Organic Chemistry

Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes

Authors

  • Eric Sidler Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland ,
  • Patrick Zwick Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland ,
  • Charlotte Kress Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland ,
  • Ksenia Reznikova Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland ,
  • Olaf Fuhr Institute for Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), P. O. Box 3640, 76021 Karlsruhe, Germany ,
  • Dieter Fenske Institute for Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), P. O. Box 3640, 76021 Karlsruhe, Germany ,
  • Marcel Mayor Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland & Institute for Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), P. O. Box 3640, 76021 Karlsruhe, Germany & Lehn Institute of Functional Materials (LIFM), School of Chemistry, Sun Yat-Sen University (SYSU), 510275 Guangzhou, China

Abstract

The synthetic access to macrocyclic molecular topologies with interesting photophysical properties has greatly improved thanks to the successful implementation of organic and inorganic corner units. Based on recent reports, we realized pseudo-meta [2.2]paracyclophanes (PCPs) might serve as optimal corner units for constructing 3D functional materials, owing to their efficient electronic communication, angled substituents and planar chirality. Herein, we report the synthesis, characterization and optical properties of four novel all-carbon enantiopure macrocycles bearing three to six pseudo-meta PCPs linked by 1,3-butadiyne units. The macrocycles were obtained by a single step from enantiopure literature known dialkyne pseudo-meta PCP and were unambiguously identified and characterized by state of the art spectroscopic methods and in part even by x-ray crystallography. By comparing the optical properties to relevant reference compounds, we show that the pseudo-meta PCP subunit effectively elongates the conjugated system throughout the macrocyclic backbone, such that already the smallest macrocycle consisting of only three subunits reaches an astounding polymer-like conjugation length. Additionally, we show that the chiral pseudo-meta PCPs induce remarkable chiroptical response in the respective macrocycles, reaching unprecedented high molar dichroism values for all-carbon macrocycles of up to 1307 L mol-1 cm-1.

Version notes

Increased accesibilty of the target macrocycles by improved reaction conditions. Add an additional member to the series. Corroborating the identity by x-ray analysis.

Content

Thumbnail image of Sidler et. al._Chemrxiv_Manuscript_final.pdf

Supplementary material

Thumbnail image of Sidler et. al._Chemrxiv_ESI_final.pdf
Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes
Supporting Information of: Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes