Orthogonal chain length control in calix[5]arene-based AB-type supramolecular polymers

New AB-type supramolecular polymers have been prepared by acid-promoted self-assembly of an aminododecyloxy-calix[5]arene monomer precursor. The number-average degree of polymerization has been found to be dependent on the concentration of the salt monomer and on the nature of the counterion (i.e., chloride, picrate or hexafluorophosphate). length regulation experiments have been carried out, employing orthogonal chain stoppers capable of selectively interacting with a given moiety of the AB-type monomer/polymer. Competitive calix[5]arene ‘caps’ and n-butylammonium ion ‘plugs’ have been used to control the extent of self-assembly of the polymer, in turn interacting with the ammoniumdodecyloxy or with the cavity end-groups of the supramolecular calixarene assembly. These experiments, conveniently carried out at a 10 mM concentration, can be easily followed by 1H NMR spectroscopy.