Vinylogous Urea-Urethane Vitrimers: Accelerating and Inhibiting Network Dynamics through Hydrogen Bonding.

Vinylogous urethane (VUO ) based polymer networks are widely used as catalyst-free vitrimers that show rapid covalent bond exchange at elevated temperatures. In solution, vinylogous ureas (VUN ) undergo much faster bond exchange than VUO and are highly dynamic at room temperature. However, this difference in reactivity is not observed in their respective dynamic polymer networks, as VUO and VUN vitrimers prepared herein with very similar macromolecular architectures show comparable stress relaxation and creep behavior. However, by using mixtures of VUO and VUN linkages within the same network, the dynamic reactions can be accelerated by an order of magnitude. The results can be rationalized by the effect of intermolecular hydrogen bonding, which is absent in VUO vitrimers, but is very pronounced for vinylogous urea moieties. At low concentrations of VUN , these hydrogen bonds act as catalysts for covalent bond exchange, while at high concentration, they provide a pervasive vinylogous urea - urethane (VU) network of strong non-covalent interactions, giving rise to phase separation and inhibiting polymer chain dynamics. This offers a straightforward design principle for dynamic polymer materials, showing at the same time the possible additive and synergistic effects of supramolecular and dynamic covalent polymer networks.

Enhancing the Equilibrium of Dynamic Thia-Michael Reactions through Heterocyclic Design.

Although the catalyst-free dynamic thia-Michael (tM) reaction has been leveraged for a range of significant applications in materials science and pharmaceutical development, exploiting its full potential has been limited by relatively low equilibrium constants. To address this shortcoming, a new series of catalyst-free, room-temperature dynamic thia-Michael acceptors bearing an isoxazolone motif were developed and utilized to access both dynamic covalent networks and linear polymers. By leveraging the generation of aromaticity upon thiol addition and tuning the electronic-withdrawing/donating nature of the acceptor at two different sites, a wide range of equilibrium constants (Keq ∼1000 to ∼100,000 M-1) were obtained, constituting a 2 orders of magnitude increase compared to their noncyclic benzalcyanoacetate analogues. Integration into a ditopic isoxazolone-based Michael acceptor allowed access to both bulk dynamic networks and linear polymers; these materials not only exhibited tailorable thermomechanical properties based on thia-Michael acceptor composition, but the higher Keq tM bonds resulted in more mechanically robust materials relative to past designs. Furthermore, solution-state formation of linear polymers was achieved thanks to the increased Keq of the isoxazolone-based acceptors.

Dynamic-bond-induced sticky friction tailors non-Newtonian rheology.

Frictional network formation has become a new paradigm for understanding the non-Newtonian shear-thickening behavior of dense suspensions. Recent studies have exclusively focused on interparticle friction that instantaneously vanishes when applied shear is ceased. Herein, we investigate a friction that emerges from dynamic chemical bridging of functionalized particle surfaces sheared into close proximity. This enables tailoring of both friction magnitude and the time release of the frictional coupling. The experiments use dense suspensions of thiol-functionalized particles suspended in ditopic polymers endcapped with benzalcyanoacetamide Michael-acceptors. The subsequent room temperature, catalyst-free dynamic thia-Michael reactions can form bridging interactions between the particles with dynamic covalent bonds that linger after formation and release in the absence of shear. This chemical friction mimics physical friction but is stickier, leading to tunable rheopexy. The effect of sticky friction on dense suspension rheology is explored by varying the electronic nature of the benzalcyanoacetamide moiety, the molecular weight of the ditopic polymers, the amount of a competitive bonding compound, and temperature. These results demonstrate how dynamic-bond-induced sticky friction can be used to systematically control the time dependence of the non-Newtonian suspension rheology.

Balancing ring and stopper group size to control the stability of doubly threaded [3]rotaxanes.

Synthesizing doubly threaded [3]rotaxanes requires the use of larger rings than more traditional singly threaded [2]rotaxanes. A key challenge in accessing stable doubly threaded [3]rotaxanes with large rings is finding the right combination of ring to stopper size. In this study, a series of doubly threaded [3]rotaxanes derived from five different sized macrocycles in the size range of 40-48 atoms and two different stopper groups, which contain 1 or 2 tris(p-t-butylbiphenyl)methyl moieties, were prepared and their kinetic stability examined. These interlocked compounds were synthesized using a metal-templated approach and fully characterized utilizing a combination of mass spectrometry, NMR spectroscopy, and size-exclusion chromatography techniques. The effect of ring size on the stability of the doubly threaded [3]rotaxane was investigated via kinetic stability tests monitored using 1H-NMR spectroscopy. By tightening the macrocycle systematically every 2 atoms from 48 to 40 atoms, a wide range of doubly threaded interlocked molecules could be accessed in which the rate of room temperature slippage of the macrocycle from the dumbbells could be tuned. Using the larger stopper group with a 48-atom ring results in no observable rotaxane, 46-44 atom macrocycles result in metastable rotaxane species with a slippage half-life of ∼5 weeks and ∼9 weeks, respectively, while macrocycles of 42 atoms or smaller yield a stable rotaxane. The smaller sized stopper is not able to fully stabilize any of the [3]rotaxane structures but metastable [3]rotaxanes are obtained with slippage half-lives of 25 ± 2 hours and 13 ± 1 days using macrocycles with 42 or 40 atoms, respectively. These results highlight the dramatic effect that relatively small ring size changes can have on the structure of doubly threaded [3]rotaxanes and lay the synthetic groundwork for a range of higher order doubly threaded interlocked architectures.

