Michael Addition-Elimination Ring-Opening Polymerization.

A cyclic thioenone system capable of controlled ring-opening polymerization (ROP) is presented that leverages a reversible Michael addition-elimination (MAE) mechanism. The cyclic thioenone monomers are easy to access and modify and for the first time incorporate the dynamic reversibility of MAE with chain-growth polymerization. This strategy features mild polymerization conditions, tunable functionalities, controlled molecular weights (Mn), and narrow dispersities. The obtained polythioenones exhibit excellent optical transparency and good mechanical properties and can be depolymerized to recover the original monomers. Density functional theory (DFT) calculations of model reactions offer insights into the role of monomer conformation in the polymerization process, as well as explaining divergent reactivity observed in seven-membered thiepane (TP) and eight-membered thiocane (TC) ring systems. Collectively, these findings demonstrate the feasibility of MAE mechanisms in ring-opening polymerization and provide important guidelines toward future monomer designs.

Modulating Polymerization Thermodynamics of Thiolactones Through Substituent and Heteroatom Incorporation.

A central challenge in the development of next-generation sustainable materials is to design polymers that can easily revert back to their monomeric starting material through chemical recycling to monomer (CRM). An emerging monomer class that displays efficient CRM are thiolactones, which exhibit rapid rates of polymerization and depolymerization. This report details the polymerization thermodynamics for a series of thiolactone monomers through systematic changes to substitution patterns and sulfur heteroatom incorporation. Additionally, computational studies highlight the importance of conformation in modulating the enthalpy of polymerization, leading to monomers that display high conversions to polymer at near-ambient temperatures, while maintaining low ceiling temperatures (Tc). Specifically, the combination of a highly negative enthalpy (-19.3 kJ/mol) and entropy (-58.4 J/(mol·K)) of polymerization allows for a monomer whose equilibrium polymerization conversion is very sensitive to temperature.

Toward Recyclable Polymers: Ring-Opening Polymerization Enthalpy from First-Principles.

Ring-opening polymerization (ROP) enthalpy ΔHROP is an important thermodynamic property controlling the polymerization of cyclic monomers. While ΔHROP can be measured, computing ΔHROP for realistic polymer systems with an error of ≃5-10 kJ/mol is critical for designing new monomer systems for depolymerizable polymers. We have developed a first-principles computational scheme in which multiple challenges in computing ΔHROP are resolved definitively including extensive exploration of conformational states and adequately addressing finite size effects. This scheme is validated on a diverse benchmark set of 42 ROP polymers for which reliable experimental values of ΔHROP are available. For this set, the ΔHROP root-mean-square error is ≃7 kJ/mol, about 3-times smaller than conventional approaches. This development opens up new pathways to build up a high-quality database of ΔHROP for downstream predictive machine-learning models and ultimately to accelerate the design of depolymerizable polymers with desired properties.

Modulating Twisted Amide Geometry and Reactivity Through Remote Substituent Effects.

The unusual reactivity of twisted amides has long been associated with the degree of amide distortion, though classical bridged bicyclic amides offer limited methods to further modify these parameters. Here, we report that the geometry and reactivity of a single twisted amide scaffold can be significantly modulated through remote substituent effects. Guided by calculated ground state geometries, a library of twisted amide derivatives was efficiently prepared through a divergent synthetic strategy. Kinetic and mechanistic investigations of these amides in the alkylation/halide-rebound ring-opening reaction with alkyl halides show a strong positive correlation between the electron donating ability of the substituent and distortion of the amide bond, leading to rates of nucleophilic substitution spanning nearly 2 orders of magnitude. The rate limiting step of the cascade sequence is found to be dependent on the nature of the substituent, and additional studies highlight the role of solvent polarity and halide ion on reaction pathway and efficiency.

Multi-State Dynamic Coordination Complexes Interconverted through Counterion-Controlled Phase Transfer.

We studied a series of dynamic weak-link approach (WLA) complexes that can be shuttled between two immiscible solvents and switched between two structural states via ion exchange. Here, we established that hydrophobic anions transfer cationic, amphiphilic complexes from the aqueous phase to the organic phase, while a chloride source reverses the process. As a result of the dynamic metal coordination properties of WLA complexes, the denticity of these complexes (mono- to bi-) can be modulated as they partition into different phases. In addition, we discovered that heteroligated complexes bearing ligands of different donor strengths preferentially rearrange into two homoligated complexes that are phase-partitioned to maximize the number of stronger coordination bonds. This behavior is not observed in systems with one solvent, highlighting the dynamic and stimuli-responsive nature of hemilabile ligands in a multiphasic solvent environment. Taken together, this work shows that the highly reconfigurable WLA modality can enable the design of biphasic reaction networks or chemical separations driven by straightforward salt metathesis reactions.