Abstract
We investigate the copolymerization behavior of a two-component system into quasi-linear self-assemblies under conditions that interspecies binding is favored over identical species binding. The theoretical framework is based on a coarse-grained self-assembled Ising model with nearest neighbor interactions. In Ising language, such conditions correspond to the anti-ferromagnetic case giving rise to copolymers with predominantly alternating configurations. In the strong coupling limit, we show that the maximum fraction of polymerized material and the average length of strictly alternating copolymers depend on the stoichiometric ratio and the activation free energy of the more abundant species. They are substantially reduced when the stoichiometric ratio noticeably differs from unity. Moreover, for stoichiometric ratios close to unity, the copolymerization critical concentration is remarkably lower than the homopolymerization critical concentration of either species. We further analyze the polymerization behavior for a finite and negative coupling constant and characterize the composition of supramolecular copolymers. Our theoretical insights rationalize experimental results of supramolecular polymerization of oppositely charged monomeric species in aqueous solutions.
Original language | English |
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Article number | 014902 |
Number of pages | 17 |
Journal | Journal of Chemical Physics |
Volume | 151 |
Issue number | 1 |
DOIs | |
Publication status | Published - 7 Jul 2019 |
Funding
R.V.B. and S.J.F. gratefully acknowledge the financial support from the German Research Foundation (http://www.dfg.de) within SFB TRR 146 (http://trr146.de). C. Berac is the recipient of a position through the DFG Excellence Initiative by the Graduate School Materials Science in Mainz (GSC 266).