diaryl-substituted cerium(IV) double-decker porphyrin (5D) it appeared at 13 °C whereas in 4T•Me and 4T•MeO they were lower than −80 °C. These results consistently support the view that the porphyrin ring rotation rates in lanthanum(III)-based porphyrins are much faster than those in cerium(IV)-based porphyrins. The difference is reasonably explained by the difference in the ion size between these two metal ions. Since these sandwich-type porphyrins can act as novel scaffolds for designing positive allosteric recognition systems,...

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