Polymer Stereocomplexation as a Scalable Platform for Nanoparticle Assembly.

DNA-mediated assembly of inorganic particles has demonstrated to be a powerful approach for preparing nanomaterials with a range of interesting optical and electrical properties. Building on this inspiration, we describe a generalizable gram-scale method to assemble nanoparticles through the formation of poly(methyl methacrylate) (PMMA) triple-helices. In this work, alkene-terminated syndiotactic (st-) and isotactic (it-) PMMA polymers were prepared and subsequently functionalized to afford nanoparticle ligands. Nanoparticles with complementary st- and it-PMMA ligands could then be spontaneously assembled upon mixing at room temperature. This process was robust and fully reversible through multiple heating and cooling cycles. The versatility of PMMA stereocomplexation was highlighted by assembling hybrid structures composed of nanoparticles of different compositions (e.g., Au and quantum dots) and shapes (e.g., spheres and rods). These initial demonstrations of nanoparticle self-assembly from inexpensive PMMA-based materials present an attractive alternative to DNA-based nanomaterials.

Light-Controllable Ionic Conductivity in a Polymeric Ionic Liquid.

Polymeric ionic liquids (PILs) have attracted considerable attention as electrolytes with high stability and mechanical durability. Light-responsive materials are enabling for a variety of future technologies owing to their remote and noninvasive manipulation, spatiotemporal control, and low environmental impact. To address this potential, responsive PIL materials based on diarylethene units were designed to undergo light-mediated conductivity changes. Key to this modulation is tuning of the cationic character of the imidazolium bridging unit upon photoswitching. Irradiation of these materials with UV light triggers a circa 70 % drop in conductivity in the solid state that can be recovered upon subsequent irradiation with visible light. This light-responsive ionic conductivity enables spatiotemporal and reversible patterning of PIL films using light. This modulation of ionic conductivity allows for the development of light-controlled electrical circuits and wearable photodetectors.

Controlling Dark Equilibria and Enhancing Donor-Acceptor Stenhouse Adduct Photoswitching Properties through Carbon Acid Design.

A novel library of tunable negative photochromic compounds, donor-acceptor Stenhouse adducts (DASAs), is reported. Tailoring the electron deficient "acceptor" moiety yielded DASAs that can be activated with mild visible and far red light. The effect of acceptor composition on reactivity, absorption, equilibrium, and cyclability is exploited for the design of high performance photoswitches. The structural changes to the carbon acid acceptor also provide access to new, more structurally diverse DASA derivatives by facilitating the ring-opening reaction with electron deficient amine donors.

Simultaneous Preparation of Multiple Polymer Brushes under Ambient Conditions using Microliter Volumes.

The fabrication of well-defined, multifunctional polymer brushes under ambient conditions is described. This facile method uses light-mediated, metal-free atom-transfer radical polymerization (ATRP) to grow polymer brushes with only microliter volumes required. Key to the success of this strategy is the dual action of N-phenylphenothiazine (PTH) as both an oxygen scavenger and polymerization catalyst. Use of simple glass cover slips results in a high degree of spatial and temporal control and allows for multiple polymer brushes to be grown simultaneously. The preparation of arbitrary 3D patterns and functional/emissive polymer brushes demonstrates the practicality and versatility of this novel strategy.

Tunable Visible and Near Infrared Photoswitches.

A class of tunable visible and near-infrared donor-acceptor Stenhouse adduct (DASA) photoswitches were efficiently synthesized in two to four steps from commercially available starting materials with minimal purification. Using either Meldrum's or barbituric acid "acceptors" in combination with aniline-based "donors", an absorption range spanning from 450 to 750 nm is obtained. Additionally, photoisomerization results in complete decoloration for all adducts, yielding fully transparent, colorless solutions and films. Detailed investigations using density functional theory, nuclear magnetic resonance, and visible absorption spectroscopies provide valuable insight into the unique structure-property relationships for this novel class of photoswitches. As a final demonstration, selective photochromism is accomplished in a variety of solvents and polymer matrices, a significant advantage for applications of this new generation of DASAs.

