title: Synthesis of Phenylene Vinylene Macrocycles through Acyclic Diene Metathesis Macrocyclization and Their Aggregation Behavior.
abstract: A series of phenylene vinylene macrocycles (PVMs) bearing substituents with various sizes and electronic properties have been synthesized through a one-step acyclic diene metathesis macrocyclization approach and their aggregation behaviors have been investigated. In great contrast to the aggregation of the analogous phenylene ethynylene macrocycles, which aggregate only when substituted with electron-withdrawing groups, these PVMs undergo exceptionally strong aggregation, regardless of the electron-donating or -withdrawing characters of the substituents. The unusual aggregation behavior of the PVMs is further investigated with thermodynamic and computer modeling studies, which show a good agreement with the recently proposed direct through-space interaction model, rather than the polar/π model. The high aggregation tendency of PVMs suggests the great potential of this novel class of shape-persistent macrocycles in a variety of applications, such as ion channels, host-guest recognition, and catalysis.
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, Colorado, 80309 (USA).
authors.forename: Chenxi
authors.initials: C
authors.lastname: Zhang
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, Colorado, 80309 (USA).
authors.forename: Chao
authors.initials: C
authors.lastname: Yu
authors.affiliation: National Renewable Energy Laboratory, Golden, Colorado 80401 (USA).
authors.forename: Hai
authors.initials: H
authors.lastname: Long
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, Colorado, 80309 (USA).
authors.forename: Ryan J
authors.initials: RJ
authors.lastname: Denman
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, Colorado, 80309 (USA). Yinghua.Jin@colorado.edu.
authors.forename: Yinghua
authors.initials: Y
authors.lastname: Jin
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, Colorado, 80309 (USA). wei.zhang@colorado.edu.
authors.forename: Wei
authors.initials: W
authors.lastname: Zhang
keywords: aggregation; dynamic covalent chemistry; macrocycles; olefin metathesis; π interactions