Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis

25 October 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Poly(disulfide)s are an emerging class of sulfur-containing polymers with applications in medicine, energy, and functional materials. However, the constituent dynamic covalent S−S bond is highly reactive in the presence of sulfide (RS−) anion, imposing a persistent challenge to control the polymerization. Here, we report an anion-binding approach to arrest the high reactivity of RS− chain end to control the synthesis of linear poly(disulfide)s, realizing a rapid, living ring-opening polymerization of 1,2-dithiolanes with narrow dispersity and high regioregularity (Mw /Mn ~ 1.1, Ps ~ 0.85). Mechanistic studies support the formation of a thiourea-base-sulfide ternary complex as the catalytically active species during the chain propagation. Theoretical analyses reveal a synergistic catalytic model where the catalyst preorganizes the protonated base and anionic chain end to establish spatial confinement over the bound monomer, effecting the observed regioselectivity. The catalytic system is amenable to monomers with various functional groups, and semicrystalline polymers are also obtained from lipoic acid derivatives by enhancing the regioregularity.


anion binding
ring-opening polymerization

Supplementary materials

Supporting Information
Experimental and computational procedures, synthesis and characterization of new compounds, GPC and NMR data for polymerization of different conditions, experimental studies on polymerization mechanism, theoretical analysis of regioregularity, computational results, and XYZ coordinates.


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