N‐Substituted Azacalixphyrins: Synthesis, Properties, and Self‐Assembly. Issue 49 (11th October 2016)

• Record Type: Journal Article
• Authors: Chen, Zhongrui; Haddoub, Rose; Mahé, Jérôme; Marchand, Gabriel; Jacquemin, Denis; Andeme Edzang, Judicaelle; Canard, Gabriel; Ferry, Daniel; Grauby, Olivier; Ranguis, Alain; Siri, Olivier
• Is Part Of: Chemistry. Volume 22:Issue 49(2016)
• Page Start: 17820
• Page End: 17832
• Publication Date: 2016-10-11
• Subjects: aromaticity -- azacalixphyrins -- macrocycles -- substituent effects -- structure–activity relationships; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201602288
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Pre‐ and postintroduction of substituents with respect to the macrocyclization step leads to previously unknown N‐substituted azacalixphyrins. The stepwise synthetic approach has been studied in detail to highlight the key role of the N‐substituents of the precursors and/or intermediates in terms of reactivity. Based on a combined experimental and theoretical investigation, the relationship between the properties of the macrocycles and their degree of substitution is rationalized. Depending on the nature of the N‐substituents, the formation of supramolecular ribbon‐like structures could also be observed, as demonstrated by combined TEM, SEM, AFM, and FTIR experiments. Abstract : Bring on N ! Unprecedented N‐substituted azacalixphyrins (see scheme) are described based on a thorough investigation that allowed the structure–reactivity relationships of the macrocycles to be rationalized according to their degree of substitution.