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Pressure Controlled Topochemical Polymerization in Two-Dimensional Hybrid Perovskite

Mechanical pressure offers unique control over the energy landscape of chemical reactions, opening up pathways that are inaccessible through conventional thermochemistry. We hypothesize that the reduced dimensionality defines the conformational space of the high-pressure reaction, giving rise to new selectivity that is unavailable in 3D systems. Here, we demonstrate this concept through the pressure-controlled topochemical polymerization of the diacetylene molecule deca‐3,5‐diyn‐1‐amine (DDA) incorporated in the two-dimensional (2D) perovskite [DDA]2PbBr4. Compression at 3 GPa drives the first topochemical polymerization through 1,2 addition, forming a polyene product at room temperature. The reaction is initiated by the mechanical bending of the linear DDA molecule, a mechanism fundamentally different from the 1,4-addition in 3D solids. Importantly, pressure hinders the second 1,2-addition by disfavoring the gauche conformation between the remaining acetylene groups, allowing for the selective formation of polyene versus polyacene products. We characterize the reaction mechanisms and products using spectroscopies (Raman, X-ray photoelectron, ultraviolet-visible), X-ray diffraction and density-functional theory simulations. These results highlight the important role of dimensionality in high-pressure chemistry, and offers a new paradigm for creating low-dimensional functional materials.

Identiferoai:union.ndltd.org:unt.edu/info:ark/67531/metadc1873821
Date12 1900
CreatorsAbu-Amara, Lama Marwan
ContributorsYan, Hao (Chemistry professor), Cisneros, Andrés G., Cundari, Thomas R., 1964-
PublisherUniversity of North Texas
Source SetsUniversity of North Texas
LanguageEnglish
Detected LanguageEnglish
TypeThesis or Dissertation
Formatvi, 41 pages : illustrations (some color), Text
RightsPublic, Abu-Amara, Lama Marwan, Copyright, Copyright is held by the author, unless otherwise noted. All rights Reserved.

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