Garrett Kukier

All Publications

• The Force Awakens a Dormant Chemiluminescent Pathway in 1,2-Dioxetane. Journal of the American Chemical Society Kukier, G. A., Diesendruck, C. E., Hait, D., Xu, R., Martinez, T. J. 2026; 148 (31): 33319-33332

  Abstract

  1,2-Dioxetanes are well-known for their chemiluminescent decomposition initiated by O-O bond scission. Under thermal conditions, this chemiluminescence has been used for molecular imaging, while mechanochemical triggering of chemiluminescence can be a powerful tool for studying stress in materials. It has been widely assumed that mechanochemical activation follows the same O-O scission pathway as the thermal case. However, our first-principles simulations of the mechanochemically triggered decomposition of 1,2-dioxetane show that the traditional O-O scission pathway is largely insensitive to applied force. Instead, a thermally inaccessible C-C bond scission pathway is stabilized by applied force and becomes energetically favored above a critical force (∼1.8-3.0 nN). This force-induced mechanistic switch is robust across various pulling directions and substituents, including the experimentally tested adamantyl derivative. These findings establish a new, fundamentally force-dependent pathway for chemiluminescence. They demonstrate that mechanical force can be used not only to accelerate a reaction, but to fundamentally change its mechanism. This presents significant opportunities for new mechanophore design and mechanochemical sensing applications.

  View details for DOI 10.1021/jacs.6c07677

  View details for PubMedID 42584639

• Violations. How Nature Circumvents the Woodward-Hoffmann Rules and Promotes the Forbidden Conrotatory 4n+2 Electron Electrocyclization of Prinzbach's Vinylogous Sesquifulvalene JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Kukier, G. A., Turlik, A., Xue, X., Houk, K. N. 2021; 143 (51): 21694-21704

  Abstract

  Woodward and Hoffmann, in their treatise on orbital symmetry in 1969, stated "Violations. There are none!" Prinzbach reported in 1978 that the electrocyclization of vinylogous sesquifulvalene occurs exclusively through the Woodward-Hoffmann orbital-symmetry-forbidden 14π-electron conrotatory pathway, despite the availability of a variety of orbital-symmetry-allowed processes. Prinzbach later demonstrated that an 18π-electron homologue exhibits the same forbidden behavior. And yet, the analogous vinylogous pentafulvalene and heptafulvalene both follow the orbital symmetry rules, each proceeding through its allowed conrotatory 12π and 16π process, respectively. We report the investigation of these reactions with ωB97X-D DFT. The physical origins of the flagrant Prinzbach violations of the Woodward-Hoffmann orbital symmetry selection rules have now been elucidated by these calculations in conjunction with extensive analyses and comparisons to electrocyclizations that obey the Woodward-Hoffmann rules. This remarkable reversal of the Rules (the 14π-electron-forbidden process is found to be 11 kcal/mol more energetically facile than the allowed process) occurs due to the high degree of polarization of this hydrocarbon, such that conrotatory electrocyclization of vinylogous sesquifulvalene behaves like a cyclopentadienide combining with a tropylium. These results are compared to other forbidden pericyclic processes driven by steric constraints and strain release or by diradical character of the reactants that facilitates the formation of diradical transition states for symmetry-forbidden reactions. We predict how strong donor-acceptor substitution can modify nodal properties to level the difference between allowed and forbidden electrocyclic reaction barriers, and we provide computational predictions of two such cases.

  View details for DOI 10.1021/jacs.1c11058

  View details for Web of Science ID 000733819700001

  View details for PubMedID 34911295

  View details for PubMedCentralID PMC8979582