Connecting Molecular Exchange Dynamics to Stress Relaxation in Phase-Separated Dynamic Covalent Networks.

A suite of phase separated dynamic covalent networks based on highly tunable dynamic benzalcyanoacetate (BCA) thia-Michael acceptors are investigated. In situ kinetic studies on small molecule model systems are used in conjunction with macroscopic characterization of phase stability and stress relaxation to understand how the molecular dynamics relate to relaxation modes. Electronic modification of the BCA unit strongly impacts the exchange dynamics (particularly the rate of dissociation) and the overall equilibrium constant (Keq) of the system, with electron-withdrawing groups leading to decreased dissociation rate and increased Keq. Critically, below a chemistry-defined temperature cutoff (related to the stability of the hard phase domains), the stress relaxation behavior of these phase separated materials is dominated by the molecular exchange dynamics, allowing for networks with a tailored thermomechanical response.

Accessing pluripotent materials through tempering of dynamic covalent polymer networks.

Pluripotency, which is defined as a system not fixed as to its developmental potentialities, is typically associated with biology and stem cells. Inspired by this concept, we report synthetic polymers that act as a single "pluripotent" feedstock and can be differentiated into a range of materials that exhibit different mechanical properties, from hard and brittle to soft and extensible. To achieve this, we have exploited dynamic covalent networks that contain labile, dynamic thia-Michael bonds, whose extent of bonding can be thermally modulated and retained through tempering, akin to the process used in metallurgy. In addition, we show that the shape memory behavior of these materials can be tailored through tempering and that these materials can be patterned to spatially control mechanical properties.

Leveraging the Polymer Glass Transition to Access Thermally Switchable Shear Jamming Suspensions.

Suspensions of polymeric nano- and microparticles are fascinating stress-responsive material systems that, depending on their composition, can display a diverse range of flow properties under shear, such as drastic thinning, thickening, and even jamming (reversible solidification driven by shear). However, investigations to date have almost exclusively focused on nonresponsive particles, which do not allow in situ tuning of the flow properties. Polymeric materials possess rich phase transitions that can be directly tuned by their chemical structures, which has enabled researchers to engineer versatile adaptive materials that can respond to targeted external stimuli. Reported herein are suspensions of (readily prepared) micrometer-sized polymeric particles with accessible glass transition temperatures (T g) designed to thermally control their non-Newtonian rheology. The underlying mechanical stiffness and interparticle friction between particles change dramatically near T g. Capitalizing on these properties, it is shown that, in contrast to conventional systems, a dramatic and nonmonotonic change in shear thickening occurs as the suspensions transition through the particles' T g. This straightforward strategy enables the in situ turning on (or off) of the system's ability to shear jam by varying the temperature relative to T g and lays the groundwork for other types of stimuli-responsive jamming systems through polymer chemistry.

Designing Stress-Adaptive Dense Suspensions Using Dynamic Covalent Chemistry.

The non-Newtonian behaviors of dense suspensions are central to their use in technological and industrial applications and arise from a network of particle-particle contacts that dynamically adapt to imposed shear. Reported herein are studies aimed at exploring how dynamic covalent chemistry between particles and the polymeric solvent can be used to tailor such stress-adaptive contact networks, leading to their unusual rheological behaviors. Specifically, a room temperature dynamic thia-Michael bond is employed to rationally tune the equilibrium constant (K eq) of the polymeric solvent to the particle interface. It is demonstrated that low K eq leads to shear thinning, while high K eq produces antithixotropy, a rare phenomenon where the viscosity increases with shearing time. It is proposed that an increase in K eq increases the polymer graft density at the particle surface and that antithixotropy primarily arises from partial debonding of the polymeric graft/solvent from the particle surface and the formation of polymer bridges between particles. Thus, the implementation of dynamic covalent chemistry provides a new molecular handle with which to tailor the macroscopic rheology of suspensions by introducing programmable time dependence. These studies open the door to energy-absorbing materials that not only sense mechanical inputs and adjust their dissipation as a function of time or shear rate but also can switch between these two modalities on demand.

A multi-stage single photochrome system for controlled photoswitching responses.

The ability of molecular photoswitches to convert on/off responses into large macroscale property change is fundamental to light-responsive materials. However, moving beyond simple binary responses necessitates the introduction of new elements that control the chemistry of the photoswitching process at the molecular scale. To achieve this goal, we designed, synthesized and developed a single photochrome, based on a modified donor-acceptor Stenhouse adduct (DASA), capable of independently addressing multiple molecular states. The multi-stage photoswitch enables complex switching phenomena. To demonstrate this, we show spatial control of the transformation of a three-stage photoswitch by tuning the population of intermediates along the multi-step reaction pathway of the DASAs without interfering with either the first or final stage. This allows for a photonic three-stage logic gate where the secondary wavelength solely negates the input of the primary wavelength. These results provide a new strategy to move beyond traditional on/off binary photochromic systems and enable the design of future molecular logic systems.

