Synthesis and Columnar Organization of Partially Fluorinated Dehydrobenz[18]annulenes

Abstract

Two diamond-shaped and partially fluorinated dehydrobenz[18]annulene macrocycles have been synthesized through a one-pot synthesis relying on fourfold Sonogashira coupling. Single crystal structures of the prepared macrocycles show continuous columnar stacks of these molecules that are mediated by the fluoroarene–alkyne, arene–alkyne, fluoroarene–fluoroarene, and alkyne–alkyne [π···π] interactions instead of the expected fluoroarene–arene [π···π] interaction.

Synthesis and Columnar Organization of Partially Fluorinated Dehydrobenz[18]annulenes

“…While the fluoroarene–arene interaction was found to direct the columnar stacks in the most symmetric hexameric macrocycles, in the case of diamond-shaped macrocycles with ortho- and meta-linked fluoroarene and arene groups, columnar stacking has been achieved via fluoroarene–alkyne interaction. Our ongoing work aims to explore the generality of this assembly pattern and its relevance in the construction of advanced materials …”