Polymerization of Cyclopropenes: Taming the Strain for the Synthesis of Controlled and Sequence-Regulated Polymers.

Cyclopropenes (CPEs) are highly strained cyclic olefins, yet there are surprisingly limited examples leveraging their high strain energy for polymerization. In the past, attempts had been made to polymerize CPEs via cationic and insertion polymerization, but side reactions often gave uncontrolled polymers with mixed backbone structures. Ring-opening metathesis polymerization (ROMP) represents an ideal strategy for polymerizing CPEs to access new types of polymers. The proximity of substituents to the olefin in the small framework of CPEs offers a modular handle to tune the kinetic barrier to propagation by the modulation of the substituents. While the first few studies focused on the homopolymerization of simple alkyl or phenyl disubstituted CPEs, we recently explored the metathesis of a wide range of CPEs with different substituents using Grubbs catalysts and discovered surprising and diverse reactivities that are contingent on the positions, sterics, and electronics of substituents. The observed reactivities ranged from living homopolymerization to catalyst deactivation to single addition to the catalyst without homopropagation. In particular, the exclusively single addition reactivity found in two families of CPEs, with either bis(methanol ester) or phenyl and methanol ester substituents at the allylic position, is unusual for any monomer and perhaps counterintuitive for highly strained cycles. These single-addition CPEs could, however, be copolymerized with low-strain cyclic olefins to generate perfectly alternating copolymers with controlled molecular weights and low dispersity and to introduce degradable backbone linkages. A single equivalent (relative to the active chain end) of such CPEs could also be added to the active chain end of living ROMP polymers to install functional terminal groups or during living ROMP to place single units of functional moieties or side chains at any desired chain locations in narrow-disperse homopolymers and block copolymers. This account summarizes the polymerization of CPEs with a focus on our journey to uncover the rich and unique metathesis reactivities of CPEs and their utility in synthesizing well-controlled and sequence-regulated polymers. It provides the first collective structure-metathesis reactivity relationships for CPEs in the context of polymer chemistry and an understanding of the interactions between the catalyst and the substituents of appended ring-opened CPEs. It may become clear from this Account that the exploration of strained cycles in polymer chemistry can be quite fruitful in discovering new chemistry and accessing new types of polymer materials.

Degradable Polyacetals/Ketals from Alternating Ring-Opening Metathesis Polymerization.

We report the synthesis of degradable polyacetals and polyketals with controlled molecular weights and low dispersities using alternating ring-opening metathesis polymerization (AROMP) of 1,1-disubstituted cyclopropenes and dioxepins. Under optimized conditions, high degrees of alternation and controlled polymerization were achieved between nonpropagating cyclopropenes and low-strain dioxepins. The high degrees of alternation allowed the resulting polymers to fully degrade into small molecules under acidic conditions at variable rates depending on the acetal/ketal structures. This synthetic strategy illustrates the use of AROMP to incorporate functionalities into both the polymer backbone as well as the side chains.

Tuning the Reactivity of Cyclopropenes from Living Ring-Opening Metathesis Polymerization (ROMP) to Single-Addition and Alternating ROMP.

Ring-opening metathesis polymerization (ROMP) has become one of the most important living polymerizations. Cyclopropenes (CPEs) remain underexplored for ROMP. Described here is that the simple swap of 1-methyl to 1-phenyl on 1-(benzoyloxymethyl)CPEs elicited strikingly different modes of reactivity, switching from living polymerization to either selective single-addition or living alternating ROMP. The distinct reactivity stems from differences in steric repulsions at the Ru alkylidene after CPE ring opening. Possible olefin or oxygen chelation from ring-opened CPE substituents was also observed to significantly affect the rate of propagation. These results demonstrate the versatility of CPEs as a new class of monomers for ROMP, provide mechanistic insights for designing new monomers with rare single-addition reactivity, and generate a new functionalizable alternating copolymer scaffold with controlled molecular weight and low dispersity.

Synthesis and Mechanochemical Activation of Ladderene-Norbornene Block Copolymers.

We have recently reported a polymechanophore system, polyladderene (PLDE), which dramatically transforms into polyacetylene (PA) upon mechanical stimulation. Herein, we optimized conditions to synthesize unprecedented block copolymers (BCPs) containing a force-responsive block by sequential ring-opening metathesis polymerization of different norbornenes and bromoladderene. Successful extension from PLDE to other blocks required careful timing and low temperatures to preserve the reactivity of the PLDE-appended catalyst. The PLDE-containing BCPs were sonochemically activated into visually soluble PA with a maximum absorption λ ≥ 600 nm and unique absorption patterns corresponding to noncontinuous activation of ladderene units. Access to polymechanophore BCPs paves the way for new stress-responsive materials with solution and solid state self-assembly behaviors and incorporation of polymechanophores into other materials.

Molecular Engineering of the Peptoid Nanosheet Hydrophobic Core.

The relationship between the structure of sequence-defined peptoid polymers and their ability to assemble into well-defined nanostructures is important to the creation of new bioinspired platforms with sophisticated functionality. Here, the hydrophobic N-(2-phenylethyl)glycine (Npe) monomers of the standard nanosheet-forming peptoid sequence were modified in an effort to (1) produce nanosheets from relatively short peptoids, (2) inhibit the aggregation of peptoids in bulk solution, (3) increase nanosheet stability by promoting packing interactions within the hydrophobic core, and (4) produce nanosheets with a nonaromatic hydrophobic core. Fluorescence and optical microscopy of individual nanosheets reveal that certain modifications to the hydrophobic core were well tolerated, whereas others resulted in instability or aggregation or prevented assembly. Importantly, we demonstrate that substitution at the meta and para positions of the Npe aromatic ring are well tolerated, enabling significant opportunities to tune the functional properties of peptoid nanosheets. We also found that N-aryl glycine monomers inhibit nanosheet formation, whereas branched aliphatic monomers have the ability to form nanosheets. An analysis of the crystal structures of several N,N'-disubstituted diketopiperazines (DKPs), a simple model system, revealed that the preferred solid-state packing arrangement of the hydrophobic groups can directly inform the assembly of stable peptoid nanosheets.

Ring-opening metathesis polymerization of 1,2-disubstituted cyclopropenes.

The ring-opening metathesis polymerization (ROMP) of 1,2-disubstituted cyclopropenes (CPs) has been explored for the first time using Grubbs 3rd generation catalyst. A range of 1,2-CPs yielded polymers with controllable MWs and low dispersitities, and allowed the synthesis of block copolymers, absent from secondary metathesis. However, there existed a competing intramolecular termination pathway for these monomers, limiting the timescale for their ROMP to stay living.