title: Influence of selectivity on the supramolecular polymerization of AB-type polymers capable of Both A x A and A x B interactions.
abstract: The supramolecular polymerization of two AB-type monomers capable of hydrogen-bond-mediated A x B heterocoupling and A x A homocoupling is discussed. The AB-type supramolecular polymerization is based on the strong interaction between self-dimerizing 2-ureido-pyrimidinone (UPy) and 2,7-diamido-1,8-naphthyridine (NaPy). In an effort to reduce the "self-stoppered" effect that is inherently present in these supramolecular polymerizations we used a novel ureido-pyrimidinone substituted with a dibutylamino group at the pyrimidinone ring. As a result of the substitution, the dimerization constant of the novel UPy unit is lowered compared to the previous UPy unit while the heterodimerization strength is retained. Unexpectedly, the increased selectivity toward heteroassociation not only influences the concentration-dependent degree of polymerization due to reduction of the "self-stoppered" effect but also has a pronounced effect on the ring-chain equilibrium by increasing the tendency to cyclize. In order to quantitatively explain our results, a model was developed that accurately predicts the degree of polymerization by taking into account homo- and heterodimerization as well as cyclization. Finally, molecular weight distributions for noncyclizing AB supramolecular polymerizations with and without a reversible A x A interaction are calculated. It is found that the molecular weight distribution becomes narrower when A x A interactions are present.
authors.affiliation: Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
authors.forename: Tom F A
authors.initials: TF
authors.lastname: de Greef
authors.forename: Gianfranco
authors.initials: G
authors.lastname: Ercolani
authors.forename: G B W L
authors.initials: GB
authors.lastname: Ligthart
authors.forename: E W
authors.initials: EW
authors.lastname: Meijer
authors.forename: Rint P
authors.initials: RP
authors.lastname: Sijbesma