Stereogenic π-Conjugated Macrocycles: Synthesis, Structure, and Chiroptical Properties Including Circularly Polarized Luminescence

Dedicated to the memory of Professor Masahiko Iyoda, who passed away on September 21, 2023.

Abstract

Highly symmetrical and aesthetically pleasing molecules have attracted the attention of organic chemists. We synthesized new highly symmetric stereogenic π-conjugated macrocycles with planar or axial chirality. Macrocyclic oligomers synthesized by Yamamoto coupling or Suzuki–Miyaura cross-coupling from the π-unit containing chirality. These cyclization reactions gave multiple oligomers in relatively high yields. We then elucidated their structures and investigated their chiroptical properties, including circular dichroism (CD) and circularly polarized luminescence (CPL). Because of the selection rule for rigid and symmetric structures, these macrocycles exhibit a high dissymmetry factor (g _abs or g _lum) for circularly polarized light in CD or CPL. Several rigid cyclic compounds retain a highly symmetric structure in the excited state and exhibit higher g _lum values than common chiral organic compounds. This Account provides a brief background regarding chiroptical properties, followed by a summary of the various macrocycles synthesized in this study. We are glad if this Account will be a source of ideas not only for chemists working with π-conjugated compounds, but also for synthetic chemists working with chiral compounds, especially those engaged in asymmetric synthesis.

1 Introduction

2 Brief Description of Chiroptical Properties

3 Stereogenic Macrocycle Based on [2.2]Paracyclophane

3.1 Stereogenic Double-decker Oligothiophene

3.2 Stereogenic Biselenophene Macrocycle

3.3 Helical Oligophenylene Linked with [2.2]Paracyclophane

4 Stereogenic Macrocycle Based on Binaphthyl

4.1 Cyclic Oligomer of Chiral Binaphthyl

4.2 Doubly Twisted Binaphthyl Dimer

4.3 Cyclic Oligomer of Binaphthyl Extended with Paraphenylene

4.4 Curved Helical Paraphenylene Anchoring Chiral Binaphthyl

4.5 Binaphthyl-Hinged [5]-Helicene

5 Summary

Key words

macrocycle - chirality - circularly polarized luminescence - [2.2]paracyclophane - binaphthyl - oligothiophene - paraphenylene - helicene

Publication History

Received: 13 August 2023

Accepted after revision: 22 August 2023

Accepted Manuscript online:
22 August 2023

Article published online:
16 October 2023

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