All Publications

  • Synthesis of Contorted Polycyclic Conjugated Hydrocarbons via Regioselective Activation of Cyclobutadienoids. Journal of the American Chemical Society Yin, X., Zheng, K., Jin, Z., Horst, M., Xia, Y. 2022


    Contorted carbon structures have drawn much attention in the past decade for their rich three-dimensional geometries, enhanced solubility, and tunable electronic properties. We report a modular method to synthesize contorted polycyclic conjugated hydrocarbons containing helical moieties in controlled topologies. This strategy leverages our previously reported streamlined synthesis of pi-systems containing four-membered cyclobutadienoids (CBDs), whose catalyzed cycloaddition with alkynes affords helical structures. Interestingly, we observed exclusive nonbay region regioselectivity in the C-C bond activation of CBDs in our system, which is opposite to the scarce previous examples of [N]phenylene activation that led to the formation of linear phenacene structures. The quantitative and regioselective nonbay region alkyne cycloaddition yielded a variety of helical carbon structures with their topologies predetermined by the CBD-containing precursor hydrocarbons. The cycloaddition can be inhibited by methyl substituents exocyclic to the four-membered ring, thus allowing selective activation of only certain desired CBD units while leaving the others intact. Calculation elucidated the basis for the observed regioselectivity. The described method provides a new route to multihelical aromatic hydrocarbons with complex yet defined geometries, facilitating the further exploration of such fascinating carbon structures.

    View details for DOI 10.1021/jacs.2c02457

    View details for PubMedID 35793470

  • Understanding the Mechanochemistry of Ladder-Type Cyclobutane Mechanophores by Single Molecule Force Spectroscopy. Journal of the American Chemical Society Horst, M., Yang, J., Meisner, J., Kouznetsova, T. B., Martinez, T. J., Craig, S. L., Xia, Y. 2021


    We have recently reported a series of ladder-type cyclobutane mechanophores, polymers of which can transform from nonconjugated structures to conjugated structures and change many properties at once. These multicyclic mechanophores, namely, exo-ladderane/ene, endo-benzoladderene, and exo-bicyclohexene-peri-naphthalene, have different ring structures fused to the first cyclobutane, significantly different free energy changes for ring-opening, and different stereochemistry. To better understand their mechanochemistry, we used single molecule force spectroscopy (SMFS) to characterize their force-extension behavior and measure the threshold forces. The threshold forces correlate with the activation energy of the first bond, but not with the strain of the fused rings distal to the polymer main chain, suggesting that the activation of these ladder-type mechanophores occurs with similar early transition states, which is supported by force-modified potential energy surface calculations. We further determined the stereochemistry of the mechanically generated dienes and observed significant and variable contour length elongation for these mechanophores both experimentally and computationally. The fundamental understanding of ladder-type mechanophores will facilitate future design of multicyclic mechanophores with amplified force-response and their applications as mechanically responsive materials.

    View details for DOI 10.1021/jacs.1c05857

    View details for PubMedID 34310875

  • Bicyclohexene-peri-naphthalenes: Scalable Synthesis, Diverse Functionalization, Efficient Polymerization, and Facile Mechanoactivation of Their Polymers. Journal of the American Chemical Society Yang, J., Horst, M., Werby, S. H., Cegelski, L., Burns, N. Z., Xia, Y. 2020; 142 (34): 14619–26


    Pursuing polymers that can transform from a nonconjugated to a conjugated state under mechanical stress to significantly change their properties, we developed a new generation of ladder-type mechanophore monomers, bicyclo[2.2.0]hex-5-ene-peri-naphthalene (BCH-Naph), that can be directly and efficiently polymerized by ring-opening metathesis polymerization (ROMP). BCH-Naphs can be synthesized in multigram quantities and functionalized with a wide range of electron-rich and electron-poor substituents, allowing tuning of the optoelectronic and physical properties of mechanically generated conjugated polymers. Efficient ROMP of BCH-Naphs yielded ultrahigh molecular weight polymechanophores with controlled MWs and low dispersity. The resulting poly(BCH-Naph)s can be mechanically activated into conjugated polymers using ultrasonication, grinding, and even simple stirring of the dilute solutions, leading to changes in absorption and fluorescence. Poly(BCH-Naph)s represent an attractive polymechanophore system to explore multifaceted mechanical response in solution and solid states, owing to the synthetic scalability, functional diversity, efficient polymerization, and facile mechanoactivation.

    View details for DOI 10.1021/jacs.0c06454

    View details for PubMedID 32786795

  • Benzoladderene Mechanophores: Synthesis, Polymerization, and Mechanochemical Transformation JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Yang, J., Horst, M., Romaniuk, J. H., Jin, Z., Cegelski, L., Xia, Y. 2019; 141 (16): 6479–83