| Autor: |
Konda SS; Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA., Brantley JN, Varghese BT, Wiggins KM, Bielawski CW, Makarov DE |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Chemical Society [J Am Chem Soc] 2013 Aug 28; Vol. 135 (34), pp. 12722-9. Date of Electronic Publication: 2013 Aug 19. |
| DOI: |
10.1021/ja4051108 |
| Abstrakt: |
While the field of polymer mechanochemistry has traditionally focused on the use of mechanical forces to accelerate chemical processes, theoretical considerations predict an underexplored alternative: the suppression of reactivity through mechanical perturbation. Here, we use electronic structure calculations to analyze the mechanical reactivity of six mechanophores, or chemical functionalities that respond to mechanical stress in a controlled manner. Our computational results indicate that appropriately directed tensile forces could attenuate (as opposed to facilitate) mechanochemical phenomena. Accompanying experimental studies supported the theoretical predictions and demonstrated that relatively simple computational models may be used to design new classes of mechanically responsive materials. In addition, our computational studies and theoretical considerations revealed the prevalence of the anti-Hammond (as opposed to Hammond) effect (i.e., the increased structural dissimilarity between the reactant and transition state upon lowering of the reaction barrier) in the mechanical activation of polyatomic molecules. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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