Expanding the application of chlorinated anilines as molecular templates to achieve a series of solid-state [2 + 2] cycloaddition reactions
Year: 2025
Type: article
Abstract: 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 ( C 6 H 3 Cl 4 N ) or 2,4,6-trichloroaniline ( C 6 H 4 Cl 3 N ). 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( C 6 H 3 Cl 4 N )·( 3,3-BPE ), 2( C 6 H 4 Cl 3 N )·( 3,3-BPE ), 2( C 6 H 3 Cl 4 N )·( 2,2-BPE ), or 2( C 6 H 4 Cl 3 N )·( 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 position the ethylene groups 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.
Source: Frontiers in Chemistry
Institutions: Webster University, University of Iowa
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $3,801
Funder: Webster University
OpenAlex ID: W4416976780