Quantitative Synthesis and Function Development of Macrocycles Based on Slow Deprotection Self-polycondensation and Dynamic Covalent Chemistry

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Mechanism for the quantitative formation of a macrocycle Cm6(cyclic hexakis(m-phenyleneimine)) from m-aminobenzaldehyde diethylacetal via water-initiated slow-deprotection polycondensation was investigated using MALDI-TOF MS and SEC. The reversibility in formation-cleavage of imine linkage, that is dynamic covalent chemistry, and.-staking interaction between flat Cm6 molecules had played a significant role in the quantitative formation. A variety of imine-type macrocycles having a functional group were successfully prepared using this method, which was found to be a potential protocol for the macrocycle synthesis. Mutual conversion between the macrocycle and the soluble linear polymers having a wide range of molecular weights by a heat stimulus was observed. The collapse-regeneration of the macrocycle was a reversible process. A mixture of two kinds of macrocycles gave a complex containing each building block. With the aid of an iminomethylene-type analogue Cm6H, which was readily prepared by the hydride-reduction of imine linkage in Cm6, a fullerene C_<60> was dissolved in a polar solvent like DMSO. Indigo carmine and new coccine dyes were precipitated from the acid solutions by addition of Cm6H.