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Single molecule force spectroscopy and computation are used to evaluate substituent effects on the disrotatory ring opening reaction of cyclobutene to butadiene, accessedviacovalent polymer mechanochemistry. 

Pterodactylane is a [4]-ladderane with substituents on the central rung. Comparing the mechanochemistry of the [4]-ladderane structure when pulled from the central rung versus the end rung revealed a striking difference in the threshold force of mechanoactivation: the threshold force is dramatically lowered from 1.9 nN when pulled on the end rung to 0.7 nN when pulled on the central rung. We investigated the bicyclic products formed from the mechanochemical activation of pterodactylane experimentally and computationally, which are distinct from the mechanochemical products of ladderanes being activated from the end rung. We compared the products of pterodactylane’s mechanochemical and thermal activation to reveal differences and similarities in the mechanochemical and thermal pathways of pterodactylane transformation. Interestingly, we also discovered the presence of elementary steps that are accelerated or suppressed by force within the same mechanochemical reaction of pterodactylane, suggesting rich mechanochemical manifolds of multicyclic structures. We rationalized the greatly enhanced mechanochemical reactivity of the central rung of pterodactylane and discovered force-free ground state bond length to be a good low-cost predictor of the threshold force for cyclobutane-based mechanophores. These findings advance our understanding of mechanochemical reactivities and pathways, and they will guide future designs of mechanophores with low threshold forces to facilitate their applications in force-responsive materials. 

Feasibility of mechanochemical depolymerization of commodity poly(olefin)s in a ball mill reactor is assessed using thermodynamic data. 

Controlledradicalpolymerizations(CRPs)areoneofthemost importantways toobtainuniform, definedmolecularweight polymerswith complex composition and architecture such as block copolymers. Anew controlledandlight-initiatedradicalpolymerizationis introducedthatmakes useofthiol initiatorsandanIr-photocatalyst.Differentreactionparametersare studiedfortheirimportanceinthecontrolledcharacteristicsofpolymerization, suchaslowdispersity,controlofmolecularweights,andstraightforwardaccess toblockcopolymers.Thelightcontrolfurthermoreallowsforsimpleswitching onandoffof thepolymerization.Weproposeamechanismfor theso-called thiol-induced, light-activated,controlledradicalpolymerization(TIRP),whichincludestheformationofdormantspeciesandtheir light-andcatalyst-dependentequilibriumwiththeactivepolymerchainend.TIRPenriches theportfolioof controlledandlightinitiatedpolymerizationmethodsby itsviabilityatmildconditions andthepossibility togrowpolymers froma largevarietyof readilyavailablethiols. 

Abstract Over 8 billion tons of plastic have been produced to date, and a 100% reclamation recycling strategy is not foreseeable. This review summarizes how the mechanochemistry of polymers may contribute to a sustainable polymer future by controlling the degradation not only of de novo developed designer polymers but also of plastics in existing waste streams. The historical development of polymer mechanochemistry is presented while highlighting current examples of mechanochemically induced polymer degradation. Additionally, theoretical and computational frameworks are discussed that may lead to the discovery and better understanding of new mechanochemical reactions in the future. This review takes into account technical and engineering perspectives converging the fields of trituration and polymer mechanochemistry with a particular focus on the fate of commodity polymers and potential technologies to monitor mechanochemical reactions while they occur. Therefore, a unique perspective of multiple communities is presented, highlighting the need for future transdisciplinary research to tackle the high-leverage parameters governing an eventually successful mechanochemical degradation approach for a circular economy. 

Proton transfer reactions are ubiquitous in chemistry, especially in aqueous solutions. We investigate photoinduced proton transfer between the photoacid 8-hydroxypyrene-1,3,6- trisulfonate (HPTS) and water using fast fluorescence spectroscopy and ab initio molecular dynamics simulations. Photoexcitation causes rapid proton release from the HPTS hydroxyl. Previous experiments on HPTS/water described the progress from photoexcitation to proton diffusion using kinetic equations with two time constants. The shortest time constant has been interpreted as protonated and photoexcited HPTS evolving into an “associated” state, where the proton is “shared” between the HPTS hydroxyl and an originally hydrogen bonded water. The longer time constant has been interpreted as indicating evolution to a “solvent separated” state where the shared proton undergoes long distance diffusion. In this work, we refine the previous experimental results using very pure HPTS. We then use excited state ab initio molecular dynamics to elucidate the detailed molecular mechanism of aqueous excited state proton transfer in HPTS. We find that the initial excitation results in rapid rearrangement of water, forming a strong hydrogen bonded network (a “water wire”) around HPTS. HPTS then deprotonates in ≤3 ps, resulting in a proton that migrates back and forth along the wire before localizing on a single water molecule. We find a near linear relationship between the emission wavelength and proton-HPTS distance over the simulated time scale, suggesting that the emission wavelength can be used as a ruler for the proton distance. Our simulations reveal that the “associated” state corresponds to a water wire with a mobile proton and that the diffusion of the proton away from this water wire (to a generalized “solvent separated” state) corresponds to the longest experimental time constant. 

Proton transfer reactions are ubiquitous in chemistry, especially in aqueous solutions. We investigate photo-induced proton transfer between the photoacid 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) and water using fast fluorescence spectroscopy and ab initio molecular dynamics simulations. Photo-excitation causes rapid proton release from the HPTS hydroxyl. Previous experiments on HPTS/water described the progress from photoexcitation to proton diffusion using kinetic equations with two time constants. The shortest time constant has been interpreted as protonated and photoexcited HPTS evolving into an “associated” state, where the proton is “shared” between the HPTS hydroxyl and an originally hydrogen bonded water. The longer time constant has been interpreted as indicating evolution to a “solvent separated” state where the shared proton undergoes long distance diffusion. In this work, we refine the previous experimental results using very pure HPTS. We then use excited state ab initio molecular dynamics to elucidate the detailed molecular mechanism of aqueous excited state proton transfer in HPTS. We find that the initial excitation results in rapid rearrangement of water, forming a strong hydrogen bonded network (a “water wire”) around HPTS. HPTS then deprotonates in ≤3 ps, resulting in a proton that migrates back and forth along the wire before localizing on a single water molecule. We find a near linear relationship between emission wavelength and proton-HPTS distance over the simulations’ time scale, suggesting that emission wavelength can be used as a ruler for proton distance. Our simulations reveal that the “associated” state corresponds to a water wire with a mobile proton and that the diffusion of the proton away from this water wire (to a generalized “solvent-separated” state) corresponds to the longest experimental time constant.