ORIGINAL RESEARCH article
Front. Chem.
Sec. Solid State Chemistry
This article is part of the Research TopicChemistry of Dynamic and Smart Molecular CrystalsView all articles
Expanding the Application of Chlorinated-anilines as Molecular Templates to Achieve a Series of Solid-State [2 + 2] Cycloaddition Reactions
Provisionally accepted
- 1Webster University, St. Louis, United States
- 2The University of Iowa College of Liberal Arts and Sciences, Iowa City, United States
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The ability to achieve a series of solid-state [2 + 2] cycloaddition reactions within related hydrogen-bonded co-crystals is reported. These multicomponent molecular solids contain either trans-1,2-bis(3-pyridyl)ethylene (3,3-BPE) or trans-1,2-bis(2-pyridyl)ethylene (2,2-BPE) as the reactant along with one of two chlorinated-anilines that behave as a template, namely 2,3,5,6-tetrachloroaniline (C6H3Cl4N) or 2,4,6-trichloroaniline (C6H4Cl3N). For each of the four unique organic solids, the co-crystallization process yields a three-component hydrogen-bonded assembly with a formula of either 2(C6H3Cl4N)·(3,3-BPE), 2(C6H4Cl3N)·(3,3-BPE), 2(C6H3Cl4N)·(2,2-BPE), or 2(C6H4Cl3N)·(2,2-BPE). In all co-crystals, these anilines template up to a quantitative yield for the photoreaction, since they are able to engage in both N-H···N hydrogen bonds and homogeneous face-to-face π-π stacking interactions which positions the ethylene group, within the different reactant molecules, in a suitable location to photoreact. These results complete the series for the remaining symmetric bipyridine-based reactants to undergo a solid-state [2 + 2] cycloaddition reaction utilizing these chlorinated-anilines. This work expands and illustrates the potential for these chlorinated-anilines to serve as reliable molecular templates that crystal engineers can utilize to control the organic solid state and achieve photoreactions.
Keywords: co-crystal, Organic solid state, [2 + 2] cycloaddition reaction, Hydrogen Bonding, Co-crystal former
Received: 03 Sep 2025; Accepted: 28 Oct 2025.
Copyright: © 2025 Groeneman, White and Unruh. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) or licensor are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
* Correspondence: Ryan H. Groeneman, ryangroeneman19@webster.edu
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