Controlling the Morphology of Dynamic Thia-Michael Networks to Target Pressure-Sensitive and Hot Melt Adhesives.

A series of multistage (pressure-sensitive/hot melt) adhesives utilizing dynamic thia-Michael bonding motifs are reported. The benzalcyanoacetate Michael acceptors used in this work undergo bond exchange under ambient conditions without external catalysis, facilitating pressure-sensitive adhesion. A key feature of this system is the dynamic reaction-induced phase separation that lends reinforcement to the otherwise weakly bonded materials, enabling weak, repeatable pressure-sensitive adhesion under ambient conditions and strong adhesion when processed as a hot melt adhesive. By using different pairs of benzalcyanoacetate cross-linking units, the phase separation characteristics of the adhesives can be directly manipulated, allowing for a tailored adhesive response.

Tough Multimaterial Interfaces through Wavelength-Selective 3D Printing.

Strong and well-engineered interfaces between dissimilar materials are a hallmark of natural systems but have proven difficult to emulate in synthetic materials, where interfaces often act as points of failure. In this work, curing reactions that are triggered by exposure to different wavelengths of visible light are used to produce multimaterial objects with tough, well-defined interfaces between chemically distinct domains. Longer-wavelength (green) light selectively initiates acrylate-based radical polymerization, while shorter-wavelength (blue) light results in the simultaneous formation of epoxy and acrylate networks through orthogonal cationic and radical processes. The improved mechanical strength of these interfaces is hypothesized to arise from a continuous acrylate network that bridges domains. Using printed test structures, interfaces were characterized through spatial resolution of their chemical composition, localized mechanical properties, and bulk fracture strength. This wavelength-selective photocuring of interpenetrating polymer networks is a promising strategy for increasing the mechanical performance of 3D-printed objects and expanding light-based additive manufacturing technologies.

Dynamic reaction-induced phase separation in tunable, adaptive covalent networks.

A series of catalyst-free, room temperature dynamic bonds derived from a reversible thia-Michael reaction are utilized to access mechanically robust dynamic covalent network films. The equilibrium of the thiol addition to benzalcyanoacetate-based Michael-acceptors can be directly tuned by controlling the electron-donating/withdrawing nature of the Michael-acceptor. By modulating the composition of different Michael-acceptors in a dynamic covalent network, a wide range of mechanical properties and thermal responses can be realized. Additionally, the reported systems phase-separate in a process, coined dynamic reaction-induced phase separation (DRIPS), that yields reconfigurable phase morphologies and reprogrammable shape-memory behaviour as highlighted by the heat-induced folding of a predetermined structure.

What happens in the dark? Assessing the temporal control of photo-mediated controlled radical polymerizations.

A signature of photo-mediated controlled polymerizations is the ability to modulate the rate of polymerization by turning the light source 'on' and 'off.' However, in many reported systems, growth can be reproducibly observed during dark periods. In this study, emerging photo-mediated controlled radical polymerizations are evaluated with in situ 1H NMR monitoring to assess their behavior in the dark. Interestingly, it is observed that Cu-mediated systems undergo long-lived, linear growth during dark periods in organic media.

Brønsted-Acid-Catalyzed Exchange in Polyester Dynamic Covalent Networks.

The effect of catalyst strength on polyester-alcohol dynamic covalent exchange was systematically studied using Brønsted acids and a low-Tg poly(4-methylcaprolactone) vitrimer formulation. Relaxation times, activation energies, and Arrhenius prefactors are correlated with pKa. Strong protic acids induce facile network relaxation at 25 °C on the order of 104-105 s, significantly faster than Lewis acid alternatives that function only above 100 °C. Activation energies span 49-67 kJ/mol and increase as pKa decreases. The opposite trend is observed with the Arrhenius prefactor. We anticipate that the quantitative understanding of Brønsted acid effects disclosed herein will be of utility in future studies that exploit acid-catalyzed dynamic covalent bond exchange.

Solution Mask Liquid Lithography (SMaLL) for One-Step, Multimaterial 3D Printing.

A novel methodology for printing 3D objects with spatially resolved mechanical and chemical properties is reported. Photochromic molecules are used to control polymerization through coherent bleaching fronts, providing large depths of cure and rapid build rates without the need for moving parts. The coupling of these photoswitches with resin mixtures containing orthogonal photo-crosslinking systems allows simultaneous and selective curing of multiple networks, providing access to 3D objects with chemically and mechanically distinct domains. The power of this approach is showcased through the one-step fabrication of bioinspired soft joints and mechanically reinforced "brick-and-mortar" structures.