Carboxyphenyl-Substituted Pyrazinoporphyrazines - Promising Linkers for Metal-Organic Frameworksстатья
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Дата последнего поиска статьи во внешних источниках: 15 февраля 2024 г.
Аннотация:Starting from the new building-block – dimethyl-4,4'-(5,6-dicyanopyrazine-2,3-diyl)dibenzoate 1, a new symmetrical porphyrazine annelated with four bis(4-carboxyphenyl)pyrazine rings and its Zn(II) complex MPyzPz(COOH)8, M = = 2H and Zn, have been synthesized for the first time. It was shown that template condensation of 1 in the presence of Zn(OAc)2 and DBU, followed by alkaline hydrolysis of the ester groups, failed to yield the target Zn(II) complex due to its degradation in strongly basic media. In contrast, template condensation of 1 in the presence of metal Mg in pentanol followed by demetallation afforded the metal-free ester derivative H2PyzPz(COOPent)8, which could be hydrolyzed to H2PyzPz(COOH)8 without degradation of the macrocycle. Its reaction with Zn(OAc)2 in DMF resulted in the insertion of Zn2+ into the tetrapyrrole macrocycle, yielding ZnPyzPz(COOH)8. The difference in hydrolytic stability of metal-free porphyrazine and its metal complex was explained by electrostatic potential analysis. Due to their structural similarity with an organic linker 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine H4TCPP, it is suggested that the synthesized pyrazinoporphyrazines can be used as linkers of novel metal-organic frameworks.