p-tert-Butylthiacalix[4]arenes containing guanidinium groups: synthesis and self-assembly into nanoscale aggregates

• Published in: Supramolecular chemistry Vol. 31; no. 7; pp. 473 - 483
• Main Authors: Andreyko, Elena A., Puplampu, Joshua B., Ignacio-De Leon, Patricia A., Zharov, Ilya, Stoikov, Ivan I.
• Format: Journal Article
• Language: English
• Published: Abingdon Taylor & Francis 03-07-2019; Taylor & Francis Ltd
• Subjects: aggregate; Aggregates; Aromatic compounds; guanidinium; nanoscale; Oxalic acid; p-tert-Butylthiacalixarene; Self-assembly; Stoichiometry
• ISSN: 1061-0278; 1029-0478
• DOI: 10.1080/10610278.2019.1628231

New p-tert-butylthiacalix[4]arenes with several different substituents at the lower rim have been synthesised. A method for the selective introduction of one or two guanidinium fragments into the structure of p-tert-butylthiacalix[4]arenes has been developed. The 1,3-alternate thiacalix[4]arenes containing guanidinium groups interact with silver nitrate and oxalic acid in methanol with a logK
assoc
of about 3.5 and 1:1 stoichiometry, while the macrocycle in the cone conformation interacts with oxalic acid with logK
assoc
of 7.4 and 2:1 stoichiometry. The new p-tert-butylthiacalix[4]arenes form nanoscale aggregates with hydrodynamic radii of about 70 nm by self-association and by mediation with silver cations and oxalic acid.